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LAYERED DOUBLE HYDROXIDES:
PRESENT AND FUTURE
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LAYERED DOUBLE HYDROXIDES:
PRESENT AND FUTURE
VICENTE RIVES
EDITOR
Nova Science Publishers, Inc.

New York
Copyright © 2001 by Nova Science Publishers, Inc.
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CONTENTS
Preface vii
Part I: Synthesis, Structure and Characterisation
Chapter 1 Layered Double Hydroxides: Synthesis and Post-Synthesis Modification 1
A. de Roy, C. Forano and J. P. Besse
Chapter 2 Crystal Structure and X-ray Identification of Layered Double Hydroxides 41
V. A. Drits and A. S. Bookin
Chapter 3 Computer Modelling of Layered Double Hydroxides 101
S. P. Newman, H. C. Greenwell, P. V. Coveney and W. Jones
Chapter 4 Study of Layered Double Hydroxides by Thermal Methods 127
Vicente Rives
Chapter 5 Infrared and Raman Spectroscopic Studies of Layered Double
Hydroxides (LDHs) 153
J. T. Kloprogge and R. L. Frost
Chapter 6 Solid-State NMR and EPR Studies of Hydrotalcities 217
João Rocha
Chapter 7 Investigating Layered Double Hydroxides by Mössbauer Spectroscopy 241
Chr. Bender Koch
Chapter 8 Surface Texture and Electron Mincroscopy Studies of Layered
Double Hydroxides 257
Vicente Rives
Part II: Applications
Chapter 9 Layered Double Hydroxides in Water Decontamination 285
María Ángeles Ulibarri and María del Carmen Hermosín
Chapter 10 Applications of Hydrotalcite-Type Anionic Clays
(Layered Double Hydroxides) in Catalysis 323
Francesco Basile and Angelo Vaccari
Chapter 11 Hydrogenation Catalysis by Mixed Oxides Prepared from LDHs 367
A. Monzón, E. Romeo and A. J. Marchi
Chapter 12 Layered Double Hydroxides and their Intercalation Compounds in
Photo-chemistry and in Medicinal Chemistry 435
Umberto Costantino and Morena Nocchetti
Chapter 13 Environmental Chemistry of Iron(II)-Iron(III) LDHs (Green Rusts) 469
Hans Christian Bruun Hansen
Index 495
PREFACE
Layered Double Hydroxides (LDH), hydrotalcite-like (HTl), hydrotalcite-type (HTt),

anionic clays, ..., are the commonest names applied to a wide family of layered materials,
despite none of these names fully corresponds to the actual situation. Also known in some
occasions as layered hydroxycarbonates, whichever the name given, these materials are not so
extended in nature as the well known cationic clays, but are very easy to prepare and they are
not generally expensive.
The first natural mineral belonging to this family of materials was discovered in Sweden in
1842, is known as hydrotalcite, and was given the general formula Mg6Al2(OH)16CO3·4H2O.
The first studies on the synthesis, stability, solubility and structure determination date back to
1930 and were mostly carried out by Feitknecht [1,2].
Essentially, the structure can be described as a cadmium iodide-type layered hydroxide
(e.g., Mg(OH)2, brucite) where a partial Mg2+/Al3+ substitution has taken place (thus the name
“layered double hydroxide”), balancing of the electric charge being achieved by location of
anions in the interlayer space (carbonate in most of the samples found in nature, so the name
“layered hydroxycarbonates”), where they co-exist with water molecules. Nowadays, solids
with this structure, but containing more than two different (a divalent and a trivalent one)
cations in the brucite-like layers, are also known.
What makes interesting to these materials is the fact that the nature of the layer cations can
be changed among a wide possible selection (almost exclusively restricted by size and charge),
and the nature of the interlayer anion can be also (almost freely) selected, among organic or
inorganic, simple or complex anions, polyoxometalates, simple anionic coordination
compounds, etc. An additional feature that makes them similar to cationic clays is the fact that
they can be also pillared, although doubts still exist in the literature about the thermal stability
of the structures formed. Also as cationic clays, the interlayer species can be rather easily
exchanged, thus increasing their applications and opening new synthetic routes to prepare
derivatives.
A unique property these solids exhibit, so making them different from cationic clays, is that
after thermal decomposition under mild conditions, they are able to recover the layered
structure, this property representing, again, a new synthetic route for analogues.
The possibilities all these properties open are surprisingly wide, and so the applications of
these materials are widening almost every day. The principal areas of interest include their use
as catalysts and catalyst supports, adsorbents, anion scavengers, anion exchangers, polymer
stabilizers, antacids, antipeptins and stabilizers. The restricted interlayer space also represents a
viii Vicente Rives
sort of “nanoreactor” to perform chemical reactions in a constrained region, which may even
modify well known properties of molecules (e.g., photochemical properties).
In recent years several reviews have appeared on these LDHs, dealing with their general
chemistry and properties [3], structure and pillared derivatives [4], analogues with interlayer
organic anions [5] or with intercalated anionic coordination compounds or oxometalates [6]
with different nuclearity degree. With respect to their applications, Cavani, Trifirò and Vaccari
published some years ago a very outstanding review [7] which has somewhat become a guide
to learn about the catalytic properties of these solids and their derivatives. A general
comparison of cationic and anionic clays has been also reported [8]. Also, special issues of one
of the leading journals on clays have been devoted to different properties of these fascinating
materials [9-11], and special sessions dealt to these materials in regional and world-wide
international conferences.
Some of these reviews are rather recent, and so we have intended to avoid any sort of
repetition or overlapping with their content, unless the scientific production in its particular
area has provided a large number of papers, worthwhile to be reviewed and summarised.
Most of these studies have insisted or are dedicated to particular areas of interest of LDHs,
i. e., synthesis, structure, particular applications, etc. However, the aim of this book is to present,
in an unified form, an updating of current knowledge about LDHs, from different points of view,
i. e., paying attention to their synthesis, their properties and, finally, their applications. We have
chosen a rather “academic” way to cope with this subject, and we have tried to present the
current knowledge about their structures and properties giving an account on the sort of
information which may be known from application of specific, but well known and easily
available, characterisation techniques. Altogether, we hope this represents an updated and
comprehensive description of LDHS from almost every point of view.
So, the first section comprises a total of eight chapters devoted to the synthesis and
physicochemical characterisation of these materials. Besse and his coworkers describe the
structure of these compounds in relation to their synthesis, their preparative methods, and also
providing a developing strategy for post synthesis modification.
Drits and Bookin perform a detailed study on the structural features of LDHs, namely, the
isomorphous substitutions in the brucite-like layers, regularities in anion locations,
order-disorder phenomena in the layers and in the interlayer, different LDH polytypes, stacking
faults, etc.
Jones and his coworkers report computer simulations to probe the interlayer structure and
dynamics of LDHs, due to the lack of detailed structural information available for these
materials, especially when containing organic interlayer anions.
One of the outstanding properties of LDHs is their ability to recover their layered structure
even after being calcined at moderate temperatures. The effect of using different atmosphere
conditions during decomposition, discriminating steps associated to dehydration,
dehydroxylation, structure collapsing and formation of crystalline phases, as well as the effect
of the nature of the interlayer anion on the final solids, are the aim of the following chapter.
Spectroscopic techniques have been also applied to characterise LDHs. The main results
reported in the literature on these solids, obtained by application of vibrational spectroscopic
techniques (Infrared and Raman) are reviewed by Kloprogge and Frost, and Rocha reports on
the application of solid state resonance techniques (mainly MAS-NMR, but also, although in a
lesser extent, EPR) to characterize the solids in order to obtain a complete description of these
systems, for different spectroscopically active nuclei studied so far.
Preface ix
Koch reports the application of Mössbauer spectroscopy to the characterization of LDHs;

although virtually restricted to LDHs containing iron, this may be present both in the
brucite-like layers, or forming anionic complexes in the interlayers, so deserving the
application of specific techniques for its study.
This section of the book ends with a chapter by Rives dedicated to the study of the surface
texture and morphology of these solids, as concluded by electron microscopies; bearing in
mind the usefulness of LDHs as catalyst precursors, it is necessary to have a precise description
of its surface texture, and its evolution along the thermal treatments applied to obtain the final
catalysts.
Obviously, some other experimental techniques could be summarized and included in
additional chapters, but the “knowledge” corpus from other techniques is rather scarce in these
moments.
The second section of the book deals with the applications of LDHs. Again, the expertise
reader with a deep knowledge of the LDHs literature may feel some applications are lacking,
but we have again tried to include those applications for which a systematic and rather
pedagogic analysis can be carried out.
So, the first chapter in this section is dedicated by Ulibarri and Hermosín to the study of the
application of LDHs and calcined LDHs to decontamination processes, mostly making us of
two important features: the ability of LDHs to exchange their interlayer anions, and the ability
of calcined LDHs of recovering the layered structure when put in contact with solutions of
anions.
Then, two chapters by Vaccari and Basile, and by Monzón and coworkers, deal with the
catalytic applications of LDHs and calcined LDHs; although these applications have been the
aim of reviews published in the last decade, the increasing number of papers in the literature on
this subject makes worthwhile to include an account of this (probably the most outstanding)
application of LDHs. Emphasis is made on present and potential applications, related to the
wide number of composition and preparation variables, as well as on upgrading from 2- to
3-dimensions by pillaring and/or intercalation processes.
Costantino and coworkers provide a chapter which includes two types of applications:
photochemical properties/applications, from the ability of LDHs to organize photoactive
species in the interlayer and/or on the surface of the microcrystals, with applications in
non-linear optics, energy storage and conversion. Applications of LDHs in Medicine are also
reviewed; this is still a rather unexplored area, but we should not forget that some of very
common drugs contain hydrotalcite in their formulation.
Finally, Hansen reports a detailed study of a material known as “green rust”, an LDH
containing Fe(II) and Fe(III), which usually occur as transient phases on corrosion of iron, and
plays an plays an important role in transitions between anoxic and oxic soils conditions, and
overall may help to understand the role of iron in Nature.
Promising applications appear every day in the literature, and probably unforeseen
applications will turn up shortly. Their versatility, wide range of composition and very
especially their low cost will probably favour in the near future an extended and widened
interest in Layered Double Hydroxides.
x Vicente Rives
Last, but not the least, it has been a pleasure for me to act as Editor of this multi-author
book. I apologize for the subjects not included, and for the potential authors who were not
invited to participate; this was only my exclusive fault. But the undoubted success of the book
will be a shared one with a bunch of excellent scientists, but, overall, good friends.
Thank you.
REFERENCES
[1] W. Feitknecht and G. Fischer, Helv. Chim. Acta 18 (1935) 555.
[2] W. Feitknecht, Helv. Chim. Acta 25 (1942) 131.
[3] F. Trifirò and A. Vaccari, in Comprehensive Supramolecular Chemistry (Eds. J. L.
Atwood, J. E. D. Davies, D. D. MacNicol, F. Vögtle, J.-M. Lehn, G. Albert, T. Bein),
Pergamon, Oxford, vol. 7 (1996) pp. 251-291.
[4] A. De Roy, C. Forano, K. El Malki, J.-P. Besse, in Synthesis of Microporous Materials
(Eds. M. L. Occelli and H. E. Robson), Van Nostrand Reinhold, New York, vol. 2
(1992) pp. 108-169.
[5] S. P. Newman and W. Jones, New J. Chem. (1998) 105.
[6] V. Rives and M. A. Ulibarri, Coord. Chem. Rev. 181 (1999) 61.
[7] F. Cavani, F. Trifirò and A. Vaccari, Catal. Today 11 (1991) 173.
[8] A. Vaccari, Appl. Clay Sci. 14 (1999) 161.
[9] A. Vaccari (guest editor), Appl. Clay Sci. 10 (1995) pp. 1-186.
[10] D. Tichit and A. Vaccari (guest editors), Appl. Clay Sci. 13 (1998) pp. 311-511.
[11] F. Basile, M. Campanati, E. Serwicka and A. Vaccari (guest editors), Appl. Clay Sci.
18 (2001) pp. 1-110.
PART I: SYNTHESIS, STRUCTURE
AND CHARACTERISATION
In: Layered Double Hydroxides: Present and Future ISBN: 1-59033-060-9
Editor: Vicente Rives, pp. 1-39 © 2006 Nova Science Publishers, Inc.
Chapter 1
LAYERED DOUBLE HYDROXIDES: SYNTHESIS AND

POST-SYNTHESIS MODIFICATION
A. de Roy, C. Forano and J. P. Besse*
Laboratoire des Matériaux Inorganiques
Université Blaise Pascal (Clermont-Fd) – UMR 6002
F-63177 AUBIERE CEDEX, FRANCE
*E-mail : jpbesse@chimtp.univ-bpclermont.fr
INTRODUCTION
The term of Lamellar Double Hydroxides (LDHs)1 is used to designate synthetic or natural
lamellar hydroxides with two kinds of metallic cations in the main layers and interlayer
domains containing anionic species. This wide family of compounds is also referred to as
anionic clays, by comparison with the more usual cationic clays whose interlamellar domains
contain cationic species. LDHs are also reported as hydrotalcite-like compounds by reference
to one of the polytypes of the corresponding [Mg-Al] based mineral. More seldom are they
named pyroaurite-like compounds, lamellar hydroxides of transition metals, mixed metallic
hydroxides, double layer hydroxides, or hybrid layer structures.
Such minerals are reported since the beginning of this century2 and the preparation of
synthetic phases is generally based on the controlled precipitation of aqueous solutions
containing the metallic cations and began with the early work of Feitknecht.3
Since the end of the sixties, an increasing interest is being given to LDHs in the fields of
structural characterisation, preparation of new compounds and new preparative methods,
anionic exchange properties, electrochemical and magnetic properties, heterogeneous catalysis,
pharmaceutical applications, etc. Several review papers and references therein give current
trends on this subject.4-6
The aim of this paper is to picture a general overview on LDHs, but we shall mainly point
out some particular features about the structure of these compounds (in relation to their
synthesis), their preparative methods and give a tentative development strategy for post
synthesis modification illustrated by some examples.
2 A. de Roy, C. Forano and J.P. Besse
STRUCTURAL DESCRIPTION
The LDH structure is based on M(OH)6 octahedral units sharing edges in order to build
M(OH)2 brucite-like layers. These octahedral units contain both divalent and trivalent metallic
cations ; the main layers are therefore positively charged, and the charge density is proportional
to the trivalent metal ratio x = MIII/(MII+MIII). The whole structure is constituted by the
stacking of such layers, intercalating charge-balancing anionic species and water molecules as
shown in Figure 1, where the heavy general chemical formula, shortened as [MII-MIII-X] is also
given.
Figure 1.-Schematic view of the LDH structure and general formula. Reprinted from A. de Roy, C. Forano, K.
El Malki and J.P. Besse, Anionic Clays: Trends in Pillaring Chemistry, in Expanded Clays and Other
Microporous Solids, edited by M.L. Occelli and H.E. Robson (Van Nostrand Reinhold, New York 1992), vol. II,
Chap. 7 pp. 108-169, reproduced with permission from the authors.
LDHs exhibit a high charge density on the main layers. For example, a x = 1/3 trivalent
metal ratio corresponds to one charge for 50 Å2 on each side of the layer, leading to one charge
for 25 Å2 in the interlamellar domains.
Trivalent metal ratio
Most of LDH systems accommodate a relatively wide range of trivalent ratios, but it is not
reported that it could vary from 0 to 1 without main structural changes. While larger ranges are
sometimes given, the most reliable limits, are based for example on a clear evolution of lattice
parameters and correspond approximately to 0.2 ≤ x ≤ 0.4 (Figure 2). Some authors describe
Layered Double Hydroxydes: Synthesis and Post-Synthesis Modification 3
systematically LDHs by the divalent versus trivalent ratio R = MII/MIII, generally with an
integer value (for example, R = 2, R = 3), corresponding to the relative proportions of metallic
cations in the reactants during the preparation. In all cases, it is not obvious that a pure LDH
phase is always obtained, while the global composition of the precipitate corresponds to the
expected value, but contains secondary phases such as hydroxides or basic salts of the divalent
or trivalent metal.
Figure 2.-Comparison of trivalent metal ratio x scale and divalent vs. Trivalent R scale, and divalent vs.
trivalent R scale, and corresponding limits for LDH compositions.
The upper limit of trivalent ratio is generally attributed to electrostatic repulsion between
neighbouring trivalent metals in the layers, which is unavoidable if x > 1/3, and also to
repulsion between the charge-balancing anionic interlamellar species. The lower limit could
correspond to a too high main distance between these interlamellar anions leading to a collapse
of the interlamellar domains. The structure of the α -variety of divalent metals hydroxides with
neutral M(OH)2 sheets and interlamellar domains containing salts or basic salts and water
molecules seems to be close to a LDH structure with x = 0, but, as far as we know, compared to
regular LDH structures there is a solution of continuity in the values of x.
The metallic cations are arranged in the layers on an hexagonal framework of parameter a0.
For particular values of x, superstructures can be expected by ordering of divalent and trivalent
cations. In hexagonal symmetry, the solutions are given by the relation 1/x = (a/a0)2, where a is
any metal-metal distance in the hexagonal framework. The first solutions are x = 1/3, 1/4, 1/7,
1/9, 1/12, 1/13, … The survey of experimental data show that the existence of such
superstructures seems clearly evidenced only in a few cases. In other cases, the use of a
stoichiometric formula is only a simplified formalization and, in fact, the studied compounds
are essentially nonstoichiometric, with a random distribution of metallic cations in the layers.
On the contrary, a particular value can be systematically observed in some systems, for
example x = 1/3 in [Zn-Cr] based LDHs. Such particular values are also often reported in
minerals, mainly with x = 1/3 and x = 1/4 (Figure 2). These structural properties are discussed
in more detail in another chapter of this book.
Metal cations in the layers
The divalent and trivalent metal cations found in LDHs belong mainly to the third and
fourth periods of the periodic classification of the elements :
- divalent cations: Mg, Mn, Fe, Co, Ni, Cu, Zn,
- trivalent cations: Al, Mn, Fe, Co, Ni, Cr, Ga.
The ionic radii are in the range 0.65 - 0.80 Å for divalent cations and 0.62 - 0.69 Å for
trivalent ones (with the main exception, Al : 0.50 Å).
Higher ionic radii (Ca, Cd and Sc, La) seem to be incompatible with the formation of true
brucite-like layers. LDHs can also be obtained with a Li-Al monovalent-trivalent and Co-Ti
divalent-tetravalent associations or with more than two different cations in the layers; this is
also generally observed in LDH minerals containing variable amounts of minor elements.
Structure of the layers
In LDHs, the octahedral environment of metallic cations is far from being a regular
polyhedron. The octahedra are strongly flattened along the stacking direction, lowering the
symmetry from Oh to D3d, as illustrated in Figure 3 for a [Zn-Al] based LDH. The higher is the
mean metal ionic radius, the more flattened are the octahedra with a lowering of the layer
thickness h and an increase of the distance a between metals – which is the same as between
OH groups on same side of the layer.
Figure 3.-Flattening of the M(OH)6 octahedron in a [Zn-Al] LDH.
This evolution is illustrated in Table 1 with results from X-ray Rietveld structure
refinement, for two [Zn-Al] and [Zn-Cr] based LDHs. The comparison of calculated and
observed M-OH distances show that a simple geometrical model based on ionic radii is unable
to provide quantitative predictions. It also appears clearly that the hydoxyl groups on each side
of the main layer do not build a really close-packing layout with such high OH-OH distances (≈
3.1 Å).
If the radius of one of the metallic cations becomes too high, the octahedral coordination is
lost by opening of one side of the octahedron on the interlamellar domain leading to additional
coordination with one interlamellar water molecule. The symmetry around the metal is lowered
from D3d to C3v. Such a behaviour is observed in minerals from the hydrocalumite group. For
[Ca-Al] based layers, three different short range distances are observed around calcium: 3
Ca-OH at 2.375 Å, 3 Ca-OH at 2.455 Å, and 1 Ca-OH2 at 2.497 Å.
Table 1.- Structural data about the layers of two [Zn-Al] and [Zn-Cr] based LDHs ;
distances are in Å and angles in degrees.
composition of main layers Zn3/4Al1/4(OH)2 Zn2/3Cr1/3(OH)2

II III
mean M -M ionic radius 0.68 0.72
M-OH distance (calc. / obs.) 2.04 / 2.053 2.08 / 2.053
a (mean M-M distance) 3.083 3.120
h (along C3 axis) 2.071 2.020
OH-OH distance (same / alter. side)3.083 / 2.729 3.120 / 2.707
OH-M-OH angle (same / alter. side)96.9 / 83.0 98.1 / 81.9
Interlamellar anions
In LDHs, the interlamellar domains contain anions, water molecules and sometimes other
neutral or charged moieties. One major characteristic of LDHs is that, in most cases, only weak
bondings occur between these interlamellar ions or molecules and the host structure. A great
variety of anionic species can therefore be located between the layers during the formation of
the lamellar structure, or by further anionic exchange.
These anions can be:
- halides : fluoride, chloride,…

- oxo-anions : carbonate, nitrate, sulphate, bromate, …
- oxo and polyoxo-metallates : chromate, dichromate, (Mo7O24)6-, (V10O28)6-, …
- anionic complexes : ferro and ferricyanide, (PdCl4)2-, …
- organic anions : carboxylates, phosphonates, alkyl sulphates, …
In relation to the size, charge and layout of these interlamellar species, the basal spacing of
the layers is dramatically modified as shown in Figure 4, which gives a selection of inorganic
and organic species. The most remarkable features are:
− the large gap between brucite and the smallest basal spacings in LDHs, corresponding to
the intercalation of an interlamellar monolayer,
− the small distance range for a series of small anions - hydroxyl, fluoride, carbonate,
chloride, attributed to a “levelling” effect of water molecules,
− he clear separation between inorganic anions intercalated LDHs with basal spacings lower
than 15 Å, even for species such as the decavanadate, and hybrid LDHs intercalating
organic anions and displaying distances larger than 15 Å.
Interlamellar structure
The structure of interlamellar domains is more difficult to characterize than the main layers.
With small anionic species, such as halides and carbonates, and up to sulphate-containing
LDHs with a basal spacing of 11Å, a regular stacking of the layers is observed in the X-ray
diffractograms. With bulky anions, the stacking of the layers displays in most cases no more
long-range ordering (turbostratic effect) and the diffractograms show only lines relative to the
basal spacing and to the structure of the main layers.
As an example, we give here the results of X-ray Rietveld structure refinement on a
[Zn-Cr-Cl] LDH (Table 2). The same R-3m space group was used for the first structural
resolution on a monocrystalline LDH mineral.7 This space group is very “low cost” with only
one refinable atomic position parameter for the main layers, and one more for the interlamellar
domain, where chloride and oxygen of water molecules are randomly distributed on a high
multiplicity position around the C3 axis. As reported in Figure 5, the hydroxyl groups are facing
one another between two succesive layers and the layout of interlamellar species is in
agreement with hydrogen-bonding onto the main layers.
Figure 4.-Evolution of basal spacing with intercalated anions.

Table 2.-Rietveld structure refinement of a [Zn-Cr-Cl] LDH.
space group R-3m a = 3.124 Å reliability :RI = 4.53 %

3R stacking c = 23.29 Å RWP = 13.25 %
atoms site x y z B11(Å2) B33(Å2)
2 Zn, 1 Cr 3 (a) 0 0 0 2.4 (2) 5.2 (4)
6 OH 6 (c) 0 0 0.3810 (2) 3.6(2) 4.8(2)
1 Cl, 2 H2O 18 (g) 0.269 (3) 0 1/2 15.7 (4) 2.45 (3)
Figure 5.-Disposition of interlamellar species in a [Zn-Cr-Cl] LDH.
This 3R rhombohedral stacking is also reported with other interlamellar halides or with
carbonates. For LDHs intercalating anions of tetrahedral shape such as sulphate, the structures
are described in hexagonal space groups (P63/mmc and P63/mcm) leading to a 2H stacking of
the layers.8
A Nomenclature for LDHs
A LDH phase is mainly described by its chemical formula, the basal spacing of the layers
and the symmetry of the stacking sequence. We have shown that the heavy general formula
given in Figure 1 could be shortened as [MII-MIII-X]. We propose now an extended symbolic
notation nx[MII-MIII-X]dss constituted of three parts :
- the qualitative chemical data between brackets, with divalent-trivalent anion symbols, in
this order and separated by hyphens,
- on the left side, quantitative chemical data: trivalent metal ratio x and hydration state n
based on a M(OH)2 formula,
- on the right side, structural data: basal spacing d of the layers in Å and their stacking
sequence ss (3R, 2H, …).
A great adaptability can be expected from this notation by the use of all or part of the full
symbol, for example in a 0.33[Zn-Cr-Cl] phase, the [Zn-Cr] symbol refers to the framework
regardless to the nature of the interlamellar anion.4
PREPARATION OF LDHS
LDHs exist as minerals with names depending on their composition and the symmetry of
polytypes9 for example :
- Hydrotalcite, Manasseite Mg, Al

- Sjögrenite, Pyroaurite, Coalingite Mg, Fe
- Stichtite, Babertonite Mg, Cr
- Takovite Ni, Al or Ni, Ni
- Reevesite Ni, Fe
- Woodwardite Cu, Al
where the interlamellar anion is mainly carbonate, and sometimes sulphate or chloride.
Their composition is generally complex with minor elements and associated phases; it is
therefore necessary to prepare synthetic phases for an extensive study of LDHs.
Coprecipitation Method
This is the most common preparative method of LDHs. It is based on the slow addition of a
mixed solution of divalent and trivalent metals salts in adequate proportions into a reactor
containing water. A second solution (alkaline solution) is added in the reactor in order to
maintain the pH at a selected value leading to the coprecipitation of the two metallic salts. A
schematic experimental device is given in Figure 6 - all of the sub-systems are not required for
every experiment.
Mechanism of Coprecipitation
The mechanism of coprecipitation is ideally based on the condensation of hexa-aquo

complexes in solution in order to build the brucite-like layers with a distribution of both
metallic cations and with solvated interlamellar anions. Observation of the precipitates and
X-ray diffraction characterization show that the co-formation of the main layers and
interlamellar domains takes place at a very early stage of the process without clear
“delaminated” state of the layers.
Origin of Interlamellar Anions
The metal cations in the obtained LDH phase are obviously issued from the metallic salts
solution, but the origin of interlamellar anions has to be discussed. If these anions are the
counter-anions of the metallic salts they come from the same solution. If the preparation is
performed at very high pH values, the interlamellar anion can be the hydroxyl anion coming
from the alkaline solution. When the alkaline solution is a sodium or potassium carbonate
solution, the intercalated anion is the carbonate because of its high selectivity for LDHs
interlamellar domains. Moreover, when the preparation is performed at relatively high pHs, one
have to work under CO2-free conditions in order to avoid carbonate contamination. Another
way to intercalate a given anion is to prepare a solution of this anion in the reactor prior to the
beginning of the coprecipitation.
So, we see that there is often competition between several anionic species, and the control
of experimental conditions can lead to the selective intercalation of one of them as the primary
interlamellar anion. Secondary interlamellar anions can replace them by further treatments
such as anionic exchange (vide infra).
Figure 6.-Experimental device for the preparation of LDHs by the coprecipitation method.
Experimental Parameters
Depending on the precipitation conditions, one can generally obtain well crystallized LDH
phases or quasi amorphous materials. Some of these experimental parameters are obvious, like:
- temperature in the reactor,

- pH of the reaction medium,
- concentration of metallic salts solution,
- concentration of alkaline solution,
- flow rate of reactants,
- aging of the precipitate,
other parameters are less obvious, such as :
- accumulation of electrolytes in the reaction medium,
- hydro-dynamics of the dilution of reactive species, related to the stirring mechanism,
geometry of the reactor including reactants injection pipes,
- complexation state of the metallic cations which, depending on the previous history of the
metallic salts solutions, can give rise to a great number of different M(OH2)u(OH)vXw
charged monomers and also to oligomers.
In order to obtain well organised phases, the operating conditions have to be optimized for
each system. In all cases, synthetic LDHs are obtained as microcrystalline platelets generally
aggregated in a “rose des sables“ morphology as shown by SEM. The low BET surface areas
measured (20-40 m2g-1) are in good agreement with the external surface of the platelets.
The effect of the precipitation pH on the formation of LDH compounds is well-evidenced
by the investigation realized on [Zn-Al-Cl], 0.33[Zn-Cr-Cl]3R and 0.33[Cu-Cr-Cl] 3R systems.
The 0.25[Zn-Al-Cr]3R LDH has been prepared in the pH range from 4.0 to 11.0. For such a
composition, a compound with a well ordered hydrotalcite-like structure forms in the pH range
from 7.0 to 10.0. At lower pH values, an amorphous compound is obtained, while at higher pH
values brucite-type Zn(OH)2 crystallizes together with the LDH phase. One must notice that,
for such pH values, the reaction of formation of the LDH corresponds to a simultaneous
precipitation of both metallic cations, the pH being greater than the precipitation pH of both
Zn(OH)2 and Al(OH)3.
In the case of the 0.33[Zn-Cr-Cl]3R phase, a pure and well ordered LDH is formed at a pH
much lower than that for [Zn-Al-Cl]3R; 0.33[Zn-Cr-Cl]3R is obtained at pH = 4.5-5.0, and badly
crystallized or amorphous materials are obtained at pH values higher than 5.0. An X-ray
diffraction study of LDH prepared from pH = 4.5 to 10 (Figure 7) shows an improvement in the
crystallinity when the pH is lowered. It should be notice that, in this case, the optimal pH of 4.5
is lower than the pH of precipitation of Zn(OH)2, and therefore the coprecipitation does not
occur in these conditions. The reaction must probably proceed via the precipitation of Cr(OH)3,
and then the reaction of Cr(OH)3 with Zn2+ cations in solution. The chemical composition of
the final product diverges from the initial M2+ and M3+ ratio.
Figure 7.-X-ray powder diffractograms of 0.33[Zn-Cr-Cl]3R prepared at pH=10.0 (a) and pH=4.5 (b).
Reprinted from A. de Roy, C. Forano, K. El Malki and J.P. Besse, Anionic Clays: Trends in Pillaring Chemistry,
in Expanded Clays and Other Microporous Solids, edited by M.L. Occelli and H.E. Robson (Van Nostrand
Reinhold, New York 1992), vol. II, Chap. 7 pp. 108-169, reproduced with permission from the authors.
The effect of the pH upon the formation of 0.33[Cu-Cr-Cl]3R is similar. The best crystallized
phase is obtained at the lowest pH value of 5.5. Below this pH, an additional unidentified phase
appears. It must be noticed that, in some cases, the pH does not have a direct observable effect
on the diffraction pattern. The typical example comes from the 0.33[Ni-Cr-Cl] phase. This phase
displays the same powder X-ray diffraction patterns characteristic of a quasi-amorphous

material, whatever the pH of precipitation from 5.5 to 11.5. However, under hydrothermal
treatment, the only phase that crystallizes is the LDH prepared at pH = 11.5.
However, no clear relationship seems to exist between the individual precipitation pH of
metals and the precipitation pH of mixed hydroxides (Figure 8). It seems reasonable to think
that, for chromium-based LDH compounds, the intermediate pH range from 6.0 to 10.0 does
not favor the formation of a well-ordered phase, probably because of the less reactivity of Cr3+
ions, which form a great number of oligomeric complexes in this domain. On the other hand,
real coprecipitation conditions are not respected for 0.33[Zn-Cr-Cl]3R, 0.33[Cu-Cr-Cl]3R, and
sometimes [Mg-Al-Cl] 3R.
The coprecipitation method was extensively used to prepare new LDH in recent years.
From the point of view of the chemical composition, we will review what is possible to put in
an LDH :
Figure 8.-pH domains for some LDHs formation. Reprinted from A. de Roy, C. Forano, K. El Malki and J.P.
Besse, Anionic Clays: Trends in Pillaring Chemistry, in Expanded Clays and Other Microporous Solids, edited
by M.L. Occelli and H.E. Robson (Van Nostrand Reinhold, New York 1992), vol. II, Chap. 7 pp. 108-169,
reproduced with permission from the authors.
Which Metals ?
Figure 9 shows the great variety of metal cation which are possible to introduce in the LDH
sheets.
A very wide range of compositions may be obtained by synthesis; for instance, even
[Li -Al3+] 10-11 and [Co2+-Ti4+] 12 associations have been described in the literature. M2+ and
+
M3+ ions having an ionic radius not too different from that of Mg2+ may be accommodated in
the octahedral sites of the close-packed configuration of the OH- ions in the brucite-like layers
to form LDHs compounds. Otherwise, ions which are too small, such as Be2+, or too large, such
as Ca2+ and Cd2+, give rise to other types of compounds,13 even though natural and synthetic
LDH compounds containing small amounts of these "large cations" have been reported. For the
trivalent ions, the useful atomic range is narrower than that for the spinel structure, and, not
with standing the instability in air, an [Mg2+-V3+-CO3] LDH compound has been synthesized,14
while up to now no Ti3+ - containing LDH compound had been reported.
Figure 9.-Association of divalent and trivalent metallic cations in LDHs. ( : monovalent; : tetravalent).
Adapted from[4].
Which anions ?
A very wide range of anions are reported in the literature :
- inorganic anions (halides and oxyanions such as CO32-, NO3-, SO42-, OH-, CrO42-, WO42-,
S2O32-, etc.) ;
- isopolyanions (V10O286-, Mo7O246-, etc.) and heteropolyanions (PMo12O403-, PW12O403-,
etc.) ;
- complex anions (Fe(CN)63-, Fe(CN)64-, etc.), and organometallic complexes ;
- organic anions (carboxylates and dicarboxylates, benzene carboxylates, alkylsulfates,
chloro-cinnamate, etc.) ,and
- layered compounds, such as the mineral chlorite (Mg,Fe,Al)6[(Si,Al)4O10](OH)8.
The major problem in obtaining pure LDH phases arises from contamination by easily
intercalated carbonate anions, which must be prevented by using very strict CO2-free
conditions. On the other hand, the pH range where the anion is stable must overlap the pH
domain of formation of the layered double hydroxide. For example, Keggin anions PW12O403-
and SiW12O404- are not stable at a pH greater than 5.0, preventing direct precipitation of [Zn-Al]
LDH, usually obtained at pH ≈ 9.0.
Which MII/MIII ratio ?
Chemical analysis of LDH usually confirms that all metal cations are precipitated and,
provided a suitable pH of precipitation is used, the initial MII/MIII ratio is always retained. A
difficult problem to deal with when one wants to determine the chemical composition of an
LDH is to know whether all of the metal cations have been precipitated as LDH, and often,
microscopic chemical analysis has not been performed on the samples. However, for a
well-ordered LDH, the deviation from the initial MII/MIII ratio is low and the prepared LDH
must be considered as highly pure. One method often neglected to characterize the domain of
composition where the LDH exists as a pure phase is to measure the variation of the cell
parameters (a and c for hexagonal unit cell) with the composition. Most of the mixed double
hydroxides can be prepared with a variable MII/MIII ratio. Table 3 gives the domain of
composition of this series, with comparable results reported in the literature.
Table 3.- Chemical composition range of various LDH
MII-MIII-X pHformation MII/MIII (R) range

[Zn-Al-Cl] 7.0 1.0 ≤ R ≤ 5.0
[Zn-Al-Cl] 10.0 1.0 ≤ R ≤ 3.0
[Ni-Cr-Cl] 11.5 1.0 ≤ R ≤ 3.0
[Ni-Cr-CO3] 13.0 1.0 ≤ R ≤ 2.0
[Cu-Cr-Cl] 5.5 1.6 ≤ R ≤ 2.3
[Zn-Al-CO3] 9.0 1.7 ≤ R ≤ 2.3
[Mg-Al-CO3] 8.0
1.0 ≤ R ≤ 3.0
[Zn-Cr-Cl] 4.5
R ≈ 2.0
[Zn-Cr-Cl] 10.0
2.0 ≤ R ≤ 3.0
[Mg-Fe-CO3] -
2.7 ≤ R ≤ 5.6
[Ni-Al-ClO4] 10.0
1.0 ≤ R ≤ 3.0
[Co-Fe-Cl] 9.0
1.8 ≤ R ≤ 4.0
[Co-Fe-CO3] 9.0
1.0 ≤ R ≤ 3.0
We can see, here again, the determining effect of the pH value. For instance, PXRD study
of the [Zn-Al-Cl]3R samples series shows that, at a neutral pH, only the LDH phase crystallizes,
the X-ray pattern being even better when Zn2+/Al3+ ≈ 3. At pH = 10.0 for a M2+/M3+ ratio ≥ 3,
[Zn-Al-Cl] coexists with Zn(OH)2, while for a ratio ≤ 1 the excess of Al3+ ions crystallize as
bayerite, Al(OH)3; the best crystalline phase is obtained for Zn2+/Al3+=3, whatever the pH. In
the case of pure [Ni-Cr-Cl]3R and [Ni-Cr-CO3]3R phases, LDH with ratio comprised from 1.0 to
3.0 and 1.0 to 2.0, respectively, have been obtained only after hydrothermal treatment.
Which hydration state ?
Generally, the LDH contains a variable amount of water molecules, one part in the
interlayer domain, the other part at the grain boundaries. The intrinsic water is that which
contributes to the total chemical composition. Its content depends mainly on the nature, the size,
and concentration of the anions, the external water partial pressure, the washing and drying
conditions, and also, in a lesser extent, on the nature of the metal cations in the layer. But we
must insist on the fact that washing and drying conditions, hydration, or thermal treatments can
modify reversibly, and sometimes irreversibly, the physical properties of the LDH, which is
necessarily explained by a change in the chemical composition.
Thermal Treatment
In many cases, optimisation of the pH value of the coprecipitation, and the aging time, does
not lead to well crystallized LDH phases, and thermal treatment often gives good results for
improving the crystallinity of the amorphous xerogel or the badly crystallized materials.
• Temperature of coprecipitation. Most of the precipitations are carried out at room
temperature, and sometimes near reflux conditions are used to favour the crystallization, but no
significant effect of the reaction temperature has been reported. Hydrothermal treatment after
precipitation is often more efficient.
• Hydrothermal treatment. In most of the cases, hydrothermal treatment in the presence of
water vapour strongly improves the crystallinity of the LDH, provided the temperature of
decomposition of the LDH is not exceeded. Two typical experiments are usually performed.
The most accessible one consists of heating a closed stainless steel reactor containing an
aqueous suspension of the LDH precursor at a temperature below the critical point under
autogenous pressure. Another method consists of heating the sample in a gold or silver sealed
tube under a high pressure of the order of 1500 bars. Synthetic takovite [Ni-Al-CO3]3R was
prepared by treating quasi-amorphous precursors at 200°C under 1500 bars for 10 days.
[Ni-Cr-X]3R LDH with X = Cl-, CO32-, SO42-, and Ni/Cr = 1.0, 1.5, and 2.0, were obtained in an
amorphous state by coprecipitation of the mixed nitrate salts at constant pH = 13.0, and
thermally treated at 300 °C and 1500 bars pressure for 18 h, in order to obtain materials with
sharp diffraction lines.
Addition rate or aging
The addition rate or ageing are two determining factors that affect the crystallinity of the
mixed double hydroxides. Even if people agree on the fact that ageing or slow addition rate
must be performed in order to prepare a well-crystallized phase, only a few systematic studies
have been reported on the influence of these parameters on the chemical composition,
morphology, or crystallinity. With an automatic titration device, it is possible to impose a slow
addition rate of about 1 ml/h. 48 h ageing is often necessary to obtain a high crystallinity. But
the conditions of ageing must be adapted to the nature of the LDH to be obtained;
[MII-MIII-NO3] will need a longer ageing time than carbonate LDH.
The urea method
Urea has a series of properties that makes its use as an agent for precipitation from
"homogeneous" solution very attractive and it has long been used in gravimetric analysis to
precipitate several metal ions as hydroxides or as insoluble salts when in the presence of a
suitable anion.15 Urea is a very weak Brönsted base (pKb = 13.8), highly soluble in water, and
its hydrolysis rate may be easily controlled by controlling the temperature of the reaction.
According to Shaw and Bordeaux,16 the mechanism of hydrolysis consists of the formation of
ammonium cyanate, as the rate determining step, and the fast hydrolysis of the cyanate to
ammonium carbonate, i.e.:
CO(NH2)2 → NH4CON
NH4CNO + 2H2O → (NH4)2CO3
The rate constant increases by about 200 times when the temperature is increased from 60
to 100°C. The hydrolysis of ammonium to ammonia and carbonate to hydrogen carbonate gives
a pH of about 9, depending on the temperature. This pH is suitable for precipitating a great
number of metal hydroxides.
After some preliminary positive tests, a wider investigation was undertaken to find the
optimal conditions to produce, with a simple procedure, LDH microcrystals of uniform size,
well crystallised, and with the required stoichiometry. The following couples of cations, as
chlorides, were considered : Mg(II)-Al(III) ; Zn(II)-Al(III) ; Ni(II)-Al(III). In the case of Zn(II),
a weighed amount of ZnO was dissolved in a stoichiometric amount of 6 mol/dm3 HCl
solution.17
LDHs with two divalent or trivalent metal cations
The flexibility of the LDH structure is clearly demonstrated by the fact that pure
compounds with two divalent metals may be obtained by coprecipitation method. So,
Ni/Mg/Al LDH with various Ni/Mg ratio are synthesized and are precursors of
high-surface-area Ni/Mg/Al mixed oxides with many catalytic applications.18 Also LDH are
obtained with two trivalent cations, for example Mg(Al, Y).19
Other Preparative Methods and Comparison
Induced hydrolysis
The induced hydrolysis20 is a two step method. The trivalent metal hydroxide is first
precipitated by an alkaline solution. The second step consist in the slow addition of this
precipitate on a solution of the divalent metal salt at a constant pH, inducing a controlled
release of trivalent metal species and formation of the LDH phase.
Salt - oxide method
This synthesis method was initially used to prepare 0.33[Zn-Cr-Cl] based layered double
hydroxide. The experimental process consists of preparing an aqueous suspension of zinc oxide
and to react it with an aqueous solution of chromium chloride in excess, for a few days at room
temperature. A single chemical composition corresponding to the formula Zn2Cr(OH)6Cl·2H2O,
characteristic of LDH-type compounds, was obtained. The same material was prepared by
pouring the chromium chloride solution into a viscous slurry of ZnO stirred during 10 h. Such
conditions have been reproduced in our laboratory and the so-obtained 0.33[Zn-Cr-Cl] phase
was characteristic of a badly-ordered material. This method has been developed in order to
prepare LDH with different combinations of divalent metals, trivalent metals, and anions, in
particular [Zn-Cr-Cl], [Zn-Cr-NO3], [Zn-Al-Cl], and [Zn-Al-NO3]. The theoretical reaction is
described by:
MIIO + xMIIIXm-3/m + (n+1) H2O → MII1-xMIIIx(OH)2Xm-x/m · nH2O + x MIIXm-2/m
The nature of the reagents leads us to name this synthesis the "salt-oxide method".
The [Zn-Cr-Cl] system.
The "salt-oxide method" is a simple solid-liquid reaction. Experimentally, this method

consists of adding small volumes of a 1M solution of chromium chloride at constant periods of
time to a 3-5 wt % ZnO aqueous suspension under vigorous stirring at a given temperature. pH
recording during the addition of the trivalent salt (Figure 10) allows one to follow the reaction
progress. Drops in pH at each addition of the acid salt, followed by a return to the initial pH
value of the buffering zinc oxide, are well shown. The reaction is completed when an excess of
CrCl3aq. no longer reacts.
This step is evidenced by the equivalent point on the potentiometric curve, and the pH
value remains constant at about 4.0 after a further addition of CrCl3aq.. X-ray diffraction studies
of small fractions of the suspension taken off at various titration points show the disappearance
of ZnO and the development of the diffraction lines of the LDH phase.
A quantitative X-ray analysis allows to calculate the stoichiometric coefficient of the
reaction when plotting the molar ratio ZnO/CrCl3 versus diffraction line intensity ratios :
IZnO/I[Zn-Cr-Cl].
The corresponding equation of the reaction is given by:
3ZnO + CrCl3 + (n+3) H2O → Zn2Cr(OH)6Cl·nH2O + ZnCl2
The chemical analysis of the [Zn-Cr-Cl] phase so obtained confirms the definite ratio
Zn/Cr = 2, previously proposed by Boehm, Steinle, and Vieweger.21 Attempts to vary the Zn/Cr
ratio in this way were unsuccessful. The relatively low weight fraction of ZnO (2-5 wt % range)
and the slow addition of the CrCl3 solution or long aging time in contact with the mother liquor
greatly improve the crystallinity of the double hydroxide (Figure 11).
Figure 10.-Stepwise potentiometric titration of a MIIO suspension by a MIIICl3 solution. Reprinted from A. de
Roy, C. Forano, K. El Malki and J.P. Besse, Anionic Clays: Trends in Pillaring Chemistry, in Expanded Clays
and Other Microporous Solids, edited by M.L. Occelli and H.E. Robson (Van Nostrand Reinhold, New York
1992), vol. II, Chap. 7 pp. 108-169, reproduced with permission from the authors.
From the point of view of the mechanism, the reaction seems to proceed first via an acidic
hydrolysis of ZnO during the addition of CrCl3aq and then a coprecipitation of the mixed Zn/Cr
double hydroxide, the formation of which is favoured at a pH range of 4 to 7. Following this
procedure, the pH value always varies during the addition, and may affect the homogeneity of
the product. The experimental device was modified in order to fix the pH at a constant value
during the experiment. This can be done by regulating the addition of the solution of CrCl3.
This method, which operates at constant reactivity of of CrCl3, does not allow us to prepare
pure 0.33[Zn-Cr-Cl]3R LDH, and small amounts of ZnO still remain in the final product.
Figure 11.-X-ray powder diffraction patterns (Cu K ) for 0.33[Zn-Al-Cr]3R, 0.33[Zn-Cr-Cl]3R and
0.33[Cu-Cr-Cl]3R. Reprinted from A. de Roy, C. Forano, K. El Malki and J.P. Besse, Anionic Clays: Trends in
Pillaring Chemistry, in Expanded Clays and Other Microporous Solids, edited by M.L. Occelli and H.E.
Robson (Van Nostrand Reinhold, New York 1992), vol. II, Chap. 7 pp. 108-169, reproduced with permission
from the authors.
Preparation of other LDH
This method of preparation has been used to prepare other LDHs, usually synthesized by
the classical coprecipitation method.
• [Zn-Al-Cl] : Pure [Zn-Al-Cl]3R (Figure 11) can be obtained by the addition of a solution
of AlCl3 to an aqueous suspension of ZnO, under the same experimental conditions.
Monitoring of the reaction by X-ray diffraction shows that, for x greater than 0.25, no more
ZnO is present and stoichiometries corresponding either to Zn2+/Al3+= 2 or to Zn2+/Al3+= 3
were obtained. For [Zn-Al-Cl]3R, a range of composition can probably be obtained.22
• [Cu-Cr-Cl] : This compound had never been prepared previously by the coprecipitation
method and the alternative salt-oxide method was successfully used to synthesized it. The
reaction proceeds at a nearly constant pH, contrary to what is observed in the former cases. The
pH drops from 6.8 after the first addition of CrCl3, and then remains constant at ca. 4.5. The
disappearance of CuO in the diffractograms (Figure 11) occurs at a Cu/Cr ratio near 2, and the
phase is characterized by the chemical formula : Cu2Cr(OH)6Cl·nH2O.23
• Others attempts to prepare new LDH phases or LDH with definite stoichiometry by this
method were unsuccessful. With Zn/Fe/Cl, Cu/Al/Cl or Cu/Fe/Cl systems, mainly
hydroxichloride phases are formed, respectively Zn5-xFex(OH)8 Cl2+x.H2O [22], a phase with
the structure of the simonkolleite, Zn5(OH)8Cl2.H2O,24 and Cu2(OH)3Cl, the paratacamite.25
With the Mg/Cr/Cl system, a new metastable phase of composition MgxCr1-x(OH)3-3xOx/2 21 is
prepared, which displays the structural properties of the bayerite β-Al(OH)3. LDH phases
based on divalent metals Ni ([Ni-Cr-Cl], [Ni-Al-Cl], [Ni-Fe-Cl]) or Co ([Co-Fe-Cl]) were not
prepared by this way because of the unreactivity of the respective oxides NiO and CoO.
Comparison of Preparative Methods
While the three methods - coprecipitation, induced hydrolysis and salt-oxide, seem to be
quite different, the mechanism for the construction of the LDH structure is probably the same;
this can also be extended to the reconstruction method described later. In all cases the aim is to
obtain in the reactive medium each constituent of the future LDH structure in the most
appropriate concentration and association state. The “best method” does not exist; depending
on the studied system and the final use of the product, one or another method has to be chosen.
POST SYNTHESIS MODIFICATION OF LDHS

The physicochemical properties and the reactivity of the LDHs are determined not only by
the chemical nature of the overall structure, but also largely by the tight interactions between
the host matrix and the guest species.
Subsequent treatments can modify as prepared LDHs. The most obvious is anionic
exchange, but moderate thermal treatments and even washing and drying processes can also
give rise to new materials.
Anionic exchange
The lamellar structure of LDH, based on a stacking of positive layers trapping anionic
species in the interlayer domains, is highly favourable to anion diffusion, and LDH is one of the
principal classes of inorganic ion exchangers.26 This property has been mainly used in order to
prepare new LDH phases by anionic exchange reactions. The reaction can be described by the
equilibrium:
[MII-MIII-X] + Y → [MII-MIII-Y] + X
This thermodynamic system is bivariant in isothermal and isopressure conditions. It can be

completely described by two extensive parameters which resume in a unique X’1 = f(X1)
relation if the total concentration of the anion in the liquid phase is retained constant (X’1 is the
molar fraction of the anion to be intercalated in the LDH, and X1 its molar fraction in the liquid
solution). In 1983, Miyata reported ion-exchange isotherms at 25°C of [Mg-Al-X/Y] for a
series of monovalent and divalent anions. All isotherms display a sigmoid shape arising from a
mixed continuous composition range of the anions in the LDH. The PXRD studies that we
performed during exchange of various systems [MII-MIII-X/Y], and more particularly of
[Zn-Cr-Cl/Y] and [Zn-Al-Cl/Y] (Y = F-, Br-, I-), did not evidence any continuous variation of
the basal spacing with increase of the molar fraction in the liquid phase of the anion to be
intercalated. Non-miscibility of the different anions in LDH and the short range of coexistence
of two LDH phases were observed.
Thermodynamically, exchange in LDH depends mainly on the electrostatic interactions
between positively charged hydroxylated sheets and the exchanging anions and, to a lower
extent, on the free energy involved in the changes of hydration.27 Another important remark
was that the equilibrium constant increases when the ionic radius of the bare anion decreases.
Exchange is therefore favoured for in-going anions with a high charge density. From
calculations of the equilibrium constant of various exchange reactions, Miyata12 gave a
comparative list of ion selectivities for monovalent anions: OH- > F- > Cl- > Br- > NO3- > I- and
divalent anions: CO32- > C10H4N2O8S2- > SO42-. For [Cu-Al-X/Y] systems, Yamaoka et al.28
determined an equivalent selectivity sequence for divalent oxoanions: HPO42-, HAsO42-, >
CrO42- > SO42- > MoO42-. Moreover, it appears that the selectivities of divalent anions are
higher than those of monovalent anions. According to these results, nitrate- and
chloride-containing LDHs appear to be among the best precursors for exchange reactions. Such
anions can easily be replaced by more selective anions, such as Fe(CN)62-, Fe(CN)63-,
Mo(CN)84-, or IrCl62-. Organic anions with long chains can also be directly intercalated by
exchange reactions on LDH precursors with inorganic anions, for example, n-CmH2m+1SO4- (n
= 8, 12, 14, 16, 18) on 0.33[ZnCr-Cl]3R 21 and 5,10,15,20-tetra(4-sulphonatophenylporphin) on
[Mg-Al-Cl]3R.29 In this way, a large variety of organic anion-containing LDHs have been
prepared.30,31
From a kinetic point of view, the rate-determining step of the reaction is the diffusion of the
in-going anions within the interlayer, provided the "infinite solution conditions" are respected.
The diffusion of big anions inside the interlayer can be prevented by a too small basal spacing
of the precursor. Exchange reactions via organic-anion-pillared precursors are then used.
Intercalation of bulk polyoxometalate anions, such as Mo7O246-, V10O286-, or H2W12O406-,was
successfully done via 0.33[Mg-Al-C6H4(CO2)2] 32 and 0.33[Mg-Al-C7H7SO3].33 Figure 12 shows

various possibilities of intercalation of anions in LDHs structure.
From the point of view of experimental considerations, this synthesis presents an ease of
implementation and, in the simplest case, an aqueous suspension of an LDH precursor is stirred
in the presence of a large excess (10 to 20 time excess) of the salt of the anion to be intercalated.
The chloride, nitrate, and carbonate precursors are easily synthesized. Nevertheless,
parameters such as the pH of exchange or the washing and drying conditions can favour or
prevent the exchange. The pH of exchange can play a different role, and it must be compatible
with the domain of stability of the hydroxylated layer and the anion to be intercalated. For
example, complete exchange of chloride by V10O286- in 0.330.7[Zn-Al-Cl]3R, 0.330.7[Zn-Cr-Cl]3R,
and 0.250.8[Ni-Al-Cl]3R, using [NH4]6[V10O286-]. 6H2O must be carried out at pH = 4.5.34,35
Moreover, when LDH precursors contain carbonate or carboxylate anions, the exchange must
be performed at pH values of about 4.5 to 6.0 in order to acidify these anions and expel them
more easily. Higher pH values (10.0-12.0) strongly favour intercalation of carbonate, and a
CO2-free atmosphere must be used if carbonation is to be prevented.
Therefore, this method of synthesis remains an easy pathway to prepare synthetic anionic
clays, and we succeeded in preparing a large number of LDH [Zn-Al-X]3R, 0.33[Zn-Cr-X]3R,
0.33[Cu-Cr-X]3R, and [Ni-Cr-X]3R, where X can be a halide or an oxoanion. Total exchange was
observed for anions, except for ClO3-, IO3-, ReO4- and ClO4-.36,37
Washing and drying process
After preparation, the LDH precipitate has to be separated from the reactive medium,
washed and dried. The following example corresponding to 0.33[Zn-Cr-SO4] phases (Figure 13)
shows that the operating conditions can strongly modify the obtained LDH.
In the 3D diagram where the basal spacing d, the temperature of thermal treatment t and the
relative humidity (RH) at room temperature %RH are reported, five structural varieties could
be identified:
- a 2H “11Å” phase which intercalate the sulphate groups and also alkaline cations (sodium
or potassium) surrounded by water molecules,
- a 3R “10.9Å” phase without alkaline cations obtained by washing of the previous one,
- a 2H “8.9Å” phase corresponding to a partial dehydration of interlamellar domains,
- a 3R “8.3Å” phase corresponding to severe dehydration at room temperature.
All of these phases can be reversibly obtained. This points out that the washing and drying
processes can be considered as post-synthesis treatments. In this example, the “as-prepared”
phase in the reactive medium is always the 2H "11 Å" phase.38
Figure 12.-Schematic representation of polyoxometalate exchange via terephthalate compound in an LDH.
Grafting of anions onto LDH layers
The last 3R “7.1 Å” phase in Figure 13 diagram corresponds to an irreversible

transformation of the structure with no more rehydration or further anionic exchange capacity.
Such transformations are related to moderate thermal treatments of several LDHs
intercalating tetrahedral oxoanions such as sulphates, selenates, phosphates, chromates and
dichromates, etc. The low basal basal spacing is incompatible with the presence of “free”
(XO4)2- anions. The only consistent hypothesis is the grafting39 of the anions onto the LDH
layers with elimination of water molecules, leading to neutral layers. The new phase has to be
considered as a layered oxy-hydroxy-salt and belongs no longer to the LDHs family. This
behaviour was also recently evidenced by XAFS.40
Figure 13.-Structural transformations of a 0.33[Zn-Cr-SO4] LDH related to the washing process, the relative
humidity of atmosphere (%RH), and temperature, t °C.
Examples: Modification of oxoanions intercalated LDHs.
The structure of the 0.670.32[MII-MIII-X]8.922H interlamellar domains is described as an

ordered arrangement of alternatively inverse interlayer SO4 tetrahedra, retaining their C3 axis
perpendicular to the layer, with one oxygen pointing to a metallic cation of a brucite-like layer
and the three other facing three OH groups of the opposite layer. The short hydrogen bonds
lengths of, respectively, 2.93 Å and 2.71 Å, reveal strong interactions between layers and
sulphate anions and lead to the 8.92 Å observed basal spacing.
Sulphate and chromate anions have the same size, with anionic radii of 2.42 Å and 2.44 Å,
respectively.23 The dichromate anion is a simple condensation of two CrO4 groups with a
Cr-O-Cr angle close to 126° (in K2Cr2O7) and displays, with such a stereochemistry a modelled
hindrance of roughly 5.5 x 2.8 Å, but flexible geometry of the Cr-O-Cr bonding can be
expected. The similar d values obtained for the Cr2O7 and XO4 LDH phases must account for a
similar orientation of the anions, Cr2O7 lying flat and parallel to the layers. This can ensure
optimal interactions of all polyhedra oxygen atoms with the OH groups.
The analysis of the structural data enable two different modes of anion-layer interactions to
be differentiated:
One first group of LDHs ([Zn-Cr-SO4], [Zn-Al-SO4], [Cu-Cr-SO4], [Zn-Al-CrO4],

[Cu-Cr-CrO4], [Zn-Cr-Cr2O7] and [Cu-Cr-Cr2O7]) display, as prepared, basal spacings near the
d value of 0.670.32[MII-MIII-X]8.922H. In all these phases, the oxo-anions are oriented in a similar
way to the SO42- ions in the reference material. Among this group, [Zn-Cr-SO4] and
[Zn-Al-SO4] appear to be structurally stable under usual storing conditions.
Other phases of this group ([Zn-Al-CrO4], [Cu-Cr-CrO4] [Zn-Cr-Cr2O7] and
[Cu-Cr-Cr2O7]) undergo a spontaneous interlayer contraction, leading to d values ranging from
7.90 Å to 7.34 Å and are referred to as "aged phases". This is the case for [Cu-Cr-CrO4]7.68; this
phase is the result of the ageing in air of [Cu-Cr-CrO4]8.42. Freshly prepared [Cu-Cr-Cr2O7] also
undergoes a contraction process (from 8.95 Å to 7.87 Å) to a structurally stable LDH.
[Zn-Al-CrO4] has also been demonstrated to contract after ageing in its mother solution. These
phases define a second group of contracted LDHs. Two other freshly prepared LDHs,
[Zn-Cr-CrO4]8.13 and [Zn-Al-Cr2O7]7.85, show short interlayer spacings and can be included in
this second group. For all of these contracted phases, intercalated oxo-anions remain
exchangeable, by chloride anions for example. In these layered structures, the shortening of the
interlayer distances is then no longer compatible with "free" oxo-anions lying as described in
the former phases.
Further investigations of the LDH contraction properties have been carried out by a study
of the effect of thermal treatment on the LDH structure. Moderate heating in air during 24 h was
performed at 150°C, temperature at which dehydroxylation has generally not yet occurred in
chloride LDHs. All the phases undergo a further contraction which then appears irreversible,
since anion exchange is no longer possible. The new phases still display PXRD patterns typical
of LDHs. The basal spacings are now included in a narrower range, from 6.80 Å to 7.20 Å, for
all the oxo-anion intercalated LDHs and [Cu-Cr-Cl]. For the other chloride phases, [Zn-Cr-Cl]
and [Zn-Al-Cl], the shortening is of lower amplitude, leading respectively to basal spacings of
7.43 Å and 7.63 Å.
Analogous short basal spacings are found for lamellar zinc and copper basic salts, in which
OH groups of the hydroxylated layer are partially substituted by planar XO3 or tetrahedral XO4
oxo-anions.41,42 On heating, the LDH precursors undergo a permanent pillaring of the
oxo-anions on the hydroxylated layers. The experimental d values fit well with calculations
based on a LDH structure where some of the OH groups have been replaced by the grafted
SO42-, CrO42- and Cr2O72- anions as shown in Figure 14. It should be noted that, in such
structural configuration, Cr2O72- anions must be grafted via two oxygen atoms.
The contracted LDH phases can now be regarded as "pre-grafted" phases in which the
anions come nearer to the metallic cations of the layer, probably pointing one apical oxygen
atom of the mono or di-tetrahedra towards the triangular apertures of the OH close-packed
monolayers, then minimising the interlayer distances.
From a mechanistic point of view, the grafting process necessarily occurs simultaneously
with partial dehydroxylation and the loss of water molecules, and then leads to the formation of
new pillared lamellar structures with neutral layers.
For the [Cu-Cr] compounds, the evolution of interlayer distances was studied with the
temperature of the thermal treatment, from room temperature up to 150 °C (Figure 15).
[Cu-Cr-Cl] displays a contraction of greater amplitude than those observed in the other
host structures. This contraction is no longer compatible with free interlayer chloride, but it is
too low to consider replacements of OH groups of the main layer by Cl- whose larger size
prevents its incorporation among the coplanar hydroxyls. It follows that the octahedral
environment of the metallic cations should become strongly distorted with a probable 4+2
coordination, often observed for the d9 copper ion in inorganic salts and minerals such as
botallackite Cu2(OH)3Br.
Both [Cu-Cr-CrO4] and [Cu-Cr-Cr2O7] are very temperature-sensitive and display a strong
decrease in their basal spacings at temperatures up to 60 °C. Fresh prepared phases are much
more reactive than the chloride and sulphate LDH. However, the shape of the two curves is
different, the chromate anion seems to be less reactive than the dichromate, which gives a fully
contracted phase above 80°C. At higher temperature, the lowest d values, shorter for chromate
than for dichromate, agree well with the schematic model of grafted phases displayed in Figure
14.
The behaviour of [Cu-Cr-SO4] is quite different at temperatures lower than 80°C, where
the initial basal spacing is retained. The contraction process is completed at 100 °C, leading to a
grafted phase with an interlamellar distance quite similar to that of [Cu-Cr-Cr2O7].
Figure 14.-Schematic view of LDH phases grafted with XO42-, and X2O72- oxoanions. Reprinted from C.
Forano, A. De Roy, D. Depège, M. Khaldi, F. Z. El Métoui and J. P. Besse, Post-synthesis modification of
layered double hydroxides, in Synthesis of Porous Materials. Zeolites, Clays, and Nanostructures, edited by M.
L. Occelli and H. Kessler (Marcel Dekker, Inc., New York 1996), pp. 607-625.
These structural post-synthesis modifications lead to an interesting improvement of the

thermal stability and to an increase of the specific surface area of the calcined phases compared
to the chloride phases.43
Figure 15.-(a) Effect of heating on the basal spacings of [Cu-Cr-X] LDHs (X=Cl, SO4, CrO4, Cr2O7).
Reprinted from C. Forano, A. De Roy, D. Depège, M. Khaldi, F. Z. El Métoui and J. P. Besse, Post-synthesis
modification of layered double hydroxides, in Synthesis of Porous Materials. Zeolites, Clays, and
Nanostructures, edited by M. L. Occelli and H. Kessler (Marcel Dekker, Inc., New York 1996), pp. 607-625. (b)
PXRD of [Cu-Cr-SO4] at various temperatures.
Polycondensation of Silicate in [Zn-Al] and [Zn-Cr] LDHs
The limited size of the oxometalate anions, their low charge density, and the high charge
density in the LDHs main sheets, do not allow to obtain consequent interlamellar
microporosity.43 Indeed, the basal spacing for the oxopolyanions containing LDH never
surpasses 14 Å, while intercalation of Al13 hydroxo-cations in cationic clays, for example,
yields a greater interlamellar expansion.44 In order to obtain new LDH microporous materials,
high expansions of the LDH sheets are needed, so pillaring of LDHs by silicate isopolyanions
has been investigated.
Intercalation of Silicate Species in [Zn-Cr] and [Zn-Al] LDH45
Intercalation of silicate species in [Zn-Cr] and [Zn-Al] compounds has been performed
either by anion exchange reactions or by coprecipitation. Such reactions occur provided the pH
of the solution is greater than 9.0, value above which silicates are soluble; otherwise, mixtures
of amorphous silica and metallic hydroxides, far from the LDH chemical composition, are
obtained. PXRD patterns of such phases are related to typical LDH diffractograms (Figure 16).
According to the method of preparation, either a phase with a low interlayer spacing (typically
7.7 Å) or a phase with a higher d value (about 12.0 Å) are prepared. For the [Zn-Cr-SiO4]
system, a unique 11.84 Å layer to layer distance LDH phase is observed, while for the
[Zn-Al-SiO4] system, depending on both the method of preparation and the pH of synthesis,
LDH with two different interlayer spacings, 12.45 Å and 7.65 Å, coexist in variable proportions.
An analogous 12 Å LDH phase had been reported by Schutz et al.46 for the chemical
composition [Mg3Al(OH)8]+[HSi2O5]-.
Figure 16.-PXRD of 0.34[Zn-Cr-SO4] and 0.25[Zn-Al-SO4] prepared by exchange reaction of chloride phases
at pH=12.0. Reprinted from C. Forano, A. De Roy, D. Depège, M. Khaldi, F. Z. El Métoui and J. P. Besse,
Post-synthesis modification of layered double hydroxides, in Synthesis of Porous Materials. Zeolites, Clays,
and Nanostructures, edited by M. L. Occelli and H. Kessler (Marcel Dekker, Inc., New York 1996), pp.
607-625.
Cell parameter refinement for 0.34[Zn-Cr- SiO4]11.84 is obtained in the typical hexagonal 3R
lattice mode as for [Zn-Cr-Cl]. Additional lines on the diffractogram of the 0.25[Zn-Al-SiO4]12.45
phase are explained as arising from a superstructural arrangement of the silicate species in the
LDH interlamellar domains. Then, the X Ray pattern can be indexed in the 1H stacking
hexagonal mode with a unit cell period of a=a0 √3 and c=d.
1
H, 29Si and 27Al solid state NMR experiments have been carried out in addition to FTIR
analysis to identify the silicate nanostructure in the [Zn-Al] interlayers. The 29Si NMR spectra
of these phases are well resolved into a series of overlapping peaks shifted by values less than 5
ppm (Figure 17). Peaks are pointed at -87, -92 and -96 ppm and -85, -90 and -94 ppm for
respectively exchanged and coprecipitated 0.25[Zn-Al-SiO4] LDHs, respectively.
Figure 17.-29Si CP-MAS NMR of 0.25[Zn-Al-SO4] prepared by anionic exchange, and 1H MAS-NMR of
[Zn-Al-SiO4] prepared by coprecipitation at pH=9.0. Reprinted from C. Forano, A. De Roy, D. Depège, M.
Khaldi, F. Z. El Métoui and J. P. Besse, Post-synthesis modification of layered double hydroxides, in Synthesis
of Porous Materials. Zeolites, Clays, and Nanostructures, edited by M. L. Occelli and H. Kessler (Marcel
Dekker, Inc., New York 1996), pp. 607-625.
These NMR chemical shift values are similar to those of 29Si in phyllosilicate minerals,47,48
where (SiO4) polyhedra polymerize by corner sharing into hexagonal layers which condense
onto brucite-like or gibbsite-like octahedral layers in a 1:1 or 2:1 manner. We can conclude that
a similar layered polymerization of SiO44- has occurred in these phases in which the silicon
environment is either of the type Si(OSi)3-y(OM)y(OH) or Si(OSi) 3-y(OM)y(OM') (with
typically M=Al and M' in octahedral site).
Structural and chemical analogy between [Zn-Al-SiO4] and [Zn-Cr-SiO4] let us assume
that polymerisation of tetrahedral silicate layers also occurs in [Zn-Cr-SiO4].
FTIR spectra are very useful in identifying the basal (SiO4) polyhedra condensed unit and
the tetrahedra mode of linkage of SiO4 units. In addition to the typical vibration bands of the
LDH framework and SiO4 units, the occurrence of a band at about 1200 cm-1 is characteristic of
the 180° Si-O-Si stretching vibration found in an inverted connecting frame between two liked
SiO4 tetrahedral groups.47 This band is observed for the [Zn-Cr-SiO4] LDH, but it never
appears for [Zn-Al-SiO4], indicative of a different mode of silicate intralayer condensation
(Figure 18).
However, the interlayering of silicate sheets between metallic hydroxylated layers cannot
occur without fitting a constrained chemical composition. Chemical analysis data for
[Zn-Cr-SiO4] is in agreement with the ideal chemical composition [Zn2Cr(OH)6]+[HSi2O5]- for
which both layers display identical charge density.
For higher divalent to trivalent metal ratio in LDH, such a charge balancing constraint must
force a transfer of excess positive charge from the octahedral to the tetrahedral layers. Indeed,
the diffusion of Al3+ ions from the brucite layers to the silicate layers is confirmed by 27Al NMR.
Both tetrahedral (δ = +55 ppm) and octahedral (δ = +12 ppm) environments for Al3+ are
identified in the NMR spectra. This Al3+ transfer creates vacancies in the brucite layer.
Figure 18.-The two condensation modes of SiO4 units in [Zn-Al-SiO4] (left), and [Zn-Cr-SiO4] (right).
Pillaring of Silicate Sheets on Double Hydroxides Layers45
[Zn-Cr-SiO4] compound
Under moderate calcination (t < 150 °C), it is observed a strong interlayer spacing
contraction (≈ 4.20 Å) of the [Zn-Cr-SiO4] phase, as shown in Figure 19. Such a strong
variation indicates an important structural change of the interlamellar domain which occurs
simultaneously with the main water loss observed on the TGA curve.
Figure 19.-Change in the d spacings for [Zn-Cr-Cl] and [Zn-Cr-SiO4] LDH vs. The calcination temperature.
Reprinted from C. Forano, A. De Roy, D. Depège, M. Khaldi, F. Z. El Métoui and J. P. Besse, Post-synthesis
modification of layered double hydroxides, in Synthesis of Porous Materials. Zeolites, Clays, and
Nanostructures, edited by M. L. Occelli and H. Kessler (Marcel Dekker, Inc., New York 1996), pp. 607-625.
Short basal spacings of 7.65 Å cannot account for free silicate layers in interlayer domains,
but must arise from a condensation process onto brucite-like layers which leads to the
formation of grafted tetrahedral-octahedral layers (Figure 20). This condensation is rendered
possible by compatible hexagonal symmetry of the two layers which possess condensable OH
groups, and by the charge density of the layers which allow a packing based on a Metal/Si ratio
equal to 3/2.
Figure 20.-Hexagonal symmetry retention under brucite. Reprinted from D. Depège, F.-Z. El Metoui, C.
Forano, A. De Roy, J. Dupuis and J.-P. Besse, Polymerization of silicates in layered double hydroxides, Chem.
Mater., 8 (1996) 952, © 1996, with permission from the American Chemical Society.
Removal of intrinsic water molecules and OH condensation are confirmed by a strong

irreversible decrease in the νO-H vibration band intensity in the FTIR spectra (Figure 21). The
thermal grafting process involves a deep change in the environments of both SiO4 units and
intralayer metallic cations, leading to a shift of the SiO4 stretching bands toward higher
energies (from 1000 cm-1 to 1100 cm-1) and the disappearance of the two typical lattice bands of
the brucite layer (520 cm-1 and 585 cm-1).
Figure 21.-FTIR spectra of [Zn-Cr-Cl] and [Zn-Cr-SiO4] LDH calcined at various temperatures. Reprinted
from C. Forano, A. De Roy, D. Depège, M. Khaldi, F. Z. El Métoui and J. P. Besse, Post-synthesis modification
of layered double hydroxides, in Synthesis of Porous Materials. Zeolites, Clays, and Nanostructures, edited by
M. L. Occelli and H. Kessler (Marcel Dekker, Inc., New York 1996), pp. 607-625.
All these results indicate that the SiO4 units polymerize in the LDH interlamellar domains
as inverted tetrahedral layers and that under mild calcination these layers undergo a uniform
grafting on the LDH brucite layers resulting in new three-dimensional structures ideally
represented in Figure 22.
[Zn-Al-SiO4] compound
For the [Zn-Al-SiO4] compounds, no change in the interlayer spacing is observed under
calcination, both 12.45 Å and 7.65 Å expanded lamellar phases remaining non contracted. No
major dehydroxylation is observed in the thermograms and the grafting process of silicate
layers onto octahedral double hydroxide layers has already occurred during the preparation,
probably induced by the transfer of part of Al3+ to the tetrahedral layers. Moreover, elemental
chemical analysis indicates an overall metal cation to silicon ratio not far from 4:1, which
would correspond to a pure nanocomposite phase with one tetrahedral layer for two octahedral
layers. Assumptions made only on interlayer distances can be proposed.
Figure 22.-Structural model for [Zn-Cr-SiO4], (a) before grafting, and (b) after grafting. Reprinted from D.
Depège, F.-Z. El Metoui, C. Forano, A. De Roy, J. Dupuis and J.-P. Besse, Polymerization of silicates in layered
double hydroxides, Chem. Mater., 8 (1996) 952, © 1996, with permission from the American Chemical
Society.
Consequently, the new lamellar structure with a 12.45 Å basal spacing should result from
an interstratification of brucite layers and 1:1 kaolinite like layers (Figure 23). An analogous
behaviour is observed in chlorite, described as an interstratified mica/brucite mineral. The 7.65
Å phase would be a simple tetrahedral/octahedral layers condensation.
Figure 23.-New interlayered LDH-silicate phases. Reprinted from D. Depège, F.-Z. El Metoui, C. Forano, A.
De Roy, J. Dupuis and J.-P. Besse, Polymerization of silicates in layered double hydroxides, Chem. Mater., 8
(1996) 952, © 1996, with permission from the American Chemical Society.
These interesting results evidence that the LDH interlayer domains can act as nanoreactors
for the polymerization of inorganic oxo-anions. Formation of tetrahedral silicate sheets via the
polymerization of SiO4 polyhedra results in new interstratified phases, never prepared so far,
which easily undergo layer to layer condensation reactions, resulting in
clay-mineral-structure-like compounds. This appears as a promising synthetic approach to
prepare, via a "chimie douce" route, new synthetic clays with tuneable metallic cations
composition. Expected new structural and chemical properties would result in interesting
catalytic applications. Coating of a silica crystallite support by LDH monolayers should
normally be obtained similarly, constituting a suitable way to obtain nanocomposite materials
based on LDH with improved surface properties.
Hybrid LDHs
LDHs intercalating organic anions are prepared by anionic exchange or by direct synthesis.
In this particular case an hybrid stacking of inorganic-organic layers is obtained. For organic
molecules with one anionic function, such as alkyl sulphates or sulphonates, or with aromatic
rings (naphthalene or anthraquinone sulfonates), hydrophobic double layers are obtained.
In-between these organic domains neutral organic species such as alcohols may be intercalated,
giving rise to a subsequent interlamellar swelling.48-52
With one anionic function at each end of an organic molecule (e. g., dicarboxylates such as
succinate, adipate, sebacate), the interlamellar anion acts as a pillar and the observed evolution
of basal spacings for a series of different anions is in good agreement with the calculated values.
This pillaring effect is also observed with macrocyclic molecules such as
para-tetra-carboxylate-phenylporphyrins49 (p-TCPP) with a 22.5 Å basal spacing as shown in
Figure 24; for the ortho-subtituted molecule (o-TCPP), the basal spacing is reduced to 18.5 Å
and a different layout is suggested.
Figure 24.-Two different layouts for para- and ortho-tetracarboxylate-phenylporphyrins in [Zn-Al] LDHs.
Reprinted from S. Bonnet, C. Forano, A. De Roy, J. P. Besse, P. Maillar and M. Momenteau, Synthesis of
hybrid organo-mineral materials: Anionic tetraphenylporphyrins in layered double hydroxides, Chem. Mater.,
8 (1996) 1962, © 1996, with permission from the American Chemical Society.
Such hybrid materials are very promising for applications such as:
- nanoscale reactors with stereoselective reactivity,

- substrates for catalytically active species and electro-active molecules,
- templates for interlamellar bidimensional polymerization.
A new challenge with hybrid LDHs is to graft the organic molecules onto the brucite-like
layer by substitution of hydroxyl groups by the anionic function or by condensation with other
functions. A model for such novel phases is, for example, the structure of the layered copper
hydroxy-acetate.
Calcination and reconstruction
For most of LDHs, during progressive calcination, surface water molecules are first lost,
then interlamellar water molecules and finally, roughly in the 200-350°C temperature range,
water corresponding to the dehydroxylation of the main layers, leading to the collapse of the
structure. For some hybrid LDHs, this step takes place before the pyrolysis of organic species,
giving an hybrid layered compound with amorphous inorganic oxide layers.
Depending on the nature of the interlamellar species, they can definitively remain
(phosphates or oxo-metalates), or be removed at more or less high temperatures (sulphate or
chloride), or lost at relatively low temperature, during the dehydroxylation step, such as
carbonates.
After dehydroxylation quasi-amorphous mixed oxides are obtained, which crystallize
progressively at higher temperatures generally as a MIIMIII2O4 spinel-like phase and the
divalent metal oxide. The ill-organized mixed oxides display generally three broad diffraction
maxima corresponding to the future strongest lines of the spinel-like phase; they are therefore
called pre-spinel oxides and it is not impossible that the transformation from the layered
structure to this oxide phase could be topotactic. These mixed oxides display generally a
relatively high specific surface (up to 150 m2g-1) compared to the as-prepared LDHs (≈ 15
m2g-1). Higher specific surfaces (250 m2g-1) can be obtained by thermal treatment of LDHs
intercalating anionic complexes or organic molecules.
After moderate calcination to pre-spinel oxide, a further step is the reconstruction of a LDH
phase in a solution containing a new anion to be intercalated. By this method, polyoxometalates
could be intercalated.52 Some authors postulate a “memory-effect” of the previous structure,
but this does not seem to be absolutely needed, since a LDH phase could be prepared from a
mixture of divalent and trivalent metal oxides. The reconstruction process can also be
performed in air, which supply water molecules and carbonates; in this case, the same anion
being re-intercalated, the only interest is to modify the textural properties of the primitive LDH.
The textural properties are also modified by reconstruction in solvents other than water, thus
evidencing a template effect of the solvent on the spatial organization of the regenerated
microcrystallites giving rise to meso-scale porosity.53
Redox modifications
We only give here a few examples.

LDHs can be involved in redox reactions by means of electroactive interlamellar species;
electronic exchanges with adequate metallic cations could also occur.54
The optimisation of Cd-Ni batteries is of major industrial importance. LDH phases
appearing during their cycling, the efficiency could be optimised by the use of materials
containing additional metals, for example [Ni-Co,Al-CO3] phases.55
LDHs can also be precursors for divided oxides and metals. For example, nickel oxide and
the spinel-like phase are obtained by calcination of [Ni-Cr-CO3]. By reduction under hydrogen
or in ethylene-glycol, it is possible to prepare mixed metallic nickel and chromium (III) oxide
as submicronic particles.56
CrIII-containing LDHs give rise to the formation of chromates by moderate heating,
generally in the 200-350°C range, but we observed oxidation to CrVI from temperatures as low
as 100°C in [Mg-Cr-CO3].57
The palladium chloride square planar complex (PdCl4)2- could be intercalated in a [Zn-Al]
matrix. Depending on the solvent (water or ethanol) nanoscale particles of metallic palladium
could be obtained as a result of a slow hydrolysis process.58
Delamination of LDH by use of surfactants
Delamination of the LDH structure intercalated with surfactants was realized by dispersion
in butanol ; translucent colloidal solution are stable for at least 8 months.59
Delamination process example
Dispersion of (DS)-Zn2Al, (Zn2Al(OH)6)(C12H25SO4·nH2O), in methanol, ethanol,

propanol or hexane under reflux conditions yields unstable colloidal suspensions, whereas
higher alcohols, such as pentanol and hexanol, give rise to stable translucent solutions. The
optimal time for completion of the delamination process depends on the nature of the LDH
material. Twelve hours reaction was required for complete delamination of Zn2Al.
Before any treatment, the samples were dried at room temperature. It is well known that the
water content has an important effect on the particle texture.60 Since the water content may also
influence the delamination process (vide infra), (DS)-Zn2Al was dried under vacuum overnight.
This treatment did not change the X-ray diffraction pattern of the material. After refluxing in
BuOH, the resulting solution was cloudy/milky, indicating that the solid was mostly highly
dispersed but had not been exfoliated. After one hour, a white powder settled to the bottom of
the vessel and this material was dried and analyzed. The phase exhibits a strong contraction of
the interlayered domain from 25.2 to 16.8 Å. This indicates a high degree of interdigitation of
the alkyl chains. Considering the thickness of the brucite-liked layer (vide supra), the surfactant
tails are tilted ca. 57° from the perpendicular axis of the inorganic layers (along c). Also, some
of the surfactant anions were removed from the interlayer space as indicated by TG analysis
(not shown). The final weight loss step, attributed to the decomposition of SO4 to SO2,
remained quantitatively high, showing that SO42- anions remained in the structure, balancing
the layer charge. Figure 25 shows the delamination and restacking of ZnAl LDH.
Thus, it appears that vacuum treatment impedes delamination of Zn2Al. The water content
plays a major role in the delamination process and we believe that the replacement of the water
molecules by the solvent molecules is the key process in exfoliation. The intercrystalline water
could also influence the delamination process. Several LDH samples were kept for three to four
weeks at various humidities (20, 40, 60 and 80 % R.H.). Comparatively, LDHs kept at low RH
did exfoliate, although at an R.H. as high as 80 % a cloudy BuOH suspension remained. In
order to prevent particle aggregation due to the effect of water, freshly prepared (DS)-LDH
materials were washed with ethanol, then butanol and directly suspended in BuOH for
delamination. The material exfoliated, as evidenced by the formation of a translucent solution.
The preparation of colloidal solutions of LDH appears to be of substantial importance for
the development of novel chemistry of the LDHs. It is now possible to develop the chemistry of
LDHs in non-aqueous conditions, e.g., for electrochemistry applications.
Ultra thin films based on LDHs can now easily be prepared by a soft chemistry route.
Preparations of novel based - LDH materials with improved chemical or porosity properties are
now envisaged through interstratified LDH/LDH, LDH/clay, LDH/polymer or nanoporous
LDH/Si or materials.61,62
The preparation of LDH/polymer nanocomposite by delamination and reconstruction is a
novel way developed in our laboratory. Nanocomposites LDH/polymer are particularly of
interest because the electrical, mechanical, optical and other physicochemical properties of
these materials are often favorably modified by the nanometer level of interphasic interactions.
Figure 25.-Pathways for LDH synthesis. DS exchange, delamination in BuOH and recovery by. drying. The
morphology of the samples is indicated by SEM and TEM pictures. Reprinted from F. Leroux, M.
Adachi-Pagano, M. Intissar, S. Chauvière, C. Forano and J.-P. Besse, Delamination and restacking of layered
double hydroxides, J. Mater. Chem., 11 (2001) 105, © 2001, with permission from the Royal Society of
Chemistry.
REFERENCES
[1] K.J. Martin and T.J. Pinnavaia, J. Am. Chem. Soc. 108 (1986) 541.
[2] N.S. Kurnakov and V.V. Chernykh, Zapiski Rossiysk. Mineral. 55 (1926) 118.
[3] W. Feitknecht and M. Gerber, Helv. Chim. Acta 25 (1942) 106.
[4] A. de Roy, C. Forano, K. El Malki and J.P. Besse, in Expanded Clays and Other
Microporous Solids, edited by M.L. Occelli and H.E. Robson (Van Nostrand Reinhold,
New York 1992), vol. II, Chap. 7 pp. 108-169.
[5] F. Trifirò and A. Vaccari. Comprehensive Supramolecular Chemistry, Vol. 7 Pergamon,
Oxford, 1996, pp. 251-291.
[6] V. Rives and M.A. Ulibarri, Coordination Chem. Rev. 181 (1999) 61.
[7] R. Allman, Acta Cryst. B24 (1968) 972.
[8] A. Ennadi, A. Legrouri, A. de Roy and J.P. Besse, J. Solid State Chem. 152 (2000) 568;
A. Ennandi, M. Khaldi, A. De Roy and J. P. Besse, Mol. Cryst. Liq. Cryst. 244 (1994)
373.
[9] V.A. Drits, T.N. Sokolova, G.V. Sokolova, and V.I. Cherkashin, Clays Clay Miner. 35
(1987) 401.
[10] R. Schöllhorn, and B. Otto, J. Chem. Soc., Chem. Comm. (1986) 1222.
[11] I. Sissoko, E.T. Iyagba, R. Sahai and P. Biloen, J. Solid State Chem. 60 (1985) 283.
[12] S. Miyata, Clays Clay Miner. 31 (1983) 305.
[13] S. Miyata and T. Kamura, Chem. Lett. (1973) 843.
[14] V. Rives, F.M. Labajos, M.A. Ulibarri and P. Malet, Inorg. Chem. 32 (1993) 5000.
[15] W.T. Reichle, Solid State Ionics 22 (1986) 135.
[16] W.H.R. Shaw and J.J. Bordeaux, J. Am. Chem. Soc. 77 (1955) 4729.
[17] U. Costantino, F. Marmottini, M. Nocchetti and R. Vivani, Eur. J. Inorg. Chem. (1998)
1439.
[18] G. Mascolo and O. Marino, Miner. Mag. 43 (1980) 619.
[19] J.M. Fernández, C. Barriga, M.A. Ulibarri, F.M. Labajos and V. Rives, Chem. Mater. 9
(1997) 312.
[20] R. Allmann and J.P. Jepsen, N. Jhb. Miner. Mh. 12 (1969) 544.; R. Allmann and H.H.
Lohse, N. Jhb. Miner. Mh.(1966) 161.
[21] H.P. Boehm, J. Steinle and C. Wieweger, Angew. Chem. Int. Ed. Engl. 16 (1977) 265.
[22] K. El-Malki, A. de Roy and J.P. Besse, Eur. J. Solid. State Inorg. Chem. 26 (1989) 339.
[23] C. Bigey, C. Depege, A. de Roy and J.P. Besse, J. Phys. IV 7 (1997) 949.
[24] W. Nowacki and J.A. Silverman, Z. Kristallogr. 117 (1962) 238.
[25] J.B. Parise and B.G. Hyde, Acta Cryst. C42 (1986) 1277.
[26] A. Clearfield, Chem. Rev. 88 (1988) 125.
[27] Y. Israeli, C. Taviot-Gueho, J.P. Besse, J.P. Morel and N. Morel-Desrosiers, J. Chem.
Soc. Dalton Trans. 5 (2000) 791.
[28] T. Yamaoka, M. Abe and M. Tsuji, Mater. Res. Bull. 24 (1989) 1183.
[29] Y. Park, K. Kurroda and C. Kato, Chem. Lett. (1989) 2057.
[30] M.A. Drezdzon, Inorg. Chem. 27 (1988) 4628.
[31] M.A. Drezdon, US Patent, 4.774.212 (1988) 14.
[32] F. Malherbe, C. Forano and J.P. Besse, Microporous Mater. 10 (1997) 67.
[33] F. Malherbe, C. Depege, C. Forano, J.P. Besse, M.P. Atkins, B. Sharma and S.R. Wade,
Appl. Clay Sci. 13 (1998) 451.
[34] T. Kwon, G.A. Tsigdinios and T.J. Pinnavaia, J. Am. Chem. Soc. 110 (1988) 3653.
[35] M. Doeuff, T. Kwon and T.J. Pinnavaia, Synthetic Metals 34 (1989) 609.
[36] K. El Malki, Thesis University Blaise Pascal - Clermont-Ferrand, France (1991).
[37] K. El Malki, A. de Roy and J.P. Besse, Nanostructural Mater. 2 (1993) 169.
[38] M. Khaldi, A. de Roy, M. Chaouch and J.P. Besse, J. Solid State Chem. 130 (1997) 66.
[39] C. Depège, L. Bigey, C. Forano, A. de Roy and J.P. Besse, J. Solid State Chem. 126
(1996) 314.
[40] L. Bigey, A. de Roy and J.P. Besse, Mol. Cryst. Liquid Cryst. 311 (1998) 221.
[41] D. Louër, M. Louër and D. Grandjean. Acta Cryst. B29 (1973) 1696.
[42] S. Yamanaka, T. Sako, K. Seti and M. Hattori, Solid State Ionics, Proc. of 8th
Conference on Solid State Ionics, Lake Louise, Canada, Oct. 20-26 (1991).
[43] A. de Roy and C. Forano, unpublished results.
[44] T.J. Pinnavaia. NATO ASI Series, ser. B 172 (1987) 233.
[45] C. Depège, F.Z. El Métoui C. Forano, A. de Roy, J. Dupuis, and J.P. Besse, Chem.
Mater. 8 (1996) 952.
[46] A. Schutz and P. Biloën, J. Solid State Chem. 68 (1987) 360.
[47] R.A. Kinsey, R.J. Kirkpatrick, J. Hower, K.A. Smith and E. Oldfeild, Am. Miner. 70
(1985) 537.
[48] J. Sanz and J.M. Serratosa, J. Am. Chem. Soc. 106 (1984) 4790.
[49] S. Bonnet, C. Forano, A. de Roy, P. Maillard, M. Momenteau and J.P. Besse, Chem.
Mater. 8 (1996) 1962.
[50] V. Prevot, C. Forano, J.P. Besse and F. Abraham, Inorg. Chem. 37 (1998) 4293.
[51] S. Therias, C. Mousty, C. Forano and J.P. Besse, Langmuir 12 (1996) 4914.
[52] U. Costantino, N. Coletti, M. Nocchetti, G.G. Aloisi and F. Eliseï, Langmuir 15 (1999)
4454.
[53] J. Qiu and G. Villemure, J. Electroanal. Chem. 395 (1995) 159.
[54] F. Kooli, C. Depège, A. Ennaqadi, A. de Roy and J.P. Besse, Clays Clay Miner. 45
(1997) 92.
[55] K.S. Han, L. Guerlou-Demourgues and C. Delmas, Solid State Ionics 84 (1996) 227.
[56] K.S. Han, L. Guerlou-Demourgues and C. Delmas, Solid State Ionics 98 (1996) 85.
[57] A. Ennaqadi, M. Khaldi, A. de Roy, C. Forano and J.P. Besse, J. Phys. IV 7 (1997)
1231.
[58] E. López-Salinas and Y. Ono, Microporous Mater. 1 (1993) 33.
[59] M. Adachi-Pagano, C. Forano and J.P. Besse, Chem. Comm. (2000) 91.
[60] S.K. Yun and T.J. Pinnavaia, Chem. Mater. 7 (1995) 348.
[61] O.C. Wilson, T. Olorunyollmi, A. Jaworski, L. Borum, D. Young, A. Siriwat, E.
Dickens, C. Oriakhi and M. Lerner, Appl. Clay Sci. 15 (1999) 265.
[62] F. Leroux, M. Adachi-Pagano, M. Intissar, S. Chauvière, C. Forano and J.P. Besse, J.
Mater. Chem. 11 (2001) 105.
Chapter 2
CRYSTAL STRUCTURE AND X-RAY IDENTIFICATION

OF LAYERED DOUBLE HYDROXIDES
V. A. Drits and A. S. Bookin

Geological Institute of the Russian Academy of Sciences Phyzevsky per.7, 1091017
Moscow, Russia
INTRODUCTION
Natural and synthetic Layered Double Hydroxides (LDHs) belong to anionic clays. Their
structure consists of hydroxyl octahedral layers having a positive charge due to coexisting
heterovalent cations. These brucite-like layers alternate regularly with charge compensating
layers of anions and water molecules that are called interlayers. LDHs are of great academic
and industrial interest owing to their various potential applications. One of the remarkable
features of LDHs is that the interlayer anions are exchangeable, and in addition, can be
exchanged with various organic and inorganic charged compounds. Because of the high
anion-exchange capacity, LDHs can be used as adsorbents for anionic pollutants in aqueous
media. Mixed cation oxides formed after thermal decomposition of LDHs can be used as
catalysts for a wide range of catalytic processes. The interlayer of LDHs can serve as a
two-dimensional matrix for various chemical reactions. Different aspects of potential
applications are considered in details in Part II of this book.
It is well known that many physico-chemical properties of LDHs are predetermined by
their structural and crystal-chemical features. Therefore, a correct interpretation of LDH
properties and their effective application requires a comprehensive study of LDH crystal
structure and chemistry. The family of LDHs is extremely wide and includes hundreds of
members. Several factors determine the structural and chemical diversity of LDHs. One of
these is the extreme compositional variability of octahedral layers that can be represented by a
wide variety of coexisting heterovalent cations. For a given set of cations, LDHs differ in the
proportion of high- and low-charged cations that determine the layer positive charge and
amount of interlayer anions. The interlayer region also can be filled by quite different organic
and inorganic anions. Some species have two or more different anions in their interlayers.
Octahedral cations and interlayer anions can be distributed with long- and short-range
order. Unambiguous determination of cation and anion ordering is a complex problem,
42 V.A. Drits and A.S. Bookin
especially when LDHs consist of fine-dispersed particles. Therefore the presence of cation
ordering is still a matter of discussion. Meanwhile, LDH varieties having the same layer cation
composition but different order-disorder in the cation distribution may have different properties.
Therefore determination of factors that control long- and short-ranged cation ordering as well
as a search for routine diffraction and spectroscopic criteria for experimental identification of
order-disorder in cation distribution are important problems in the crystal chemical
characterization of LDHs.
For long time, the general opinion has been that there are only two possible stacking
sequences of the structural units formed by an octahedral layer and an interlayer leading to two
polytypes. One is a two-layer hexagonal (2H) and the other, a three-layer rhombohedral (3R)
stacking of successive layers. Both polytypes are characterized by the same topology of
interlayers formed by the nearest OH-sheets of the neighboring layers. LDH polytypes,
however, are more diverse, and a polytype cannot be completely described by simply indicating
a number of brucite-like layers in the unit cell. Therefore one of the main problems in the
structural study of LDHs is determination of the actual layer periodicity along the c axis.
Analysis of the experimental XRD patterns published in the literature for natural and
synthetic LDH compounds has shown that the presence of stacking faults is a typical structural
feature of these materials. Unfortunately, in most publications the nature of stacking faults has
not been discussed. At the same time, the presence of stacking faults can change the nature of
layer-interlayer bonding and thus modify LDH properties.
The aim of this chapter is to:
--describe the range of isomorphous cation substitutions admissible in the brucite-like layers
and the resulting changes in the structure;
--provide insight into regularities controlling anion positions in LDH interlayers;
--discuss order-disorder phenomena in both brucite-like layers and interlayers and the
reliability of their determination by experimental data;
--deduce the possible diversity of LDH polytypes;
--formulate diffraction criteria for routine polytype identification;
--discuss the nature of possible stacking faults;
--describe the main structural and crystal chemical features of the most representative natural
and synthetic members of the LDH family.
LAYERS AND INTERLAYERS

Brucite Layer
Figure 1 shows projections of an octahedral layer on the ab and ac planes. In this layer,
each octahedron shares its six edges with those of the nearest six neighboring octahedra. If the
apices and centers of the octahedra are hydroxyl groups and divalent cations, respectively, then
the layer is electroneutral. In particular, a layer in which the octahedral cations are Mg2+, is the
basic structural unit of brucite. The brucite layer, as well as the brucite structure, can be
described in terms of a close packing of anions and cations. As usual for closed-packed crystals,
we shall denote non-equivalent crystallographic sites of OH groups within brucite layers by
capital letters A, B and C, and the cation positions in these layers, by the corresponding
Crystal Structure and X-ray Identification of Layered Double Hydroxides 43
lowercase letters. Let us assume that the lower surface of the brucite layer is a hydroxyl sheet in
which OH groups occupy the A sites, that cations fill in the octahedral b positions, and that the
upper surface is formed by OH groups in the C sites. Such a layer can be written as AbC.
Brucite has a one-layer hexagonal structure which can be described by the stacking sequence
AbCAbC...
In the actual brucite structure, OH groups are shifted along the c axis to decrease the layer
thickness and shared-edge lengths and to increase the layer lateral dimensions. It is common to
say that such a transformation of ideal octahedra into antiprisms provides better screening of
cations and gains in electrostatic interaction. The Mg-OH bond lengths being preserved, the
flattening increases the layer lateral dimensions (Figure 2). In order to estimate this effect, let us
compare some structural parameters of brucite with those to be observed for regular octahedra,
assuming that Mg-OH = 2.102 Å.1 Because the edge length, l0, and thickness, h0, of a regular
octahedron are related to the Me-OH distance, d0, as l0=√ 2d0, and h0=2√2d/√3, the lattice
period and thickness of the idealized brucite layer are a0 = l0 = 2.973 Å and h0 = 2.427 Å,
respectively. In the actual brucite structure, a = 3.142 > a0 and h = 2.112 Å < h0.
X-nH2O
X-nH2O
X-nH2O
Figure 1.-Projection of a brucite-like layer on the ab and ac planes.
The distortion of brucite layers does not change their hexagonal symmetry (a = b = 3.142
Å, γ = 120°, c = 4.766 Å), and the space group of a brucite layer, as well as a brucite structure,
is P 3 m1.1
Figure 2.-Flattering and elongation of an ideal (solid line) to a distorted (dashed line) octahedron. Other
notations are the same as in Fig. 1. Distortions are out of scale.
Brucite-Like Layers
The main crystal chemical peculiarity of these layers is that they have heterovalent cation
composition resulting in a positive layer charge. The cation composition of brucite-like layers
of natural and synthetic LDHs can be represented by various cationic pairs such as Me2+Me3+,
Me+Me3+, Me2+Me4+ with Me+ = Li, Me2+ = Mg2+, Fe2+, Ni2+, Co2+, Zn2+, Mn2+, etc; Me3+ =
Al3+, Ga3+, Fe3+, Co3+, Mn3+, V3+, etc; Me4+ = Mn4+, Ti4+ etc.2-10 Coexistence of three types of
cations present in different proportions in the same layer is an additional factor responsible for
the cation diversity of LDHs.11,12 Most of natural and synthetic LDHs contain di- and trivalent
cations, and the structural formula of the brucite-like layers can be written as
[Me1-x2+Mex3+(OH)2]x+. For natural and synthetic LDHs, the x values vary within a wide
interval. However, there is a certain discrepancy in the determination of the limiting values of
this parameter. For natural Mg,Al-minerals, the upper limit of x is 0.35 and corresponds to
Mg:Al = 2:1.2 The possible minimum x value is not strictly determined and varies within
0.17-0.20 corresponding to the Mg:Al ratio of 4:1 or 5:1.2 A similar range of the limiting x
values is determined for LDHs synthesized from solutions at normal p and T=60°C.13
According to Miyata14 the lowest value of x can be decreased down to 0.1 with Mg:Al = 9:1.
Synthesis of LDHs at high p,T conditions significantly increases the upper limit of x up to 0.6.15
Replacement of Mg for other divalent cations also increases the upper limit of x for natural and
synthetic LDHs. For example, for Cu,Al- and Zn,Al-bearing minerals the x values vary within
0.23-0.62 and 0.38-0.43, respectively.16 Similar values were determined for synthetic LDHs.
For synthetic Mg,Ga-bearing LDHs obtained by the coprecipitation technique, very low
contents of Ga have been obtained. For example, low-charged samples have Mg:Ga = 5:1,4
7.7:1 and 12.9:1.9
The Relationship between x and Layer Cell Parameter a
Most investigations were made on Mg,Al systems with carbonate anions in the interlayers.
Smaller Al for the larger Mg substitution decreases the mean Me-OH distance and the a cell
parameter. The experimental plots of a vs x for Mg,Al, Ni,Al, and Mg,Ga LDHs are given in
Figure 3. For all the systems, there is a range of x where a linearly decrease with x. The slopes
of the linear parts are 0.30, 0.272 and 0.13,9 respectively.
The following calculations help to understand such behaviour.2 As mentioned above, the a
parameter for an idealized octahedral layer is √2dMe-OH, where dMe-OH is the sum of cation rMe2+
and hydroxyl rOH- ionic radii. The mean cation radius, r, is given by
r = (1 - x)rMe2+ + xrMe3+ = rMe2+ - x(rMe2+ - rMe3+)
and the cell parameter a is given by
a = √2(rOH- + r) = √2[rOH- + rMe2+ - x(rMe2+ - rMe3+)]
The negative slope of a with x is
∆a/∆x = - √2(rMe2+ - rMe3+)

With the Shannon17 ionic radii, rMg2+ = 0.720 Å, rAl3+oct = 0.535 Å, rNi2+ = 0.690 Å and rGa3+
= 0.620 Å, the calculated values of ∆a/∆x are 0.26, 0.22 and 0.14 for the Mg,Al, Ni,Al and
Mg,Ga systems, respectively. Similar effects are observed for other Me2+,Me3+ systems, for
which cation radii of Me3+ are smaller than that of Me2+. Similar radii of Ni and Mg account for
similar slopes of the lines for the Mg,Al and Ni,Al systems, whereas the lower slope for the
Mg,Ga system is due to close cation radii of Ga and Mg.
Brindley and Kikkawa2 noted that the linear dependence between a and x, extrapolated to x
= 0, i.e., zero Al substitution, gave extrapolated a values of 3.144 Å and 3.110 Å for the Mg,Al
and Ni,Al systems, respectively. The a parameter of brucite, 3.142 Å, agrees very well with the
extrapolated value for the Mg,Al system. The extrapolated value for the Ni,Al system agrees
less with the value 3.126 Å18 for Ni(OH)2. Note, that in the Mg,Ga system9 the agreement
between the brucite and the extrapolated to zero Ga (a = 3.132 Å1) cell parameters is not so
good also. Deviations may take place mainly because the extrapolated values strongly depend
on the small changes in the slope of the observed lines or because the geometric approach is
valid only within a certain interval of substitutions. Beyond this interval linear relationship
between x and a no longer works. For the Mg,Al LDHs synthesized at high p,T15 the linear
dependence between x and a is valid only for x ≤ 0.33 (Mg:Al = 2:1), whereas for x > 0.33, the
a value does not depend on x and equals 3.042 Å (Figure 3). Therefore, if the x value
determined for a synthetic or natural Mg,Al sample from the linear relationship is equal to
0.33-0.35, the actual content of Al may be higher than the calculated one.
Order-disorder in Isomorphous Cation Distribution
Distribution of heterovalent cations in LDH octahedral layers may be either completely

random, or ordered, or it can be characterized by intermediate order. Theoretically, long-range
cation ordering should depend on the Me2+:Me3+ ratios. According to Brindley and Kikkawa,2
the Me3+ octahedral sites should be as far apart from each other as possible in order to minimize
mutual cation repulsion and, first of all, to avoid edge-shared Me3+-Me3+ cationic pairs. To
satisfy this condition for Me2+:Me3+ = 2:1, the heterovalent cations have to be distributed in
such a way that each Me3+ position is surrounded by six Me2+ positions, and each Me2+ site has
three Me3+ and three Me2+ sites as the nearest neighbors. Figure 4a shows that the hexagonal a
parameter of the supercell is given by a=√ 3a0, where a0 is the parameter of the sub-cell, which
makes no differentiation between the cations (Figure 4b). This distribution corresponds to the
maximum possible degree of order for the given Me2+:Me3+ ratio.
1
Our estimate, Figure 3.
Figure 3.-Cell parameter, a, vs. Me3+ content, x.
The next strictly ordered distribution of Me2+ and Me3+ may occur for Me2+:Me3+ = 3:1. In
this case, the supercell parameter a = 2a0, and each two nearest Me2+ cations are separated by a
Me3+ cation (Figure 4c). Other different supercells may also occur for other Me2+:Me3+ ratios:
in the general case for a sample with Me2+:Me3+ = Q:1, the layer supercell parameter is given by
a = a0√(Q+1). But it is precarious to infer the Me2+:Me3+ ratio from the cell parameter. For
example, structures with both 7:1 and 5:3 composition can have the same cell with a = a0 √8.
Composition of LDHs Interlayers
The interlayers of LDH structures consist of various anions and water molecules. The
anions can be represented either by single anions like Cl-, (OH)-, or triangular planar groups
like CO32-, NO3-, or three-dimensional tetrahedral (SO42-, CrO42-) or octahedral [Fe(CN)6]4-
groups, or two-dimensional tetrahedral silicate sheets.2,6,10,19-25 Natural LDHs usually contain
CO32- and, less often, Cl- and SO42 − .2,6,26-30 Interlayers of some natural and synthetic LDHs,
along with anions and water molecules, contain various cations (Ca, Na, Mg, etc).
Figure 4.-Unit cells in ordered LDHs; (a) a = a0; (b) a = √3a0; (c) a = 2a0.
In contrast to cationic silicate clays, LDHs having high surface charge density preserve
their high ability to anion-exchange. Therefore, these compounds can be intercalated with
various organic and inorganic anions,23,31,32 which act as pillars between brucite-like layers.
Recently Rives and Ulibarri33 reviewed an extremely large family of synthetic LDHs
intercalated with complex metal coordination anions and oxometalates.
Structural Formulae, Unit Cell Parameters and Nomenclature of Natural

LDHs
Structural formulae for most LDHs can be expressed as [Me1-x2+Mex3+(OH)2][Ax/mm-nH2O],

where Am- is the m-valent anion.
For natural LDHs the chemical composition is the main fundamental characteristic feature
to distinguish individual minerals and to name them. At present, the following major cation
compositions have been recognized among LDHs minerals: Mg3Al (hydrotalcite-manasseite),
Mg3Fe (pyroaurite-sjögrenite), Ni5.5Fe3+2.5(honessite-reevesite), Ni3Al (takovite), Cu2Al
(woodwardite), Mg3Cr3+ (stichtite), etc.
Owing to the anion-exchange ability, the same LDH mineral may contain different anions
in its interlayers. Different effective diameters of anions determine different thickness of the
interlayers. The combined thickness of the brucite-like layer and the neighboring interlayer is
another important structural feature of LDHs. This parameter, c0, determines a minimum repeat
distance along the c axis. For example, CO3-bearing LDHs have c0 = 7.5-7.8 Å, whereas among
SO4-bearing LDHs two varieties occur with c0 of 8.8-8.9 Å and 10.8-11.2 Å, respectively. The
c0 values of Cl-bearing LDHs are 7.7-8.0 Å.
Table 1 contains the list of names, structural formulae and unit cell parameters for LDH
minerals described in the literature. One may note that the system of nomenclature for LDH
minerals cannot be regarded as satisfactory. Rationalizations of the nomenclature were
discussed in reference 6. The authors suggested the following limitations on naming new
member of this group:
-different polytype modifications as well as varieties of the same polytype that display
different layer superperiodicity should not be given new names;
-varieties that have the same sequence of brucite-like layers and interlayers but differ in the
composition of the interlayers should also not be given new mineral names if the LDH
varieties posses anion-exchange properties;
-varieties differing in the amount of charge on the brucite-like layer and the value of c0 if
latter depends on humidity and/or temperature, should not be given new mineral names.
Table 1. Names, compositions and cell parameters of natural species of LDHs.
Name and chemical composition of mineral Unit-cell parameters (Å) References

a c
Hydrotalcite 3.054 3c0 = 22.81 34
[Mg6Al2(OH)16][(CO3) 4H2O]
Manasseite 3.10 2c0 = 15.6 35
[Mg6Al2(OH)16][(CO3) 4H2O]
Quintinite 2H 3.042 2c0 =15.2 6
[Mg4Al2(OH)12][(CO3) 3H2O]
Quintinite 2H 2√3a0=10.55 2c0 =15.2 3
6
[Mg4Al2(OH)12][(CO3) 3H2O]
Mixed-layer quantinite-like mineral √3a0=5.27 2c0 =15.2 3
7
[Mg4Al2(OH)12][(CO3) 3H2O]
Quintinite 3T 2 √3 a 0 = 3c0 =22.71 36
[Mg4Al2(OH)12][(CO3) 3H2O]
10.558
Pyroaurite 3.109 3c0 =23.41 3
8
[Mg6Fe3+2(OH)16][(CO3) 4.5H2O]
Pyroaurite 3.10 3c0 =23.04 3
9
Mg4Ni2+2Fe3+2(OH)16 ][(CO3) 4H2O
Sjögrenite 3.113 2c0=15.61 19
[Mg6Fe3+2(OH)16][(CO3) 4.5H2O]
Charmarite 2H 2√3a0 =10.985 2c0 = 15.0 36
[Mn4Al2(OH)12][(CO3) 3H2O]
Charmarite 3T 2√3a0 = 10.985 3c0 = 22.65 36
[Mn4Al2(OH)12][(CO3) 3H2O]
Reevesite 3.1 3c0 = 23.4 4
0
[Ni6Fe3+2(OH)16][CO3 · 4H2O]
Stichtite 3.10 3c0 = 23.4 35
[Mg6Cr2(OH)16][(CO3) ·4H2O]
Stichtite 2a0=6.169 6c0 = 46.66 4
1
[Mg5.94Ca0.01)5.95(Cr1. 29Al0. 5 1Fe3+ 0.25)2 .05(OH)15.1]
[(CO3)1.47·3.7H2O]
Stichtite 3.085 3c0 = 23.4 4
2
[Mg5.94Ca0.01)5.95(Cr1. 29Al0. 5 1Fe3+ 0.25)2 .05(OH)15.1]
[(CO3)1.47·3.7H2O]
Barbertonite 3.10 2c0 = 15.6 4
3
[Mg6Cr2(OH)16][(CO3) 4H2O]
Coalingite 3.12 3c0 = 37.5 4
4
[Mg10Fe3+2(OH)24][(CO3) 2H2O]
Coalingite-K 3.13 17.2 44
[Mg16Fe3+2(OH)36][(CO3) 2H2O]
Desautelsite 3.114 3c0 = 23.39 4
5
[Mg6Mn3+2(OH)16][(CO3) 4H2O]
Reevesite 3.081 3c0 = 23.05 27
[Ni6Fe3+2(OH)16[CO3 4H2O]
Table 1. Names, compositions and cell parameters of natural species of LDHs. (cont’d)
Name and chemical composition of mineral Unit-cell parameters (Å) References

a c
Takovite 3.025 3c0 = 22.59 4
6
[Ni6Al2(OH)16][(CO3,OH) ·4H2O]
Takovite 3.018 3c0 = 22.59 4
7
[Ni4.94Mg0.10Ca0.02Fe3+0.13Al2.81(OH)14.42]
[(CO3)2.27·5.42H2O]
SO4-Hydrotalcite 3.04 3c0 = 26.55 4
8
[Mg4Al2(OH)12][(SO4) 3H2O
11-Å phase √3a0 =5.28 11.16 6
[(Mg3.96Al1.98Fe3+0.06)(OH)12][Na0.56(SO4)1.30
7.3H2O]
Green rust 3.174 10.94 4
9
[Fe22+Fe3+(OH)6][(SO4)0.5 3H2O]
Wermlandite 3a0 =9.303 2c0 = 22.57 11
[Mg7(Al0.57Fe3+0.43)2(OH)18][(Ca0.6Mg0.4)(SO4)2
12H2O]
SO4-exchanged takovite 3.024 3c0 = 26.73 27
[Ni6Al2(OH)16][(SO4) nH2O] (30% RH)
SO4-exchanged takovite 3.024 3c0 = 32.46 27
[Ni6Al2(OH)16][(SO4) nH2O (100% RH)
Honessite 3.083 3c0 = 26.71 27
[(Ni5.55Mg0.10Fe3+2.35)(OH)16][(SO4)1.18·nH2O]
Hydrohonessite 3.09 10.80 28
[Ni2+5.43Fe3+2.57(OH)16][(SO4)1.28 0.98NiSO4
6.95H2O]
Hydrohonessite 3.087 3c0= 33.4 27
[Ni2+5.43Fe3+2.57(OH)16][(SO4)1.28
0.98NiSO46.95H2O]
Shigaite 3a0 =9.512 3c0= 33.074 29
[(Mn2Al1)(OH)6][(1/2 SO4) nH2O]
Woodwardite 3.066 10.9 30
[Cu4Al2(OH)12][SO4 (2-4)H2O]
Glaucocerinite 3.07 10.88 5
0
[(Cu,Zn)5Al3(OH)16][SO4 nH2O]
Iowaite 3.119 3c0 = 24.25 5
1
[(MgFe3+1.32)(OH)12][Cl1.22·1.95H2O]
Meixnerite 3.046 3c0 = 22.92 22
[Mg6Al2(OH)16][(OH)2 ·4H2O]
Motukoreaite 3.062 3c0 = 33.51 5
2
[Mg1.82Mn0.03Zn0.02Al1.12(OH)5.15]
[(Na0.07K0.01)(CO3)0.63(SO4)0.40 2.74H2O]
16.5-Å phase 3.042 c0 =16.50 6
[Mg8Al4(OH)24][(SO4)1(CO3)1 6H2O]
18.5-Å phase 3.046 3c0 = 55.62 6
[Mg8Al4(OH)24][(SO4)1(CO3)1 13 H2O]
Mountkeithite 3a0 =10.698 2c0 = 22.50 5
3
[(Mg8.15Ni0.85Cu0.02)(Fe3+1.31Cr1.02Al0.65)(OH)24]
[(CO3)1.11(SO4)0.38(Mg1.76Ni0.18)(SO4)1.94(H2O)9.39]
Carrboydite 3a0 =9.141 10.34 5
4
[(Ni,Cu)6.90Al4.48(OH)21. 69][(SO4,CO3)2. 78 3.67H2O]
Chlormagaluminite √3a0 =5.29 2c0 =15.46 26
[(Mg3.55Fe2+0.27Na0.05)(Al1.93Fe3+0.07Ti0.01)(OH)12]
[Cl1.48(1/2CO3)0.24) H2O]
If these restrictions were accepted the only criterion remaining for assigning new mineral
names within the group of LDH minerals was the chemical composition of the brucite-like
layer. It might be used one name for the entire compositional series (Me2+1-xMe3+x)(OH)2. This
name would be modified by symbols to indicate the interlayer composition and polytype
modification. However, because of historical reasons, in the present nomenclature some
minerals having the same chemical composition but different names because their structures
correspond to different polytypes (hydrotalcite-manasseite, pyroaurite-sjögrenite, etc.). Other
minerals having almost identical the layer cation composition differ either by type of interlayer
anion (CO3-bearing reevesite vs. SO4-bearing honessite) or by different degree of hydration of
interlayers containing the same anion type (8.84 Å-honessite vs. 11.0 Å-hydrohonessite).
Nevertheless, the conventional names of LDH minerals are used in this chapter.
EXPERIMENTAL METHODS: A BRIEF OUTLINE

One of the main tools for structural and crystal-chemical study of LDHs is X-ray
diffraction (XRD). Diffraction methods allow us to determine unit-cell parameters and the
mutual atomic arrangement within the unit cell. These methods are also used to study the nature
of various structural defects, their contents and distribution. Most of the natural and synthetic
LDHs are crystallized in the form of fine dispersed crystallites. Therefore powder X-ray
diffraction methods are applied for their identification and structural study.55
Determination of Unit-cell Parameters

The identification of an LDH structure is based on the analysis of the positions and
intensities of the peaks observed in the XRD patterns. The first step in the analysis is to
determine unit-cell parameters. One of the key structural parameters of LDHs is the basal
repeat distance, c0, normal to the (00l) plane, which equals the thickness of the brucite-like
layer plus interlayer. To determine this parameter, it is useful to record an XRD pattern from an
oriented specimen. The plate morphology of LDHs particles provides their preferable
orientation on the sample holder surface. Oriented samples are widely used for the study of
cationic clays, and different techniques for preparation of oriented samples are described in
reference 56. In particular, such specimens may be prepared by sedimentation of a dispersed
suspension of clay-sized material. Such specimens should be smooth, flat, thick and dense
enough. XRD patterns of oriented LDH samples contain the so-called basal reflections having
00l indices. Positions of these reflections or, to be more precise, their spacings, d(00l), are
related with c0 as c0 = nd(00l) (l, n = integers). The relationship between l and n depends on the
number of the brucite-like layers, m, per unit cell. For a one-layer LDHs polytype, l = n, the
experimental c0 is the unit cell c parameter and its value equals the spacing of the first
low-angle basal reflection. For a m-layer polytype, the actual period c = mc0 and the first low
angle reflection has 00m indices, although its spacing equals to c0. The rational relationship
between c0 and basal reflection spacings reflects the perfect layer periodicity along the c axis.
The rational positions of basal reflections, however, may be destroyed because of
interstratification effects, small thickness of coherent scattering domains (CSD) or other
imperfections.57
The interstratification in LDHs can results from coexistence, within the crystal, of
interlayers having different thicknesses and distributed with different degrees of order-disorder.
Different interlayer thicknesses may be due either to the presence of different anions and
amount of water molecules in the interlayers or to alternation of anion-bearing and anion-free
interlayers, when brucite-like layers are held together by H-bonds. Irregular interstratification
of interlayers of the latter type was found in K-caolingite.44
Thin CSDs lead to a displacement of the first low-angle basal reflection from its Bragg's
position to a lower diffraction angle. Because of this effect, the set of the basal reflections
becomes partially irrational; the measured spacing of the first reflection is higher than the
actual period of c0 and thus d(001) > nd(00n) (n > 1). Other basal reflections preserve their
rational positions and therefore they should be used for determination of c0. Thus, the
irrationality due to thin CSDs is apparent and should not be mistaken for the one shown by
crystals containing interstratified interlayers of different thickness. Determination of the origin
of the basal reflection irrationality in LDHs can be based on diffraction methods developed for
investigation of mixed-layer structures of cationic clay minerals.56-59
Powder XRD patterns from non-oriented samples, in addition to basal reflections, contain
hkl reflections, whose positions are determined by the unit-cell parameters. Most of the natural
and synthetic LDHs are described by hexagonal unit cells with a = b ≈ 3 Å, c = mc0, α = β = 90°,
γ = 120°. To determine these parameters, the following procedure can be applied. One of the
characteristic features of powder XRD patterns of LDHs is that, as a rule, they contain a couple
of sharp and strong reflections located within the interval 60-65º 2θ (Cu-Kα radiation) (Figure
5). If isomorphous cations are distributed at random, then the low angle reflection has the 110
indices.
In order to determine the actual periodicity of c, the values of d(10l) and d(11l) should be
calculated for each mc0 (m = 1,2,3…), using the relationship between d(hkl), hkl and hexagonal
unit cell parameters:
1/d2(hkl) = 4(h2+hk+k2)/3a2 + l2/c2
The actual c value provides coincidence within the errors of the calculated and
experimental d(hkl).
In the case of ordered cation distribution in the brucite-like layers, for example, with the
supercell a = √3a0, the 10l and 11l indices determined for disordered cation distribution should
be replaced by 11l and 33l. Examples of indexing of the XRD patterns for one-, two- and
three-layer LDHs with different c0 values and random and ordered cation distribution are given
in Table 2.
Figure 5.-XRD pattern of 11 Å phase.
In some cases the indexing procedure may fail. One of the reasons is that the actual layer
symmetry is not pure hexagonal. Even a slight deviation from the layer hexagonal symmetry
leads to particular diffraction effects. To reveal the actual symmetry of the brucite-like layers, it
is convenient to choose a base-centered unit cell with the parameters a, b, c = mc0, α = β = γ =
90º and b ≈ a√ 3. If b ≠ a√ 3 each of the 110 and 11l reflections characteristic for the hexagonal
unit cell in the interval 60-65º 2θ will be split into two diffractional peaks. For example, if b >
√3a the 110 reflection will be replaced by two closely spaced peaks having 200 and 110 indices,
and if b < √ 3a, the sequence of indices of the split reflections will be inverted.
The relationship between hkl, orthogonal unit cell parameters and d(hkl) values d2(hkl) =
(h2/a2 + k2/b2 + l2/c2)-1 can be used to determine a0, b0 and c parameters from the d-values of the
00l and the split 200, 110, 20l and 11l reflections.
Remarkable examples of hydroxides having orthogonal base-centered unit cells with b ≠ √
3a are gibbsite and synthetic Al2Li(OH)6(CO3)0.5 3H2O. The latter consists of the gibbsite-like
layers in which Li cations occupy the sites that are vacant in gibbsite layers.60 The layer unit
cells of the Al,Li phase and gibbsite are almost the same because the vacant sites in gibbsite are
large enough to be suitable for Li cations (a = 5.07 Å, b = 8.68 Å, ( = 90º). Because b = √ 2.93a,
and a = a0√ 3, the XRD pattern contains a pair of the split strong 330 and 600 reflections instead
of the 330 single peak characteristic for the the hexagonal unit cell.60
Another reason for discrepancy between the experimental and calculated d(hkl) is that the
studied LDH structure may contain stacking faults.57 As in the case of one-dimensional
disorder, the presence of stacking faults shifts the observed hkl reflections from their Bragg's
positions. For example, such reflection displacements should be observed if, within a LDH
crystal, structural fragments of different polytypes are distributed at random. This effect will be
considered in details below.
Structural Analysis
In order to determine the atomic arrangement within the unit cell, intensities of the hkl
reflections should be analyzed. The choice of a particular method for structural analysis
depends on the size of the crystals under study and the perfection of their structure. The most
effective and precise diffraction techniques are based on the study of single crystals. Indeed, the
theory and methods of classical structural analysis of single crystals achieved such a high level
that in order to determine and refine a crystal structure, one has to fulfil only one condition - to
have a sufficiently large, defect-free single crystal. These methods have been widely and
effectively used to study crystal structures of many LDHs.11,20,29,37,61
In the case of crystal compounds, for which sufficiently large crystals do not exist, the
Rietveld technique can be applied.62-64 This method allows us to refine structural details
(atomic coordinates and atomic site occupancies) for LDH compounds, if their idealized
structural model is known. The most common reason for the failure of a Rietveld refinement is
the presence of disorder, such as stacking faults or irregular interstratification of different layer
types typical for layer structures. Therefore this technique can be applied only for defect-free
crystalline compounds. At present, according to our knowledge, this technique has been
applied only once to refine the crystal structure of synthetic hydrotalcite.4
One of the effective methods for the structure study of fine-dispersed crystal compounds is
based on the trial-and-error approach.58 To apply this technique, a structural model is built, for
which the powder XRD pattern is calculated, and then the calculated and experimental
positions, intensities and profiles of the reflections are compared. The model is accepted as
representing the actual crystal structure if the calculated XRD pattern is in good agreement with
the experimental one, and is rejected in the opposite case. The main advantage of this approach
is that it can be applied to both defect-free and defective crystal structures. One of its main
disadvantages is that simulations of an XRD pattern for a defective structure is a
time-consuming procedure.
Table 2. Indices of reflections (hkl), experimental (dexp) and calculated (dcal) spacings for the one-, two- and three-layer LDHs.
hkl dexp dcal | dexp -dcal| hkl dexp dcal | dexp -dcal| hkl dexp dcal | dexp -dcal|
002 7.56 7.56 0 001 11.16 11.16 0 003 18.54 18.54 0
004 3.78 3.78 0 002 5.58 5.58 0 006 9.27 9.27 0
101 2.60 2.60 0 100 4.58 4.58 0 009 6.18 6.18 0
006 2.52 2.52 0 101 4.24 4.23 0.01 00.12 4.63 4.64 0.01
102 2.486 2.486 0 003 3.72 3.72 0 00.15 3.71 3.71 0
103 2.334 2.332 0.002 102 3.543 3.539 0.004 00.21 2.648 2.649 0.001
104 2.160 2.161 0.001 004 2.790 2.790 0 012 2.626 2.629 0.003
105 1.987 1.988 0.001 110 2.646 2.644 0.002 104 2.591 2.592 0.001
008 1.890 1.888 0.002 111 2.574 2.574 0 107 2.504 2.505 0.001
106 1.821 1.821 0 112 2.391 2.396 0.005 018 2.466 2.461 0.005
108 1.536 1.536 0 201 2.245 2.245 0 10.10 2.384 2.386 0.002
110 1.521 1.521 0 005 2.232 2.234 0.002 10.13 2.246 2.246 0
112 1.490 1.491 0.001 113 2.156 2.158 0.002 10.19 1.96 1.961 0.001
109 1.416 1.412 0.004 202 2.120 2.122 0.002 10.22 1.825 1.827 0.002
114 1.410 1.411 0.001 203 1.951 1.954 0.003 01.23 1.783 1.784 0.001
200 1.316 1.312 0.004 114 1.920 1.922 0.002 10.25 1.701 1.704 0.003
10.10 1.311 1.311 0 006 1.860 1.867 0.007 01.26 1.662 1.661 0.001
115 1.706 1.708 0.002 110 1.523 1.523 0
205 1.599 1.598 0.001 116 1.503 1.503 0
300 1.528 1.528 0 119 1.479 1.479 0
301 1.514 1.516 0.002
117 1.365 1.369 0.004
a=3.042 Å, c= 2 c0 =15.12 Å a=a0√ 3 =5.293 Å; c = c0 = 11.16 Å a=3.046 Å, c= 3c0 = 55.62 Å
ONE-DIMENSIONAL STRUCTURAL MODELS OF CO3- AND

SO4-BEARING LDHS
CO3-Bearing LDHs
Triangular CO3 groups are arranged with their bases parallel to the layer surface and are
located at the centerline of the interlayer (Figure 6a). For synthetic MgAl, NiAl, MgGa LDHs a
decrease of the c0 parameter with increasing of the x-value has been observed.2,4,9 A similar
effect can be noted for the natural Mg,Al LDHs: the c0 parameter is equal to 7.45-7.6 Å when
Mg:Al = 26,34,36,37 and to 7.70-7.80 Å when Mg:Al = 3.38,65
The observed relationships between c0 and x (Figure 7) can be attributed to an increase in
electrostatic interaction between positive brucite-like layers and negative interlayers with an
increase in their charge. Brindley and Kikkawa2 noted that the separation of the straight lines c0
= f(x) for the Ni,Al and Mg,Al systems at each given x is about the same as that between the c
parameters of Mg(OH)2 and Ni(OH)2. When the c0 = f(x) lines are extrapolated to x= 0, the
resulting values of c0 are 8.52 Å and 8.37 Å and the difference is 0.15 Å, whereas the difference
between the c parameters of Mg(OH)2 and Ni(OH)2 is 0.16 Å. It means that when the
electrostatic attraction is reduced to zero, interlayer thickness of LDHs in the Mg,Al and Ni,Al
compounds is the same and the difference in the c0 parameters is determined only by the
difference of the Mg(OH)2 and Ni(OH)2 layer thickness.
Figure 6.-One-dimensional model for different DLH structures; (a) CO3-bearing variety; (b) 8.84 Å
SO4-bearing variety; (c) 16.5 Å ordered mixed-layer phase consisting of the CO3-bearing 7.56 Å and
SO4-bearing 8.9 Å layers; (d) SO4-bearing 11 Å phase containing Na in interlayers; (e) 18.5 Å ordered
mixed-layer phase consisting of the CO3-bearing 7.56 Å and SO4-bearing 10.94 Å layers.
Figure 7. Relationship between cell parameter, c0, and Me3+ content, x.
SO4 - Bearing LDHs
SO42- tetrahedra in the interlayers are equally probable in either of two orientations when
their three-fold axes parallel to [001] (Figure 6b). As was mentioned above, among natural and
synthetic SO4-bearing LDHs, two modifications occur, which have the c0 parameter equal to
8.8-8.9 Å and 10.8-11.2 Å, respectively.
A 8.85 Å-phase has been described among synthetic24 and natural16,20,21,27,48 varieties.
Figure 6c shows the z coordinates and the composition of the atoms that correspond to each z
value for the 8.85 Å Mg,Al one-dimensional structural model. The satisfactory agreement
between the calculated and experimental 00l reflection intensities recorded for 8.85 Å
-hydrotalcite supports this model.6 The principal difference between the 8.85 Å and 11 Å
SO4-bearing varieties in their natural state is that the 11 Å phase, along with SO42- and water
molecules, contains Ca, Na and Mg in the interlayer. Such complex cation-anion interlayer
composition has been determined in woodwardite,21,30 motukoreaite,52,61 hydrohonessite,27
mountkeithite,53 wermlandite,11 11 Å SO4 hydrotalcite6 and shigaite.29 Schematically, a
one-dimensional model for 11 Å phase having the composition
[Mg4Al2(OH)12][Na0.56(SO4)1.306H2O] is shown in Figure 6d. Na cations are situated in the
center of the interlayer and are coordinated by six H2O molecules. As in the case of the 8.8 Å
phase, SO42- tetrahedra occur in two opposite but equally probable orientations. Figure 8a
shows the agreement between the experimental intensities of basal reflections and those
calculated for the model in question.
Ordered Interstratification of Interlayer Anions
Two natural LDHs varieties which have an ordered mixed-layer structure consisting
of a regular alternation of SO4- and CO3-bearing interlayers have been described.6 One of
these varieties, which consists of regularly alternating 7.56 Å layers (i.e., a brucite-like layer
plus a CO3-bearing interlayer) and 8.94 Å layers (i.e., a brucite-like layer plus an SO4 -
bearing interlayer), was called a 16.5 Å CO3 - SO4 mixed-layer phase.6 Its composition is
[Mg3.46Al1.47Fe3+0.07(OH)12][(SO4)0.68(CO3)0.34 3H2O]. The positions and distribution of anions
and water molecules in the interlayers of the model shown in Figure 6d are the same as those of
7.6 Å CO3- and 8.85 Å SO4-layers. The intensities of the basal reflections calculated for this
model are in a good agreement with the experimental intensities, Figure 8b. The second variety,
called 18.5 Å CO3-SO4 mixed-layer phase, consists of regularly alternating 7.56 Å CO3-bearing
and 11 Å SO4-bearing layers, Figure 6e. Its composition is
[Mg4Al2(OH)12][(CO3)0.5(SO4)0.64(Na 6H2O)0.282.8H2O. Figure 8c compares the calculated and
experimental intensities of basal reflections for the 18.5 Å CO3-SO4 phase.
Figure 8. Experimental (dotted line) and calculated (solid line) basal reflections for the 11, 16.5 and
18.5 Å phases.
It is quite likely that the compound 6CaO 2Al2O3 CuSO4 CaCl2 24H2O with c = 16.7 Å,
described in reference 65 possibly has a similar mixed-layer structure in which 7.75 Å
Cl-bearing and 8.85 Å SO4-bearing (Ca7Cu1Al4)(OH)24 layers regularly alternate along the c
axis.
A very peculiar mixed-layer structure has been described by Arakcheeva et al.37 In this
structure, CO3-bearing interlayers regularly alternate with CO3-free interlayers filled by water
molecules. Because of similar scattering powers of CO3 and 3H2O and almost identical
thicknesses of both types of the interlayers, the periodicity along the c axis recorded in the
experimental XRD pattern was equal to 7.55 Å. To reveal such a mixed-layer phase
experimentally, that is, to distinguish its from the CO3-bearing LDHs having homogeneous
interlayer composition, a single crystal structural analysis has to be applied.
Behavior of SO4 - Bearing Phases on Ethylene Glycol or Glycerol

Saturation
Water molecules in SO4-bearing interlayers can be replaced by molecules of ethylene

glycol or glycerol.6,21 Typically, the thickness of the SO4-bearing layers which contain adsorbed
ethylene glycol is 12.36 Å regardless of whether the thickness of the initial layer was 8.9 Å or
11 Å.6 Figure 9 shows a series of 00l reflections from air-dry (a) and the ethylene
glycol-saturated (b) 11 Å phase where d(001) = 12.36 Å, and Figure 10 shows XRD patterns of
a sample containing a mixture of the 8.85 Å, 11 Å and 16.5 Å phases obtained before (a) and
after (b) ethylene glycol saturation. The XRD pattern of the ethylene-glycol saturated sample
contains two different series of 00l reflections having the periodicities of 12.36 and 19.92 Å. In
the mixed-layer structure, the interlayers containing CO3 did not interact with molecules of
ethylene glycol, whereas interlayers containing SO4 expanded, leading to an increased layer
thickness of 7.56 Å + 12.36 Å = 19.92 Å in full agreement with the value of d(00l) measured on
the XRD pattern. The 18.5 Å phase also expanded to 19.92 Å.
On glycerol saturation, not all the phases expanded; moreover, the same phase expanded to
different degree in different samples. For example, the XRD pattern of the 11 Å phase after
glycerol saturation showed additional 00l reflections at 13.68 Å, 6.80 Å and 4.56 Å, suggesting
expansion of only part of the sample (Figure 10c). This effect can be associated with structural
heterogeneity of the 11 Å microcrystals, possibly due to different positive charges on the
brucite-like layers and/or different concentration of cations and anions in the interlayers. On the
other hand, it is possible to assume that SO4 interlayers can adsorb either two or one layer of
glycerol molecules. In this case, adsorption of one layer of these molecules may lead to the
same layer thickness as for the air-dried sample, which was observed in the XRD pattern
obtained for the glycerol-saturated 11 Å phase. This interpretation looks quite plausible
because part of the 8.85 Å layers in the 16.5 Å phase expanded to 13.68 Å giving a periodicity
of 21.24 Å = 7.56 Å + 13.68 Å due to adsorption of two layers of glycerol molecules. The other
part of the 8.85 Å layers in the 16.5 Å phase expanded only to 11.0 Å due to adsorption of only
one layer of glycerol molecules giving a period of 18.6 Å.
Mixed-Anion Interlayer Composition
Among natural and synthetic LDHs some varieties have a mixed-anion composition of the
interlayers. This is not surprising when coexisting anions have similar sizes, as in the case of
natural chlormagaluminate26 or hydrocalumite66 represented by Cl- and CO32- solid solution, or

synthetic Mg,Ga LDHs containing in the interlayers CO32- and NO3-.4 However, for some 11 Å
minerals, chemical, XRD and IR analyses indicate the presence of both SO42- and CO32- anions
in the same interlayers, because the experimental XRD patterns of these samples contain
rational series of basal reflections with c0 ≈ 11 Å characteristic for pure SO4-bearing LDHs.
Such a mixed-anion interlayer composition was determined, for example, for carrboydite,54
motukoreaite52 and mountkeithite.53 The arrangement of CO3 in the interlayers of these
minerals is still unclear.
Figure 9. Basal reflections of the 11 Å phase: (a) air-dry; (b) ethylene glycol-saturated and (c)
glycerol-saturated.
Figure 10. Basal reflections of a natural mixture of the 8.85 Å, 11 Å and 16.5 Å phases: (a) air-dry; (b) ethylene
glycol-saturated and (c) glycerol-saturated.
POLYTYPE DIVERSITY OF THE LDH COMPOUNDS

It is well known that natural and synthetic LDHs usually crystallize in two polytype
structures, one with a two-layer hexagonal stacking sequence (polytype 2H) and one with a
three-layer rhombohedral sequence (polytype 3R). The hexagonal stacking of the brucite-like
P 3 m1 layers is characterized by the space group P 6 3/mmc and the rhombohedral stacking
results in the symmetry of space group R 3 m. One-layer and six-layer polytypes of different
chemical compositions have also been described.6,28 Recently Bookin and Drits67 showed the
possibilities for the discovery of new polytype members were far from being exhausted. These
authors noted that, up to now, polytype classifications have been limited to the information on
the number of brucite-like layers in the unit cell, because the interpretation of experimental
XRD data obtained for fine-dispersed powders of hydrotalcite-like minerals was often limited
to the analysis of the positions, and not the intensities of reflections. Such an approach misses
certain, rather important structural regularities associated with the stacking of consecutive
brucite-like layers. Therefore, Bookin and Drits67 deduced systematically the theoretically
possible polytypes, calculated the XRD powder patterns for most polytypes, and formulated
diffraction criteria to distinguish between polytypes with same unit cells. The XRD patterns
were calculated for the structural models of the derived polytypes with random distribution of
isomorphous layer cations and interlayer anions. In addition, these authors calculated the
intensities of XRD reflections for the one-layer polytype with ordered cation distribution.
Simultaneously, Hofmeister and von Platen68 considered structural models of 3R1 and 2H1
polytypes with ordered cation distributions and calculated XRD patterns corresponding to these
models. The main results of these works will be described below.
Notations
Let us assume that the first brucite-like octahedral layer, in terms of close packing, is
symbolically represented as AbC. To shorten the notation, we shall omit symbols of cation
positions since they depend entirely on the arrangement of hydroxyls. In the theoretical
simulation of idealized polytypes, we assume that the OHs in the lower sheet of the next
brucite-like layer in a stack can occupy any of the A, B, or C positions. If they reside in the C
sites, OHs form prisms in the interlayer (Figure 11a). This type of interlayer will be referred to
henceforth as a P-type interlayer and denoted with an equal sign. If the hydroxyls in the lower
sheet reside in either A or B sites, the OHs form octahedra (Fig. 11b). Such interlayers will be
referred to as O-type and denoted with a dash to distinguish them from the P-type interlayers.
...AC-AC... 1H
Note that in the one-layer polytype all the cations reside in the b position on a line normal
to the layers.
In the above notation we can describe a one-layer polytype with an O-type interlayers as:
Figure 11. Mutual arrangement of the brucite-like layers forming (a) P- and (b) O-type interlayers.
Two-Layer Polytypes
All two-layer polytypes can be derived from the scheme presented in Figure 12. Of the six
illustrated structures, #1 describes the one-layer polytype, while the pairs #2 and #4, and #3 and
#6 are symmetrically equivalent. Thus there are three different hexagonal two-layer polytypes:
...AC=CA=AC... 2H1
...AC-AB-AC... 2H2
...AC-BA=AC... 2H3
In this notation, a digit stands for the number of layers, a letter denotes symmetry, and a
numerical subscript corresponds to the particular polytype.
In the polytype ...AC=CA=AC..., all interlayers are of P-type and the cations occupy only
the b sites as in polytype 1H. The polytype ...AC-AB-AC... has all interlayers of the O-type and
cations of the brucite-like layers alternate in b and c sites. The last polytype, ...AC-BA=AC...,
has alternating interlayers of both types.
Figure 12. Schematic derivation of two-layer polytypes.
Three-Layer Polytypes
The scheme for the derivation of all three-layer polytypes can be constructed on the same
principle as presented in Figure 12. Let us simulate the possible three-layer polytypes
separately depending on the type of the interlayers.
A three-layer crystal with P-type interlayers is represented by the unique sequence:
...AC=CB=BA=AC... 3R1
This polytype has rhombohedral symmetry (3R) and the distribution of cations over the
possible sites is the most homogeneous.
All three-layer polytypes with O-type interlayers can be derived from the schematic
diagram shown in Figure 13. Polytype 5 is the one-layer crystal, and the others represent three
symmetrically independent three-layer polytypes.
...AC-BA-CB-AC... #8 3R2
...AC-AB-AB-AC.. #1, #2, #4, #6, #10, #11 3H1
...AC-AB-CB-AC... #3, #7, #9 3H2
The first structure in this group has rhombohedral symmetry while the other two have
hexagonal symmetry. In the 3R2 and 3H2 polytypes, cations are homogeneously distributed
over the possible sites as in the 3R1 polytype.
Figure 13. Schematic derivation of three-layer polytypes with O-type interlayers only.
The group of symmetrically independent polytypes with interlayers of both types is

represented by five possible structures, all hexagonal:
...AC-AB=BA=AC... 3H3
...AC-AC=CA=AC... 3H4
...AC-AB=BC-AC... 3H5
...AC-AB-CA=AC... 3H6
...AC-AC-BA=AC... 3H7
Six-Layer Polytypes
Of the great number of possible six-layer polytypes, we are only interested in those which
have rhombohedral symmetry because they are the only ones described in the literature6. To
construct a six-layer polytype of this symmetry it is necessary to take a pair of layers and stack
the pairs by shifting them along the [ 1 10] direction, by one third of the unit cell. To simulate all
polytypes, it is sufficient to apply the described procedure to all different pairs, which are the
three two-layer polytypes listed above, and a pair of identical layers. This gives five
symmetrically independent polytypes:
...AC-AC-BA-BA-CB-CB-AC... 6R1
...AC-AC=CB-CB=BA-BA=AC... 6R2
...AC=CA-BA=AB-CB=BC-AC... 6R3
...AC=CA-CB=BC-BA=AB-AC... 6R4
...AC-AB-CB-CA-BA-BC-AC... 6R5
Among them, there is not a single structure with all interlayers of the P type. Two structures
contain only O-type interlayers and three structures contain alternating P and O interlayers.
Out of numbers six-layer polytypes with a hexagonal lattice symmetry (6H), the group
with all interlayers of P type is of a particular interest because the interlayers of this type, as will
be shown below, correlate with carbonate anions. The derivation is straightforward and gives
nine polytypes:
…AB=BC=CB=BA=AB=BA=AB… 6H1
…AB=BC=CB=BA=AC=CA=AB… 6H2
…AB=BC=CB=BC=CB=BA=AB… 6H3
…AB=BC=CA=AC=CB=BA=AB… 6H4
…AB=BA=AC=CB=BC=CA=AB… 6H5
…AB=BA=AC=CA=AB=BA=AB… 6H6
…AB=BA=AC=CA=AC=CA=AB… 6H7
…AB=BA=AB=BC=CB=BA=AB… 6H8
…AB=BA=AB=BA=AC=CA=AB… 6H9
Thus, as in the case of many other minerals and synthetic compounds consisting of layers
having pseudohexagonal symmetry, polytypes having equal number of layers per unit cell, but
differing substantially in layer arrangements, are theoretically possible for the LDH compounds.
There can be three two-layer polytypes differing in interlayer type. In one of them, interlayers
are of the P-type, in another, all interlayers are of the O-type, and the third has alternating
interlayers of both types. Among the nine three-layer polytypes, there is one structure with all
interlayers of P-type, three structures with interlayers of O-type and five structures having
heterogeneous interlayers. Thus, all polytypes may be divided into three groups: homogeneous
interlayers of P-, or O-type, and alternating interlayers of both types.
STRUCTURAL MODELS OF LDH POLYTYPES AND THEIR X-RAY

DIFFRACTION FEATURES
3D Models
Since different polytypes with the same number of layers per unit cell and the same lattice
symmetry show similar reflection positions, the only way to identify a polytype using a powder
XRD pattern is to analyze peak intensities. The problem was to build structural models for each
polytype taking into account the possible cation and anion composition, order-disorder in
cation and anion distribution as well as atomic coordinates and site occupancy.
Structure refinements of numerous layer silicates have shown that approximations of ideal
models provide acceptable results because the relative intensities of strong, medium, and weak
reflections change rather little between ideal and real structures.69 Nevertheless, the main
crystal chemical features characteristic for LDHs have been taken into account to calculate
XRD patterns.67,68 In the structural model with random cation-anion distribution, OH groups
and cations of brucite-like layers occupy special sites in the basic unit cell (a=a0): (0, 0, z); (2/3,
1/3, z) and (1/3, 2/3, z) respectively, where z- coordinates were taken from the one-dimensional
models (Figure 6). The cation composition of brucite-like layers was confined to cationic pairs
Mg,Al; MgFe3+ and NiFe3+ with Me2+:Me3+ equal 2 and 3. Hofmister and von Platen68
postulated that most of LDH structures have complete order in cation distribution. They
assumed that for Me2+:Me3+ = 2:1, the isomorphous layer cations form a supercell with a = √
3a0 (Figure 4a) and for Me2+:Me3+ = 3:1, a supercell with a = 2a0 (Figure 4c). Positions of the
layer hydroxyls have been changed to minimize the cation electrostatic interaction and to get
the mean bond length characteristic for each kind of the layer cation. For example, ordered
Mg,Al brucite-like layers should have interatomic distances equal to dAl-OH = 1.90 Å and dMg-O
= 2.10 Å determined for gibbsite70 and brucite,1 respectively.
For CO3-bearing structures with random cation distribution, positions of the C atoms are
predetermined by those of the layer cation. For polytypes with ordered cation distribution, the
C atoms are located above or below Al or Fe3+.68 According to Allman19 and Allman and
Jepsen,34 three oxygen atoms of the planar CO3 group may be randomly distributed among six
possible sites giving the impression of a rotating anion. Hofmeister and von Platen68 assumed
that the incorporation of CO32- in a P-type interlayer results in a hexagonal stacking sequence of
OH- groups of the adjacent layers with the oxygens of CO3. The sequence of anions forming a
P-type interlayer can be, in this case, written as AOHBOAOH or AOHCOAOH where AOH are the
positions of OH-groups forming the interlayer and belonging to adjacent brucite-like layers,
and BO and CO are possible idealized sites for the oxygen atoms of CO3 anions. According to
the experimental data, however, in the P-type interlayers, each oxygen atom of the CO3 anion is
located along the c axis between two nearest OH groups of the neighboring brucite-like layers
and forms hydrogen bonds responsible for layer interaction.4,37,71 It means that the oxygens of
carbonate anions locate near the lines connecting the OHs of adjacent layers (see Figure 11).
The mutual arrangement of the surface hydroxyls and oxygens of the carbonate groups can be
written as AOHAOAOH. Of course, this is an idealized sequence because O atoms of each CO3
are shifted to the C atom, as the O - O distances equal to 2.2 Å are significantly shorter OH-OH
distances equal to a0. If one neglects this deviation from close packing, then the positions of the
interlayer anionic oxygen atoms are uniquely determined by the positions of the hydroxyl
groups that form P-type interlayers. The oxygen atoms of the interlayer water molecules locate
at the same sites as those of CO32- and are hydrogen bonded to an OH group of the main layer,
leaving the water molecule free to rotate around its the two-fold symmetry axis.71
Sulfate tetrahedra in SO4-containing polytypes have two opposite orientations along the c
axis, so that one face of the tetrahedron is parallel to the layer surface. The positions of three
sulfate oxygen atoms that form a tetrahedral face are similar to the positions of the carbonate
oxygen atoms, that is, they are located just under or above the layer hydroxyls. If three sulfate
oxygen atoms form hydrogen bonds with OH groups of the lower layer, then the interaction of
the fourth tetrahedral apex with nearest layer or interlayer species depends on the interlayer
thickness. For the 8.85 Å polytype, the apical oxygen atom can form a hydrogen bond with a
hydroxyl of the upper layer. For the 11 Å polytype, this oxygen atom is hydrogen bonded to
three nearest water molecules, which, in turn, are bonded to hydroxyls of the upper layers.29,61
XRD Features of LDH Polytypes with Random Cation-Anion Distribution
Tables 3 to 5 list d-values, hkl indices, and intensities of reflections calculated for one-,
two-, and three-layer polytypes. Analysis of the data shows that relative intensities of
reflections of the basic unit cell (a0 ≈ 3 Å) vary within a rather small interval when Mg is
replaced by Ni, or when Al is replaced by Fe3+ (columns A and B, F and H in Table 3). Due to
the small difference in scattering powers, the substitution of Fe2+ or Cu for Mg, and Cr3+ for Al
does not strongly modify the XRD pattern either. Similarly, small changes are found in these
intensities due to the presence or absence of interlayer anions (columns B and C, E and F, G and
H in Table 3). In all the cases, strong reflections remained strong, and weak reflections
remained weak.
Thus, the intensities of reflections corresponding to polytypes with disordered cation-anion
distribution (a = a0) are determined largely by the mutual arrangement of brucite-like layers
and depend weakly on variations in cation composition of brucite-like layers and scattering by
interlayer anions (but not the anions themselves, because they determine the c0 distance).
Table 3. Intensities of XRD reflections in the 1H polytype with different chemical compositions of brucite-like layers and interlayers, and with
disordered cation and anion distribution in the ab plane (a = 3.050 Å).
Anion CO32- SO42-

c(Å) 7.56 8.83 10.83
hkl d(Å) A B C hkl d(Å) D hkl d(Å) E F G H
100 2.641 52 31 8 100 2.641 34 100 2.641 6 11 35 37
101 2.494 100 85 58 101 2.531 86 101 2.566 39 48 85 62
102 2.165 90 100 100 102 2.267 100 102 2.374 86 100 100 100
103 1.823 63 76 70 103 1.966 85 103 2.132 100 81 100 74
104 1.537 40 48 44 104 1.694 62 104 1.891 79 81 84 67
110 1.525 24 34 43 110 1.525 32 105 1.675 54 70 61 58
111 1.495 39 50 44 111 1.503 52 110 1.525 36 56 33 36
112 1.414 25 23 15 105 1.468 39 111 1.510 61 44 55 39
105 1.312 24 28 24 112 1.441 30 106 1.490 36 33 42 33
113 1.305 14 7 1 113 1.354 12 112 1.468 32 33 38 32
113 1.405 11 15 21 19
107 1.335 25 30 23 26
A) Ni3Fe without scattering by interlayer.

B) Mg2Al without scattering by interlayer.
C) Mg2Al 1/2CO3+2.2H2O interlayer.
D) Ni3Al without scattering by interlayer.
E) Mg2Al without scattering by interlayer.
F) Mg2Al 1/2SO4+11/2H2O interlayer.
G) Ni3Fe without scattering by interlayer.
H) Ni3Fe 1/2SO4+11/2H2O interlayer.
There are several problems in the identification of LDH polytypes from powder XRD data.
Intensities of the basic unit cell reflections in the 2H1 polytype with SO42- anions in both
hydrated states (Table 4) are similar to those of the one-layer polytype (Table 3). This may be
due to the similarity in the distribution of cations in the brucite-like layers. Weak 103 and 105
reflections at 2.41 Å and 2.11 Å (low hydration state) and at 2.48 Å and 2.26 Å (high hydration
state) seem to be the unique features that allow recognition of the 2H1 polytype. It may be
difficult to distinguish between the 2H2 and 2H3 polytypes for SO4-varieties, although they are
dramatically different in their structures. On the contrary, some polytypes can be easily
distinguished between. For example, reflections in the 10l series with l = 2n should be stronger
for the 2H1 polytype, whereas reflections with l = 2n + 1 should be stronger for the other two
polytypes (Table 4).
Several empirical rules may be used to distinguish between the three-layer polytypes
(Table 5). The hexagonal polytypes differ from the rhombohedral polytypes by the presence of
strong reflections with (-h + k + l) ≠ 3n. The following simple diffraction criteria may be used
to differentiate between the 3R1 and 3R2 modifications. XRD patterns of the 3R1 polytype with
CO3 or SO4 contain strong 012, 015 and 018 reflections (l = 3n - 1). In contrast, XRD patterns
of the 3R2 polytype should contain strong 101, 104, 107 and 10.10 reflections (l = 3n + 1). The
rule is equally valid for the varieties with light (Al,Mg) and heavy (Ni,Fe) cations.
The criteria for the discrimination of hexagonal polytypes depend on the nature of the
interlayer anion. In the case of SO4-varieties, in polytype 3H1, all 10l reflections including 100
show intensities of the same order, whereas in polytype 3H2, reflections 10l with l = 3 are much
weaker than the others. For CO3-varieties, the 3H1 polytype has the strongest 10l reflections
with l = 3n, whereas for the 3H2 polytype, strong reflections have l = (3n + 1) with n = 1, 2, 3.
XRD Features of LDH Polytypes with Ordered Cation-Anion Distribution
For structures with cation and anion ordering in the ab plane where a ≠ a0, superlattice
reflections appear that do not obey the rules described above. Their intensities depend heavely
on the scattering power of the Me3+ and Me2+ cations and on the type of anions in
interlayers.74,67,68 For example, the Mg2Fe3+ variety of the 1H polytype shows a set of
superlattice reflections, the strongest being 100, 101, 102 (Table 6).
Similar effects are observed for the CO3-bearing 2H1 and 3R1 polytypes (Table 6). XRD
patterns of Mg,Fe-varieties contain rather strong super-reflections when Mg:Fe3+ = 2:1 (a = √
3a0) and Mg:Fe3+ = 3:1 (a = 2a0). In particular, these superreflections have indices 100, 102 and
104 for the 2H1 and 101, 012, 104, 015 for the 3R1 polytypes with a = 2a0 (Table 6). In contrast,
all superreflections for the Mg,Al-varieties are extremely weak, irrespective of the Mg:Al
ratios. The results of the calculations have shown that ordered Al,Mg-varieties cannot be
determined by powder XRD patterns. It is likely, however, that the cation ordering is
accompained by the corresponding order in the interlayer anions. In this case the cation
ordering in 1H, 2H and 3R, SO4-bearing Mg,Al varieties may be identified by the presence of a
strong 100 super-reflection (Table 6). For Mg,Fe varieties, superstructures may be displayed by
the presence of two or three weak 10l superreflections with low l values.
Table 4. Intensities of XRD reflections in different two-layer polytypes with disordered cation* distributions in the ab plane (a = 3.050 Å).
Anion: CO32- SO42-

c0(Å): 7.560 8.830 10.830
c(Å): 15.120 17.660 21.660
hkl d(Å) 2H1 2H2 2H3 hkl d(Å) 2H1 2H2 2H3 hkl d(Å) 2H1 2H2 2H3
100 2.641 3 10 2 100 2.641 42 12 12 100 2.641 40 12 11
101 2.602 27 21 30 101 2.612 0 80 75 101 2.622 0 80 72
102 2.494 60 41 22 102 2.531 92 40 25 102 2.566 86 36 27
103 2.340 77 82 96 103 2.410 21 90 100 103 2.481 16 90 88
104 2.165 90 82 35 104 2.267 100 50 30 104 2.374 93 50 32
105 1.989 100 50 100 105 2.115 18 100 96 105 2.255 20 100 100
106 1.823 43 100 26 106 1.966 100 40 30 106 2.132 100 47 32
107 1.672 73 2 59 107 1.824 0 80 75 107 2.009 12 90 88
108 1.537 20 68 15 108 1.694 75 22 20 108 1.891 86 35 26
110 1.525 67 59 52 109 1.575 0 54 50 109 1.779 0 76 68
111 1.517 0 0 0 110 1.525 36 45 42 10.10 1.675 68 22 19
112 1.495 90 79 71 111 1.519 0 0 0 10.11 1.579 0 55 48
113 1.460 0 0 0 112 1.503 65 76 70 110 1.525 36 45 40
109 1.418 43 40 36 113 1.476 0 0 0 111 1.521 0 0 0
114 1.414 24 21 19 10.10 1.468 48 15 13 112 1.510 64 80 72
115 1.362 0 0 0 114 1.441 36 42 40 113 1.491 0 0 0
115 1.400 0 0 0 114 1.468 43 54 48
10.11 1.372 0 33 32 115 1.438 0 0 0
116 1.354 15 18 17 116 1.405 23 30 26
117 1.305 0 0 0 117 1.368 0 0 0
*Cations are Mg,Al for CO3-bearing varieties and Ni,Al for SO4-ones
Table 5. Intensities of XRD reflections in different 3-layer polytypes with disordered cation distribution in the ab plane (a = 3.050 Å).
Anion CO32- SO42-

c0(Å) 7.560 8.830 10.830
c(Å) 22.680 26.490 32.490
hkl d(Å) 3R1 3R2 3H1 3H2 hkl d(Å) 3R1 3R2 3H1 3H2 hkl d(Å) 3R1 3R2 3H1 3H2
100 2.641 0 0 4 0 100 2.641 0 0 54 0 100 2.641 0 0 57 0
101 2.624 1 20 10 22 101 2.628 28 54 55 66 101 2.633 29 49 58 66
102 2.573 41 0 14 14 102 2.590 69 22 58 54 102 2.607 62 23 60 53
103 2.494 0 0 66 28 103 2.531 0 0 79 8 103 2.566 0 0 75 6
104 2.394 1 83 28 81 104 2.454 14 94 65 95 104 2.512 15 85 67 88
105 2.283 100 1 36 37 105 2.364 100 13 68 56 105 2.447 92 14 67 55
106 2.165 0 0 100 40 106 2.267 0 0 100 14 106 2.374 0 0 100 13
107 2.047 1 100 36 100 107 2.166 15 100 71 100 107 2.296 13 100 74 100
108 1.933 91 4 47 50 108 2.065 91 17 65 58 108 2.214 100 14 74 58
109 1.823 0 0 58 12 109 1.966 0 0 80 7 109 2.132 0 0 97 11
10.10 1.721 15 52 28 59 10.10 1.871 23 68 60 77 10.10 2.050 18 89 74 93
10.11 1.625 36 19 36 49 10.11 1.780 53 27 54 52 10.11 1.969 80 20 67 57
10.12 1.537 0 0 27 0 10.12 1.694 0 0 48 0 10.12 1.891 0 0 74 4
110 1.525 41 40 69 71 10.13 1.614 30 32 42 47 10.13 1.816 26 57 59 71
111 1.522 0 0 0 0 10.14 1.539 23 30 36 40 10.14 1.744 46 28 54 52
112 1.511 0 0 0 0 110 1.525 36 37 94 54 10.15 1.675 0 0 48 0
113 1.495 56 54 94 96 01.15 1.468 0 0 32 1 110 1.525 35 35 77 53
114 1.473 0 0 0 0
10.13 1.456 25 14 17 24
Table 6. Intensities of XRD reflections in 1-, 2- and 3-layer polytypes with ordered cation distribution in the ab plane.
Anion SO4 CO3

a(Å) 5.283 6.228 6.226
c(Å) 10.830 23.39 15.610
hkl d(Å) I(hkl) hkl d(Å) I(hkl) hkl d(Å) I(hkl)
100 4.575 17* 28** 100† 101 5.256 27†† 100 5.392 32#
101 4.215 28 16 1 012 4.898 25 102 4.436 36
102 3.495 18 26 0 104 3.965 11 104 3.161 12
103 2.834 10 10 0 015 3.534 11 110 3.113 6
110 2.642 17 16 2 110 3.114 6 112 2.892 10
111 2.566 58 69 27 113 2.892 11 200 2.696 17
112 2.374 92 100 40 107 2.840 4 201 2.657 17
104 2.330 7 6 0 021 2.679 5 202 2.548 53
113 2.132 100 89 36 202 2.628 75 114 2.434 6
105 1.958 4 5 0 116 2.433 7 203 2.394 66
114 1.891 84 89 37 205 2.336 153 106 2.343 4
106 1.679 3 2 0 027 2.099 7 204 2.218 89
115 1.675 58 69 28 208 1.982 111 205 2.040 31
300 1.525 36 46 21 02.10 1.767 28 206 1.872 88
301 1.510 60 55 23 20.11 1.670 39 214 1.807 5
116 1.490 41 42 16 220 1.557 45 208 1.581 53
302 1.468 36 33 12 223 1.527 61 220 1.536 41
107 1.466 2 2 0 02.13 1.497 33 222 1.526 57
117 1.335 28 29 12
*Mg2Fe without scattering by interlayers, 1H

**Mg2Fe+1/2SO4+11/2H2O, 1H
†
Mg2Al+1/2SO4+11/2H2O, 1H
††
Mg9Mn3+1/2CO3+6H2O, 3R1
#
Mg6Fe2+CO3+41/2H2O, 2H1
Structural Disorder and Intensity of 10l Superreflections
Calculations of 10l superreflections described were made for LDH structural models
having ideal three-dimensional periodicity and ideal cation ordering within the brucite-like
layers. Let us consider now the influence of different structural imperfections on the intensity
of 10l superreflections taking, as an example, a LDH structural model for which Me2+:Me3+ =
2:1 and heterovalent cations are distributed with superperiod a = √ 3a0 (pyroaurite with perfect
ordering). In this model, successive brucite-like layers are shifted with respect to each other by
1/3 of the long diagonal of the sub-cell with the parameter a0, as the brucite-like layers are
shifted in 3R1 polytype. The super-cell with a = √3a0 (Figure 4) and c = 3c0 has hexagonal
symmetry and extinctions typical for the rombohedral lattice (-h + k + l) = 3n are not valid for
the studied model. For simplicity, it is assumed that interlayer species are distributed in
accordance with the sub-cell and therefore their contribution into intensity of 10l
superreflections can be ignored. Under such conditions, the intensity of these reflections
depends mostly on the scattering powers of Me2+ and Me3+ cations: the higher the difference
between their scattering powers, the higher I(10l). Figure 14 shows a fragment of XRD pattern
(thick solid line) calculated for a pyroaurite-like model with Mg:Fe = 2:1. It can be seen that the
intensity of the 100 reflection (1/d = 0.22 Å-1) is only 15% that of 110 reflection (1/d = 0.38 Å-1)
characteristic for random cation distribution. The intensities of 10l (l > 1) reflections decrease
with increasing l.
Let us assume now that the adjacent layers in the model are shifted with respect to each
other by 1/3 of the long supercell diagonal ([1 1 0], [210] and [120] directions). Because the
length of the diagonal is 3a0, such displacements do not modify the rombohedral stack of the
successive brucite-like layers but change the mutual arrangement of Mg and Fe3+ in adjacent
layers (Figure 15). Figure 14 shows XRD pattern calculated for a model containing 20% of
additional displacements by a0 (dotted line) and for a model with very high content of the faults,
in which the positions of Fe and Mg in adjacent layers are not correlated (thin solid line). With
low defect concentration the XRD peaks are flatten but the modulations remain visible. For the
case of disorder, a set of 10l reflections is transformed into a two-dimensional diffraction band
typical for turbostratic structures. As expected, the intensity of the 100 reflection does not
depend on the layer stack, but is determined by the distribution of isomorphous cations within
the supercell.
In order to estimate the role of the factors responsible for the intensity of 100
superreflection, let us assume that in the supercell shown in Figure 4a, isomorphous cations
occupying their possible octahedral sites with coordinates (0, 0), (2/3, 1/3) and (1/3, 2/3) have
scattering factors f1, f2 and f3, respectively. It can be shown that the intensity of the 100
reflection is proportional to [f1-1/2f2-1/2f3]2. In the pyroaurite-like model, Fe3+ and Mg cations
are distributed as shown in Figure 4a f1 = fFe3+, f2 = f3 = fMg and I(100) ≈ (fFe3+ - fMg)2. Let us
assume now that the ideal sequence of Mg and Fe cations Fe-Mg-Mg-Fe… along [ 1 10] [210]
and [120] is distorted because of the presence of defective cation subsequences
Fe-Mg-Mg-Mg-Fe… and Fe-Mg-Fe… that occurr with equal probability. Such defects do not
change the stoichiometry of the cation composition, but modify cation occupancy of octahedra
within the averaged supercell. The mixed cation composition of the octahedral sites smoothes
the difference between scattering powders f1, f2 and f3 and thus decreases the intensity of the
100 reflection. Calculations show that this reflection preserves around 20% of its initial
intensity if a sample contains 33% of defective cation subsequences described (Figure 16).
Even if all theses cation subsequences occur with equal proportions, it does not mean that there
is a complete cation disorder because neither Fe-Fe… nor Fe-Mg-Mg-Mg-Mg-Fe…
subsequences are allowed.
Figure 14. XRD patterns calculated for 3R1 structures with a defective stacking of layers having perfect
Mg-Fe3+ ordering.
Figure 15. Disordered Me3+/Me2+ cation distribution through the layers in the 3R1 polytype. Within each
layer cations are ordered within a cell having a = a0v3. Light large circles - Me2+, dark large circles - Me3+.
Small circles - OHs below (open circles) and above (filled circles) the Me plane.
Figure 16. Dependence of the 100 supercell reflection intensity on occurrence probability of defective
Fe-Mg-Mg-Mg-Fe and Fe-Mg-Fe cation subsequences in the brucite-like layers of the composition Mg2Fe.
Another factor which is responsible for decreasing the intensity of the 100 reflection is the
deviation from stoichiometry when Mg:Fe3+ > 2:1. In such a system, cation subsequences
Fe-Mg-Mg-Fe… and Fe-Mg-Mg-Mg-Fe… may alternate along [1 1 0], [120] and [210]
directions. In the average supercell, octahedral sites should have mixed cation composition
providing a decrease in the 100 reflection intensity. Even a small deviation from the
stoichiometry should be accompanied by a dramatic decrease in the 100 reflection intensity.
Defects of the former type occuring together with the defects of the latter type increase the 001
peak weakening (Figure 17).
Figure 17. Intensities of the 100 supercell reflection calculated for non-stoichiometric compositions. The
legend lists Fe3+:Mg ratios and the conjunction probabilities for the Fe-Mg-Mg-Mg-Fe fragment to follow the
Mg-Fe-Mg fragment.
Thus, equally probable occurrencies of Me3+-Me2+-Me2+-Me2+-Me3+ and Me3+-Me2+-Me3+

cation subsequences in the stoichiometric system with Me2+:Me3+ = 2:1, as well as the
deviation from stoichiometry, are the two main sources of problems, which make it is difficult
to determine the long-range cation ordering in LDHs by powder XRD.
Stacking Faults
One of the common features of layer crystals including LDHs is that their structures
contain stacking faults. The existence of these faults is predetermined by the very nature of
layer crystals because, on the one hand, within them interlayer interaction is much weaker than
intralayer interaction, and, on the other hand, layers have high symmetry (as a rule, hexagonal
or trigonal). Therefore layers in a layer pair may stack in several ways that are energetically
similar. In such defective structures, the layers preserve their two-dimensional (2D) periodicity,
but the 3D periodicity of a crystal is distorted, either because of interstratification of layer types
having different azimuthal orientations but similar or identical 2D periodicity or because of
irregular stacking of identical layers resulting from additional translations. The presence of
stacking faults strongly affects diffraction patterns, and changes in them depend on the nature
and proportion of stacking faults. In particular, symmetric and sharp reflections normal for 3D
structures may shift from the Bragg's positions and transform into broad and asymmetric
diffraction bands.
These diffraction features are typical for the numerous powder XRD patterns of LDHs
published in the literature. In particular, the XRD patterns contain symmetrical and narrow 11l
peaks and broad and asymmetric 10l bands, whose profiles resemble those of two-dimensional
diffraction bands common for turbostratic structures. Moreover, the 10l peaks are shifted from
positions expected for the cell defined by the 11l peaks.
In the simplest case, a crystal may consist of type I layers that would form a regular 3D
structure, and type J layers producing defects. In the general case, probability to find a given
layer at any place in the layer stack may be determined by the number of the proceeding layers.
This value, R, is a measure of the interaction between the nearest layer types and of the short-
range order in their sequence.
If the occurrence probability of a given layer type does not depend on the nature of the
nearest preceeding layer, then R = 0 and I and J layers are randomly stacked. In this case, the
occurrence probability of defects WJ (WI = 1 - WJ ) is the only parameter that controls the
changes in a diffraction pattern resulting from defects. If I and J layers alternate with R = 1, then,
to characterize the structure, four additional probability parameters PII, PIJ, PJI and PJJ will be
needed, where Pij (i, j = I, J) is the conjunction probability of layer type j to follow layer type i.
These parameters are interrelated, and only two independent probability parameters (WJ and PJJ)
are required to describe any layer sequence in a structure with R = 1. Other occurence
probabilities can be calculated as discussed in references 57 and 58. If PJJ < WJ then the layers I
and J are interstratified with a tendency to ordering. In the extreme case of PJJ = 0, the
maximum possible degree of order in the layer alternation occurs. If PJJ > WJ, then the layers
have a tendency to segregation, the complete segregation being reached at PJJ = PII = 1. In this
case, a crystal consists, in fact, of two individually diffracting parts. These parts should be
either different polytypes or twins.
A crystal built of identical layers can also contain stacking faults if successive layers are
shifted by several additional translations. The statistical description of such structures is
identical to that given above, with translations taking as variables.
In general, to determine the defect structure, one has to know the nature of interstratified
layers or translations, their proportions and conjunction probabilities. The number independent
probability parameters is determined by R.
Let us apply the general statistical description to LDH structures and, in particular, to the
3R1 polytype as the most common structure. As discussed above, six possible brucite-like
layers: AB, AC, BA, BC, CA, and CB, can follow one another in such a way that in any layer
pair, the OH-groups form the P-interlayer. If all layer types occur with equal probabilities, WAB
= WBC = WCA = WBA = WCB = WAC = 1/6, the conjunction probabilities PABBC = PBCCA = PCAAB
= PBAAC = PCBBA = PACCB = 1 and the other Pij = 0, then the structure will contain
sequences …AB=BC=CA… and symmetrically related …BA=AC=CB…, i.e., two
enantiomorphous 3R1 polytypes.
There are several possibilities for the stacking faults to occur in the 3R1 polytype. For
example, let us consider a defective 3R1 structure, where all interlayers belong to the P-type,
hereafter refered as Model A. In this structure AB layers may be replaced, with some
probability, by AC layers, BC layers, by BA layers, CA layers, by CB layers and viceversa. A
defective structure containing 10% of the defects of the type described should have the
following conjunction probabilities:
PABBC = PBCCA = PCAAB = PBAAC = PCBBA = PACCB = 0.9,

PABBA = PBCCB = PCAAC = PBAAB = PACCA = PCBBC = 0.1,
other PIJ = 0 (I, J = AB, AC, BA, BC, CA, CB).
Pairs AB-BA, BC-CB, CA-AC and so on formed in such defective structure are typical for
the 2H1 polytype. When the proportion of defects increases, the thickness of 2H1 fragment
grows. When the amount of "defects" reaches 100%, the defect-free 2H1 polytype is formed.
Figure 18 shows XRD patterns of both 3R1 and 2H1 polytype, as well as defective 3R1
polytypes with 20 and 50% of the defects in question. Calculations were made for Mg,Al
variety with CO3 interlayer anions (c0 = 7.56 Å). The crystals are disk-shaped, with the
diameter and thickness of 300 Å and 20 layers, respectively. It can be seen that the 11l peaks
preserve their positions and intensities, whereas 10l peaks move toward lower diffraction
angles. With high proportion of defects, peaks 10.10 and 10.11 sink into the background, and
102, 105 and 108 bands become asymmetric because the slow decline in the direction of higher
θ angles.
Figure 18. XRD patterns calculated for 3R1 polytype structures containing stacking faults (Model A). The
legend contains the values for the defect occurrence probability.
The second model for the 3R1 defective structure (Model B) is based on translational
defects. Let us assume that a crystal is built of one kind of layers, e.g. AB layers. Such layers
stacked with the translation t1 = (1/3, 2/3, c0) construct the 3R1 polytype, and the same layers
stacked with the translation t2 = (2/3, 1/3, c0) yield the 3R2 polytype. Indeed, a shift by vector t1
transforms AB layer into BC layer, BC into CA and so on. The same operation with vector t2
transforms AB layer into CA layer. The interlayers between two consecutive layers are of the
P-type and the O-type for translations t1 and t2, respectively. Let us consider t1 translation as
regular and t2 as defective. With low content of these defects, sequences AB-CA=AB typical to
the 2H3 polytype appear. When the amount of defects increases, the size of the 3R1 polytype
fragments decreases and fragments AB-CA=AB are transformed into AB-CA-BC of the 3R2
polytype. The higher the contents of defects, the thicker the stacks of the 3R2 polytype. When
the amount of defects reaches 100%, the structure become the defect-free 3R2 polytype. Figure
19 shows XRD patterns calculated for 20and 50% of defects. The statistical parameters for the
20% defects are W1 = 0.8, P11 = P21 = 0.8 and P12 = P22 = 0.2. Here subscripts 1 and 2 refer to t1
and t2 translations, respectively.
Figure 19. XRD patterns calculated for 3R1 polytype structures containing stacking faults (Model B). The
legend contains the values for the defect occurrence probability
The XRD features noted for the defects in Model B are similar to those observed in Model
A: 11l peaks are insensitive to the defects, whereas 10l move to lower angles. Because the
peaks are shifted in the same direction in both models, it is difficult to reveal the nature of
defects, taking into account only the peak positions, especially in the case of high contents of
defects. The profiles of 10l peaks, however, allows distinction between different defect types.
The 10l peaks in the XRD patterns shown in Figure 19 do not have low-angle tails, and
reflections 10.10 and 10.11 do not disappear but give a common band at about 55° (2θ).
To illustrate this, Table 7 contains data for a synthetic pyroaurite-like phase with Mg:Fe =
4:1. Experimental peak positions were taken from72 and the calculated ones were found as
described in the “Experimental Methods” section. The table demonstrates significant
discrepancy between dexp(10l) and dcal (10l) with dexp(10l) > dcal (10l) and good agreement for
the 11l reflections. Positions of the 00l peaks vary within the experimental error. 2D character
of 10l bands indicates that in this structure the defects are such that all interlayers belong to the
P-type. The same type of an XRD pattern was given in Figure 6 in reference 4 for a Mg,Ga
LDH. The authors fit it with a model that they describe as "fault probability for a specific layer
sequence to be arranged in rombohedral or hexagonal stacking". It was shown above, however,
that 2 rombohedral and 10 hexagonal polytypes are possible among two- and three-layer
structures. Both Models A and B could satisfy the authors' description. The comparison of the
XRD patterns given in reference 4 with the calculated ones presented in Figure 18 shows that
the structure in question should correspond to Model A.
Table 7. Experimental and calculated spacings for a synthetic pyroaurite-like phase with
Mg:Al = 4:1.
hkl d*exp d**cal dcal - dexp

003 7.83 7.83 0.00
006 3.91 3.91 0.00
012 2.65 2.63 -0.02
015 2.37 2.34 -0.03
018 2.02 1.99 -0.03
110 1.56 1.56 0.00
113 1.53 1.53 0.00
116 1.44 1.45 0.01
119 1.34 1.34 0.00
*reference 72.
**a=3.12 Å, c=23.47 Å.
In the same paper another sample having different XRD features (Figure 8 in reference 4)
was described. Its XRD pattern has two peculiarities: first, it contains the 100 superreflection,
second, the 11l subcell reflections have more symmetrical shapes. The authors used another
model of defects, which they describe as "defects of O-type interlayers in 3R polytype". There
are, however, 3 different translations that change the type of interlayers. Therefore it is not clear
which defect types and in what proportion the authors used to fit the experimental pattern of
this sample. The XRD pattern for 50% of defects in Figure 19 shows the same features as the
experimental pattern, so that Model B should apply to this sample. If this is the case, the
author's idea that these stacking faults only slightly change the interactions between interlayer
matter and OHs of brucite-like layers is incorrect. The prismatic configuration seems more
suitable for the triangular carbonate group than the octahedral one. The reason for the presence
of defects corresponding to Model B may be associated with the specific anionic composition
of the interlayer in the sample in question. Its chemical composition shows that most of the
CO32- anions were replaced by NO3- anions, so that the resulting amount of anions is about
twice as that in other samples.
POLYTYPE DIVERSITY OF EXPERIMENTALLY STUDIED LDHS

As it was shown, the main contributor to the diffraction patterns of the polytypes with
disordered cation distribution is the mutual arrangement of brucite-like layers. The
contributions of interlayer anions and H2O molecules are marginal. These results allow us to
consider the XRD patterns calculated for the structural models with the particular chemical
composition and random cation-anion distribution as the “abstract” pictures of the LDH
polytypes and to use them to identify a particular polytype using the experimental XRD data.
Analysis of the polytype diversity in the LDH family and of the factors that control various
structural modifications may be important for studing the relationships between their structure,
composition and properties, rational classification and nomenclature of the compounds.
Polytypes with Interlayer CO 23− - Anions
Natural and synthetic LDHs with interlayer CO32 − - anions are the most common in this
family and have been studied in greater detail than other anion varieties. Out of the large
number of refined structures, not a single variety has one-layer polytype. Refinements of
hydrotalcite34 and pyroaurite38 have shown that their structures are, in the notation described
above, the 3R1 polytype, and that manasseite35 and sjögrenite19 are the 2H1 polytype.
Comparison of the hkl reflection intensities calculated for CO3-bearing polytypes with those
published in the literature for CO3-bearing LDHs has shown that all these varieties belong
either to the 3R1 or 2H1 polytypes. Note that among natural CO3-bearing LDHs, the 3R1
polytype modifications occur more often than 2H1. In addition, the cation composition of the
3R1 minerals is more variable than for 2H1 (Table 1).
Among the large number of synthetic CO3-bearing LDHs, there are no compounds having
the 2H1 polytype. However, Gastuche et al.13 described a synthetic sample which was identified
as a mixture of 3R and 2H polytypes. Indexing of the XRD pattern of this sample shows that it
consists of a mixture of 3R1 and 2H3 polytypes (Table 8). The 2H3 polytype with a = √ 3a0 is
identified by the presence in the XRD pattern diagnostic 113 and 115 reflections (see 103 and
105 peaks in Table 5).
Table 8. Indexing of XRD pattern from an intergrowth of the 3R1 and 2H3 polytypes
(sample 4 in reference 13).
3R1* 2H3**
Iexp dexp (Å) hkl dcal (Å) hkl dcal (Å)
100 7.63 003 7.60 002 7.60
<5 br 4.57 100 4.57 100 4.57
100 3.81 006 3.80 004 3.80
75 br 2.60 111 2.60
10 2.53 009 2.53 006 2.53
27 vbr 2.36 113 2.34
2.26 115 2.285
22 vbr 2.01 115 1.99?
1.91 118 1.937
<5 1.897 00.12 1.900 008 1.900
60 sh 1.523 300 1.524 300 1.524
60 sh 1.493 303 1.494 302 1.494
13 sh 1.415 306 1.415 304 1.415
*a=3.048√ 3 Å = 5.279 Å, c=3*7.60 Å = 22.80 Å
** a=3.048√ 3 Å = 5.279 Å, c=2*7.60 Å = 15.20 Å
Along with the 3R1 polytype with three-dimensional periodicity, many synthetic structures
contain stacking faults whose nature has been discussed above.
There has been uncertainty as to polytype identification of stichtite and reevesite. First
described with a three-layer cell, stichtite35 and reevesite40 were later found to contain
additional reflections that led to doubling of the number of layers in the cell.73 Later it was
found that XRD pattern of a stichtite specimen shows stichtite peaks with three-dimensional
order and peaks from a disordered product of its transformation, which takes place under
exposure to light or X-rays.42 The positions of all experimental reflections of stichtite proper
can be indexed in terms of a three-layer cell instead of a six-layer one, and the peak intensities
of stichtite resemble those of hydrotalcite, suggesting that these two minerals are isostructural.
The same interpretation of the reevesite XRD patterns has shown that this mineral has the 3R1
structure. Recently, Song and Moon12 described natural and synthetic reevesite samples and
showed the existence of the complete solid solution between Fe3+ and Co3+. The XRD patterns
of the reevesite samples contained very broad 10l reflections, whose positions, however, were
close to those characteristic for 3R1. In contrast, the XRD patterns of the Co-rich samples,
along with 00l, contained only 100 and 110 two-dimensional diffraction bands. This means that
natural and synthetic reevesite specimens have the 3R1 structure containing stacking faults,
whereas the synthetic Co-rich samples have turbostratic structures.
SO4-Bearing Polytypes with the Minimum Periodicity C0 = 8.8 Å
Among natural and synthetic SO42- varieties having co = 8.8 Å, only three-layer polytypes
have been described. The synthetic crystalline phase with the composition [Mg3Al](OH)8
1
/2SO4 nH2O has unit cell parameters a = 3.05 Å and c = 25.79 Å = 3*8.6 Å.24 Since the
extinctions typical for rhombohedral structures are observed in the XRD pattern, the choice of
polytypes is limited to 3R1 or 3R2. The reflections 012, 015, and 018 are present in the XRD
diagram while 101, 104, and 107 are missing, indicating that the phase is the 3R1 polytype,
according to the diffraction criteria outlined previously.
Bish21 described two samples of natural takovites in which the carbonate anion was
replaced by the sulfate. The idealized crystal-chemical formula for these products can be
written as (Ni3Al)(OH)8(SO42-)0.5nH2O. XRD patterns of sulfate-treated samples contain basal
reflections with c0 = 8.9 Å at relative humidity < 50%. The XRD pattern of the untreated and
treated samples can be indexed in terms of three-layer hexagonal cells with a = 3.02 Å. The
XRD pattern of the untreated specimen contains strong 10l reflections with l = 2, 5 and 8,
showing that the structure is the R1 polytype. Based on the questionable indexing of the XRD
pattern made in reference 21 for the 8.9 Å phase, Bookin et al.74 concluded that the phase was
the 3R2 polytype. However the reindexing has shown that the reflections in the XRD pattern of
the 8.9 Å sample have another indices, which differ from those of the 3R2 polytype reflections
(Table). It is most likely that the 8.9 Å phase corresponds to the 3H7 polytype because only for
this polytype, the layer sequence AC=CB=BA=AC in the initial 3R1 takovite sample may be
transformed during the anion exchange into AC-AC-BA=ACdue to a displacement of the CB
layer by one third of the long cell diagonal.
Honessite found near a chrome deposit (Unst, Shetland) was mixed with hydrohonessite
and reevesite.27 The three varieties have the same composition of the brucite-like layers,
[Ni2,8Fe1,23+](OH)8, but differ in the interlayer composition, thereby suggesting to the authors a
genetic affinity. Reflections in the honessite XRD pattern were indexed in a cell with a = 3.08 Å
and c = 26.71 Å = 3*8.90 Å. Relative intensities of 10l and 11l reflections identify this phase as
the 3R1 polytype. The same diffraction features were observed for woodwardite from
Saxony.16,50 Therefore, the layer sequence in this mineral corresponds to the 3R1 polytype.
Raade et al.50 described a sample from Lanrion (Greece) as a three-layer mineral related to
woodwardite. It has the formula (ZnCu)2Al(OH)6(SO4)0.53H2O and hexagonal cell parameters:
a = √ 3a0 = 5.306 Å and c = 3*8.92 = 26.77 Å. However, all reflections in the XRD pattern have
l = 3n (Table 2 in reference 50). This means, that the actual structure of the mineral has
one-layer periodicity along the c axis and can be identified as the 1H polytype with a = 3.063 Å
and c = 8.94 Å. Thus SO4-varieties having c0 = 8.9 Å occur not only as three-layers polytypes
but also as the one-layer one.
A three-layer Mg,Al-mineral with interlayer SO42- anions was found mixed with barite
amid products of low-temperature alteration of volcano-sedimentary rocks on a North Atlantic
seamount.48 Reflections in the XRD pattern were indexed in a hexagonal cell with a = 3.05 Å
and c = 26.50 Å = 3*8.83 Å. The presence of peaks violating the rhombohedral lattice
extinctions (reflections with d equal to 2.53 Å and 2.276 Å can be indexed as 103 and 106)
suggests that the sample may be either one of the hexagonal 3H polytypes or a mixture of 1H
and 3R polytypes. In the latter case, the questionable reflections have indices 101 and 102 for
the one-layer cell. The intensities calculated for the 3R1 polytype (Table 5) do not agree with
experimental data for this sample. The 015 and 018 reflections are the most intense among the
calculated peaks, yet they are very weak experimentally, and the 107 reflection is the strongest
among the experimental ones although it has a calculated intensity of zero. Disagreements are
also present between the experimental data and the pattern for the 3R2 polytype. If we assume
that the one-layer polytype is present in the sample, then, along with reflections at 2.53 Å and
2.27 Å, the diffraction pattern should contain equally intense reflections at 2.64 Å, 1.96 Å, and
1.69 Å (Table 3, Column D). Therefore, it appears that the sample is not a mixture of 1H and 3R
polytypes, but probably one of the hexagonal polytypes. Because of a significant amount of
barite in the sample and difficulties in discriminating between the 3H2 and 3H3 polytypes (Table
5), it is difficult to choose unambiguously between them. However, the fact that only two of the
four reflections with (-h+k+l) ≠ 3n are seen in the diffraction pattern in Figure 4a48 favors the
3H2 polytype.
SO4-Bearing Polytypes with the Minimum Periodicity C0 = 11 Å
In contrast to carbonate, the SO4-bearing phases with c0 = 11 Å, as well as the 8.95 Å

variety, included examples of the one-layer polytype. One of them is an unnamed mineral from
Jurassic salt-bearing deposits (Guardak, Central Asia) with brucite-like layers of
[Mg2Al](OH)6.6 The other is hydrohonessite from ore wastes (Otter Shoot, West Australia) with
a cation composition of [Ni2,7Fe2,33+](OH)8.28 Both one-layer minerals are characterized by
similar c0 values (11.16 Å and 10.80 Å, respectively), although their a dimensions are different.
In the Mg,Al-mineral, a = 5.29 Å, indicating an ordered distribution of SO4 tetrahedra in the
interlayer. Al and Mg cations in the brucite-like layers are probably also ordered because
Mg:Al = 2:1 and a = √3a0. In hydrohonessite, interlayer anions are distributed at random and a
= a0 ≈ 3.09 Å.
Motukoreaite was described as a four-layer polytype75 having a = 3a0 = 9.336 Å.

Brindley52 considered it a three-layer non-rhombohedral polytype, and Bookin et al.74 showed
that reflections in the powder XRD pattern perfectly fit a one-layer unit cell with a = 5.28 Å and
c = 11.16 Å. The idealized chemical composition, [Mg2Al](OH)6 1/2 (CO3,SO4) nH2O, and the
XRD pattern of motukoreaite is identical to that of the material from Guardak mentioned above,
suggesting that both specimens may be the same mineral with 1H polytype and ordered SO42-
groups in the interlayers.
There are several multilayer SO4-bearing varieties, shigaite,29 motukoreaite,61
wermlandite11 and Ca,Al-hydroxide,20 whose structures have been refined from single-crystal
diffraction data. However, if these structures are considered from the point of view of layer
stacking, brucite-like layers in these varieties are stacked according to the one-layer polytype
rule.74 It was found that Me2+ and Me3+ octahedra in the brucite-like layers of shigaite and
motukoreaite have ordered distribution with a period equal to √ 3a0, in full agreement with the
layer cation composition. The actual unit cell parameter, a = 3a0, results from specific
distribution of interlayer species. Successive brucite-like layers in shigaite and motukoreaite
are shifted by one third of the cell long diagonal, which is equal to 3√ 3a0. Therefore, in the
projection along the c axis, Me3+-rich and Me2+-rich octahedra of the successive brucite-like
layers coincide, and this layer stacking corresponds to the one-layer polytype. The observed
three-layer periodicity along the c axis is related to the ordered distribution of cations and
anions in successive interlayers of shigaite and motukoreaite in accordance with their
rhombohedral symmetry.
Ca- and Al-octahedra in Ca,Al-hydroxide are significantly distorted and, therefore, the OH
positions of brucite-like layers deviate from the ideal sites in the close-packed stacking by up to
0.4 Å.20 Within this approach, the layer stacking in Ca,Al-hydroxide corresponds to the
one-layer polytype, and the three-layer periodicity is due to the exchange of the positions of the
Ca- and Al-octahedra and SO42- anions.
Wermlandite has a two-layer cell and a = 3a0 ≈ 9.3 Å, which agrees with R2+:R3+ = 7:2.11
The R3+ cations in wermlandite, as well as in shigaite and motukoreaite, are positioned one
above the other along the normal to the layers. The two-layer periodicity in the minerals is
derived from the azimuthal orientation of the dumbbell bases of SO42- anions in the consecutive
interlayers.
Three-layer minerals with c0 ≈ 11 Å have also been reported in the literature. In the XRD
patterns of two samples of sulfate-treated takovite with c = 32.47 Å = 3*10.82 Å and 32.50 Å =
3*10.83 Å, the 012, 015, 018, and 01.11 reflections are stronger than 101, 104, 107, and 10.10,
suggesting the 3R1 polytype.67
Carrboydite, Ni7Al4.5(OH)22(SO4,CO3)2.8 3.7H2O, was discovered in a nickel mine near
Calgary, West Australia, along with a carrboydite-like phase that the authors called the “11Å
phase”.54 Judging from the chemical analysis, carrboydite contains primarily Ni2+ and Al3+ in
the ratio of about 3:2. The authors described the carrboydite structure in terms of a one-layer
cell with c = 10.34 Å and a = 3a0 = 9.14 Å. The model proposed for carrboydite contains
caolingite-like double brucite-like layers sharing the same hydroxyl sheet. Bish21 noted that the
diffraction pattern of SO4-exchanged-takovite looked like those of carrboydite and the "11 Å
phase". Since the cation composition of takovite is similar to that of carrboydite (but with a
smaller proportion of Al), Bish suggested that neither carrboydite nor the "11 Å phase" were
based on the double brucite-like layer model. Based on similarities in the peak intensities
between the "11 Å phase" XRD pattern and the model calculations, Bookin et al.74 suggested
that the "11 Å " phase was composed of single brucite-like layers stacked according to the 3R1
polytype.
In contrast with hydrohonessite from West Australia, which has a one-layer unit cell,28 a
Shetland sample of hydrohonessite was found to have the three-layer cell with c = 33.4 Å =
3*11.1 Å.27 The presence of the 101 reflection and the absence of the 012 reflection
distinguishes the XRD pattern of the Shetland hydrohonessite from that of "11Å phase" of the
same periodicity and suggests that it is the 3R2 polytype.
In addition to 3H2 hydrotalcite with c0 = 8.8 Å, products of low- temperature alteration of
volcano-sedimentary rocks of North Atlantic seamounts were found to contain a three-layer
mineral with c0 = 32.4 Å = 3*10.8 Å.48 Although admixtures interfere with peak intensity
estimates, qualitative analysis of the diffraction pattern (Figure 4b in reference 48) gives
evidence of rhombohedral symmetry and the presence of a reflection with d(012) = 2.605 Å, as
well as intense reflections with d(018) = 2.215 Å and d(01.11) = 1.973 Å, suggest that this
mineral is the 3R1 polytype.
Polytypism of LDH Containing O H − , C l − , and CrO 24− - Anions
The charge compensation in natural and synthetic hydrotalcite-like minerals can be

provided by anions other then SO42- or CO32-. Mascolo and Marino76 described a synthetic
mineral with the composition Mg1-xAlx(OH)2+xnH2O, similar to that of natural meixnerite.22 In
this mineral, hydroxyl groups seem to be the interlayer anions. The unit cell is rhombohedral
with c = 23.0 Å indicating that the structure in question may be similar to three-layer
hydrotalcite. Analysis of the XRD pattern showed that both the positions and relative
intensities of hkl reflections are identical to those of the 3R1 polytype with CO32- anions in
interlayers, which implies the same layer stacking as in meixnerite.
Pausch et al.15 synthesized OH-bearing LDHs in the system MgO-Al2O3-H2O at pH2O = 1
kbar and T = 100-350ºC. Hydrotalcite-like specimens have the x values between 0.25 and 0.44.
At higher temperature and at higher level of Al, the so-called disordered HP phase was formed.
The XRD pattern of the first phase is identical of that of 3R1 hydrotalcite, whereas the XRD
pattern of HP contained broad 10l and sharp 00l and 11l reflections. Pausch et al.15 concluded
that HP is a transition phase between hydrotalcite and manasseite because its XRD pattern
differ from that of natural hydrotalcite. Table 9 contains the intensities and spacings of
reflections recorded for HP synthesized at x = 0.25, T = 150°C and p = 1 kbar. For this phase, c0
= 7.40 Å and a0 = 3.04 Å. Attempts were made to index the XRD reflections on the basis of
hexagonal cells with c = n*7.40 Å. Comparison of the experimental d(hkl) values with the
calculated ones shows that the best agreement is achieved for n = 3 and a = a0√ 3 = 5.265 Å
(Table 9). The presence of 10l reflections with l = 3n + 1 suggests that the HP phase is the 3R2
polytype. The incorporation of interlayer hydroxyls in O-type interlayers of the HP phase is
likely to result in a cubic stacking sequence formed by nearest OH-groups of the neighboring
layers and the interlayer OH-groups. In P-type interlayers of hydrotalcite-like compounds,
interlayer OH-groups and the nearest OHs of the adjacent layers are positioned at the same
normal to the (001) plane.
Table 9. Indexing of the experimental XRD pattern of the synthetic HP sample obtained in
reference 15.
hkl dexp dcal*

003 7.40 7.40
006 3.71 3.70
111 2.61 2.614
114 2.37 2.378
117 2.00 2.025
11.10 1.68 1.697
300 1.52 1.520
303 1.49 1.489
a=3.04√ 3 Å = 5.265 Å, c=3*7.40 Å = 22.20 Å
Refinement of chlormagaluminite (MgFe2+)4Al2(OH)12[Cl(CO3)0.5]22H2O showed that its

structure is the 2H1 polytype.26 In contrast, the powder XRD pattern of iowaite
Mg4Fe13+(OH)10Cl1 nH2O 76 contains strong 012, 015 and 018 reflections that are diagnostic for
the 3R1 polytype.51 Both polytype modifications have the same type of interlayers, which
provides an opportunity for identical local environment for interlayer Cl anions.
Diffraction data for a synthetic Al-Mg-phase containing interlayer CrO42--anions24 are
practically identical to those for the SO4-bearing phase prepared in the same work and
discussed above. Hence, it probably is the 3R1 polytype.
Multilayer Polytypes with Interstratified Interlayers of Different

Composition
Arakcheeva et al.37 refined the crystal structure of a manasseite-like mineral of the

composition (Mg4Al2)(OH)12CO32- 3H2O. The parameters of the hexagonal unit cell are a = √
3a0 = 5.28 Å, c = 2c0 = 15.15 Å, space group P 6 2m. In the crystal structure, adjacent layers are
rotated with respect to each other by 180° and their surface OH groups form P-type interlayers.
However, in contrast to manasseite, in which each interlayer contains the same content of CO32-
anions and water molecules, adjacent interlayers in the structure in question have different
compositions: one of them is filled by carbonate anions and the other contains H2O molecules.
As in manasseite interlayers, each O atom of the interlayer net is located just above and below
the nearest OH groups of the neighboring brucite layers.
Therefore, in terms of close packing, the sequence of the layer and interlayer atoms can be
denoted as AbCCCO3CbAAH2OAbC where CCO3 and AH2O are the sites for oxygen atoms of
CO3 and H2O, respectively. Both brucite-like layers and interlayer spaces are bound by
hydrogen bonds, in which the acceptors are oxygen atoms of the interlayer CO3 anions and H2O
molecules. Note that in the structure, the C atoms of the interlayer CO3 anions are distributed in
accordance with the layer period of √ 3a0. Taking into account that the C atoms and layer
cations are located on the same lattice rows parallel to [001] and that Mg:Al = 2:1, Arakcheeva
et al.37 supposed that Al cations in the brucite-like layers are distributed with the same
periodicity and each Al is surrounded by six Mg-octahedra. However, this assumption does not
agree with the same values for the mean bond lengths for non-equivalent octahedra equal to
2.04 Å and 2.05 Å, respectively.
In the Caspian depression salt-bearing deposits (Inder dome), a mineral was discovered
with regularly alternating SO4- and CO3-bearing interlayers and rhombohedral cell parameters
a = 3.05 Å and c = 55.62 Å.6 Its crystal-chemical formula is
[Mg4Al2(OH)12](CO3)0.5(SO4)0.5 nH2O. This phase can be regarded as a mixed-layer mineral
with regularly alternating CO3- and SO4-bearing interlayers whose thicknesses are 7.56 Å and
10.98 Å, respectively, resulting in the total thickness of two layers, c0 = 18.54 Å. These layer
pairs are stacked according to the rhombohedral law to produce a six-layer cell with c = 3c0 =
55.62 Å. Since the possible polytype for this phase is limited only to rhombohedral structures, it
can be described by one of the sequences 6R1 to 6R5. In fact, nine different structural models
should be considered, since polytypes with alternating types of interlayers (6R2, 6R3, and 6R4)
should give two different XRD patterns, each depending on the spacings of P- and O-type
interlayers. Table 10 lists the experimental d-values and peak intensities and the results of the
calculation for the 6R4 polytype, in which O-type interlayers are occupied by sulphate groups
and P-type interlayers are occupied by carbonate groups.
The Main Crystal Chemical Features of LDH Polytypes
The range of the diversity in LDH polytypes depends on the nature of the interlayer cation.
Structural studies show that, as a rule, CO32- anions are positioned in the interlayer so as to have
their oxygens forming hydrogen bonds with OH-groups of the adjacent brucite-like layers.65
This can be easily achieved only in structures with P-interlayers where oxygen atoms of the
CO32- anion are positioned at equal distances from the OH-sheets near the straight lines that join
hydroxyls of the adjacent layers (Figure 11a). This explains why the one-layer polytype with
O-type interlayers has not been found among CO3-bearing minerals, and why, among all the
two- and three-layer varieties, two structures 3R1 and 2H1 having P-type interlayers prevail.
New indexing of the XRD patterns from CO3-bearing samples described by Frondel43 and
Gaustiche et al.13 shows that the 2H3 polytype, in which P- and O-type interlayers alternate, can
also exist. Theoretically, nine hexagonal six-layer varieties with P-interlayers are possible as
well, but six-layer polytypes have not been found among CO3-varieties.
The above holds true for other anions arranged in a 2D triangle (e.g., NO3-). A similar
conclusion, supported by a smaller number of experimentally verified examples, follows for
LDHs with halogen anions and hydroxyls. In terms of crystal chemistry, it is not clear, why
such anions would be positioned over OH-groups of the brucite-like layers instead of over the
layer cations. Remarkably, at high T and x, the OH-bearing disordered Mg,Al phase was
crystallized as the 3R2 polytype having O-type interlayers. It is likely that stacking faults in
some synthetic LDHs with NO3-, Cl-, and OH- anions may form O-type interlayers.
Although the natural and synthetic CO3-bearing 3R1 and 2H1 polytypes have the same
P-type interlayers, they differ in occurrence. For example, most synthetic LDHs, independent
of their layer cation composition, are 3R1. Among natural CO3-bearing LDHs, the 3R1 polytype
also prevails although findings of the 2H1 are described (Table 1).
Table 10. Experimental (exp) and calculated (cal) peak positions and intensities of the
6R4-hydrotalcite XRD diagram.
hkl dexp (Å) dcal* (Å) Iexp** Ical

003 18.54 18.54 15 33
006 9.27 9.270 100 100
009 6.18 6.180 33 23
00.12 4.64 4.635 8 3
00.15 3.706 3.708 46 34
00.18 3.090 0
00.21 2.649 2.649 1 1
101 2.635 0
012 2.629 2.626 2 2
104 2.592 2.592 11 9
015 2.567 0
107 2.505 2.504 5 5
018 2.461 2.466 2 0
10.10 2.386 2.383 4 3
01.11 2.339 1
10.13 2.246 2.245 7 4
01.14 1.198 0
10.16 2.101 0
01.17 2.006 2.054 <1 1
10.19 1.961 1.960 8 14
01.20 1.914 0
10.22 1.827 1.825 1 3
01.23 1.784 1.783 1 1
10.25 1.704 1.701 1 2
01.26 1.761 1.662 1 4
10.28 1.587 1
01.29 1.551 1
110 1.523 1.523 4 7
113 1.518 0
116 1.503 1.503 3 1
119 1.479 1.478 1 1
11.12 1.452 1.447 <1 0
*a=3.064 Å, c=55.62 Å
**Intensities of basal reflections were measured on the diagram of oriented film and normalized to 100%.
Intensities of other reflections were measured on the diagram of randomly oriented sample and
normalized to fit alculated pattern.
Moreover, among the 2H1 polytypes, the varieties with Me2+/Me3+ = 3 occur more often
than those with Me2+/Me3+ = 2. One of the possible explanation is that despite the identical
local hydroxyl environment of CO32- anions in the P-type interlayers of the 3R1 and 2H1
polytypes, they differ in two essential features, which become clear from the symbolic
notations:
2H1
AbCCbAAbC…
AbCCaBBcAAbC… 3R1
First, the polytypes have different azimuthal orientations of the brucite-like layers:
adjacent layers in the 2H1 polytype are rotated by 180° with respect to each other, whereas in
the 3R1 polytype, all layers have the same orientation. Second, the polytypes differ in the
mutual arrangement of the layer cations. In the 2H1 polytype, the layer cations are positioned at
the same close packing sites, that is, on the same lines parallel to [001] whereas in the 3R1
polytype, the layer cations within the cell do not overlap but are located in the successive layers
in accordance with the cubic close packing sequence. In other words, the layer cation
distribution in the 3R1 structure is more homogeneous than that in the 2H1 polytype. The more
screened electrostatic layer cation interaction is therefore one of the factors that favor the
crystallization of the 3R1 modification. The less frequent occurrence of the 2H1 polytype with
Me2+:Me3+ = 2:1 is in agreement with this assumption, because an increase in the amount of
trivalent cations in brucite-like layers should increase their electrostatic interaction. Allman
and Lohse78 and Allman38 assumed that the 3R1 polytype is stable at lower temperatures,
whereas the 2H1 modification requires higher energy for its crystallization. This assumption
seems to be in agreement with the structural features of the 2H1 and 3R1 polytypes described.
Hofmeister and von Platen68 noted that the substitution of divalent for trivalent cations is
accompanied by a distinct change of polarization of the hydroxyl environment. This factor also
can play a negative role in the 2H1 polytype formation.
If the interlayer contains tetrahedral SO42- and CrO42- anions, the polytype diversity
increases dramatically. The reason is that basal oxygens of SO42- or CrO42- tetrahedra can form
hydrogen bonds with hydroxyls of either the upper or the lower interlayer surface, Figure 1. If
the position of the tetrahedral base with respect to the brucite-like layer’s hydroxyl sheet is rigid
enough, the apical oxygens are bound to the hydroxyls of the adjacent sheet of this interlayer
through water molecules. This allows the next brucite-like layer to have a different position
relative to the apical oxygens of the tetrahedra and relative to the preceding layer. As a result,
the minerals containing these anions may form structures with both P- and O-type interlayers.
Table 11 lists the polytype data for the SO42- varieties described. These data suggest that
neither the chemical composition of brucite-like layers nor the degree of hydration affect the
type of interlayer of the polytype. Mg,Al-varieties were assigned to four structural modification
because each of 8.85 Å and 11.0 Å phases has one O- and one P-interlayer variety. The 3R1
polytype with c0 = 8.6 Å can be regarded as the dehydration product of the 1H or 3R1 varieties
with c0 = 11.0 Å, whereas the 2H2 polytype cannot be derived from these polytypes solely by
layer displacement due to dehydration. The two hydrohonessites in Table 2 have similar cation
compositions in the brucite-like layers and O-type interlayers, although they differ in the
number of layers in the unit cell. Two different hydrated varieties of SO42- -exchanged takovite
retain the three-layer periodicity of the original takovite, but have different mutual layer
arrangements and different interlayer types. We must assume, therefore, that the polytype
modification, even under the most common conditions of hydration-dehydration, is determined
by the thermodynamic parameters of the medium rather than by those of the mineral phase.
Order-Disorder in Cation Distribution Long-Range Order
Determination of the long- and short-range order in cation distribution is one of the
important and complex problems in crystal-chemical study of natural and synthetic LDHs.
From the practical point of view, ordered or segregated modes in cation distribution in LDHs
are critical to obtain, upon decomposition, mixed oxides with a homogeneous cation
distribution. At present, there are contradictory notions concerning order-disorder in cation
distribution in the actual crystal structure of natural and synthetic LDHs.
Hofmeister and von Platen68 postulated that most LDH structures have complete order in
cation distribution but this order is not easy to reveal, since superreflections are hidden because
of high pseudosymmetry, stacking faults and other structural imperfections. The following
crystal chemical arguments were used to justify the validity of this postulate:
- Stoichiometry in natural and synthetic compounds normally implies fixed ratios of

Me2+:Me3+ equal to 2:1 and 3:1. The Me2+:Me3+ = 2:1 corresponds to the upper limit for
compounds crystallizing under normal temperature and pressure.
- In ionic structures with Me2+ and Me3+ cations having the same next-neighbor topology,
a direct contact between Me3+ coordination octahedra should not occur according to the
Pauling’s rules.
- Cations with typical Jahn-Teller distortion of their coordination polyhedra, like Me3+ and
Cu2+, are not expected to be randomly distributed, with cations preferring a more
symmetrical crystal field character.
Theoretically, these arguments strongly support the idea of complete cation order,
especially when Me2+:Me3+ = 2:1. However, there is, as a rule, no direct evidence of cation
ordering in fine-dispersed LDHs in diffraction data because powder XRD patterns of most
LDHs do not contain superreflections. In order to confirm their point of view and to explain the
observed diffraction effects, Hofmeister and von Platen68 calculated powder XRD patterns for
the 3R1 and 2H1 polytypes having ordered and random cation distributions. The results of these
calculations have been described above and here we shall only emphasize the main conclusion:
for the Mg,Al system, it is practically impossible to differentiate CO3-bearing LDHs with
random or order cation distribution using powder XRD, because the intensities of
superreflections are extremely small. For cations whose scattering powers substantially differ
from each other, superreflection intensities could be comparable with those of the sub-cell
reflections. However, these reflections are absent not only in powder, but also in single-crystal
XRD patterns of pyroaurites and sjögrenites. Hofmeister and von Platen explained their
absence by structural imperfections and intergrowth of structural fragments having Me2+:Me3+
ratios 3:1 and 2:1. These general considerations, however, were not supported by convincing
argumentation. For example, intergrowth should disturb stoichiometry observed for sjögrenites
and pyroaurites, and the intensity of 100 superreflection does not depend on the layer stacking
if cation distribution within the brucite-like layers is completely ordered.
Table 11. Polytype diversity of SO4-bearing LDHs.
Mineral Brucite-like layers composition c0 (Å) Layer sequence Polytype Inter-layer type
Synthetic hydrotalcite Mg3Al(OH)8 8.6 ...AC=CB=BA=AC... 3R1 P
Woodwardite (Cu,Al)(OH)2 8.43 ...AC=CB=BA=AC... 3R1 P
SO4-takovite Ni3Al(OH)8 8.9 ...AC-AC-BA=AC... 3H7 mixed
SO4-hydrotalcite (N. Atlantic) Mg3Al1(OH)8 8.8 AC-AB-CB-AC... 3H2 O
Ca, AL hydroxide Ca2Al(OH)6 8.9 AC-AC... 1H* O
Woodwardite-related mineral (ZnCu)4Al2(OH)6 8.92 ...AC-AC... 1H O
SO4-hydrotalcite (M. Asia) (Mg4Al2)(OH)12 11.2 ...AC-AC... 1H O
Hydrohonessite (W. Australia) (Ni2.7Fe1.33+)(OH)8 10.8 ...AC-AC... 1H O
Wermlandite (Mg7(Al,Fe3+)2(OH)18 11.3 ...AC-AC... 1H** O
Motukoreaite (Mg5.6Al3.4)(OH)18 11.17 ...AC-AC... 1H* O
Shigaite (Mg2Al1)(OH)6 11.02 ...AC-AC... 1H* O
Hydrowoodwardite (Cu1-xAlx)(OH)2 10.63 ...AC=CB=BA=AC... 3R1 P
SO4-hydrotalcite (N. Atlantica) (Mg3Al)(OH)8 10.8 ...AC=CB=BA=AC... 3R1 P
Carrboydite (Ni3Al2)(OH)10 10.3 ...AC-AC... 1H O
Hydrohonessite (Ni2.7Fe1.3)(OH)8 11.1 ...AC-BA-CB-AC... 3R2 O
Glaucocerinite ((Zn,Cu)5Al3)(OH)16 10.88 ...AC=CB=BA=AC... 3R1 P
*Real polytype has three-layer periodicity
**Real polytype has two-layer periodicity
Bellotto et al.4 proposed a different point of view to account for the long-range cation
ordering in natural and synthetic LDHs with different Me2+:Me3+ ratios. They investigated
crystal-chemical features of synthetic CO3-bearing compounds using the Rietveld structure
refinement technique and some other diffraction and spectroscopic methods. The XRD patterns
of the Mg,Al LDH, with Mg:Al ratios equal to 2.0 and 5.0, were characterized by a high
structural order, that is, their structures did not contain stacking faults. The crystal structure of
these compounds was, therefore, refined by the Rietveld technique, and the results did not
reveal any trace of cation order even for the compound with Mg:Al = 2:1. In contrast, the
compounds synthesized in Mg,Ga and Ni,Al systems with Me2+:Me3+ = 2.0, 2.5 and 5.0
contained significant amount of stacking faults. Among these phases, only one with Mg:Ga =
2:1 was characterized by a supercell with a = √3a0 as indicated by the 100 reflection at 4.63 Å.
The following crystal chemical interpretation of the observed diffraction data was proposed in
reference 4. As was mentioned, one of the common structural features of LDHs is the flattening
of the brucite-like layers along the c axis and their expansion along the plane. The authors
assume that the compression of the layers is limited by the close approach of oxygen atoms
along shared octahedral edges. To make this clear, they compared the shared OH-OH distances
and layer thicknesses for brucite, dioctahedral gibbsite and the refined Mg,Al compounds. For
brucite, the OH-OH distance is 2.785 Å and the layer thickness is 2.113 Å, whereas these
parameters for gibbsite are 2.635 Å and 2.05 Å, respectively. According to Belloto et al.,4 the
value 2.635 Å should be critical because it corresponds to Al3+ octahedral shared-edges length.
For the studied Mg,Al compounds, the Rietveld refinement shows that, for the phase with
Mg:Al equal to 5 and 2, the layer thickness is 2.001 Å and 1.959 Å, respectively. As a result, the
shared OH-OH lengths are 2.676 Å for Mg:Al = 5 and 2.632 Å for Mg:Al = 2. Thus disordered
cation distribution for the compound with Mg:Al = 2 preserves the layer distortion brought
about by the ordering process. In contrast to the Mg,Al system, cation ordering can occur in
Me2+, Me3+ systems when the cations have similar ionic radii as for Mg:Ga = 2. In this case, the
ordering does not lead to major distortions of octahedra and further decrease in the OH-OH
distances. According to the Rietveld refinement, in the Mg,Ga compound with Mg:Ga = 2,
Ga-O and Mg-O distances of 1.95-1.90 Å and 2.02 Å, respectively, are rather close, and
ordering is possible.
In the light of the calculations described above, these results can be explained by the fact
that the 100 superreflection should be extremely weak for the Mg,Al compound even for
Mg:Al = 2:1, whereas its intensity should be significant for the Mg,Ga compound with Mg:Ga
= 2 because scattering power of Ga is higher than that of Al.
Precise refinement of the shigaite crystal structure29 has shown that neither is the
brucite-like layer flattening a decisive factor responsible for the cation ordering. In this mineral,
Mn:Al = 2:1 and complete cation ordering takes place, whereas the shared octahedral edges
(2.586-2.610 Å) are significantly shorter than those in gibbsite (2.635 Å) and in Mg,Al
hydrocarbonate (2.632 Å).
In order to evaluate the role of various factors responsible for the cation ordering and its
being displayed in diffraction effects, it is useful to analyze the literature data available (Table
1). Among synthetic LDHs, cation ordering is determined unambiguously only for two
varieties. The single crystal refinement of Ca,Al hydroxide shows that Ca and Al are ordered in
accordance with Ca:Al = 2 when each Al is surrounded by six nearest Ca cations and
edge-shared Al-Al octahedra are absent.20 The reason for superperiodicity in synthetic
Al,Li-hydrocarbonate is that Li occupies the gibbsite large vacant octahedra distributed as in all
dioctahedral species with a ≈ 5.1 Å.
Single crystal refinements of shigaite,20 motukoreaite61 and wermlandite11 have provided
significant insight into the relationships between cation ordering and supercells revealed by
diffraction methods. These minerals have the same hexagonal layer cells with a = 3a0 but
different Me2+:Me3+ ratios (Table 1). As mentioned above, Mn and Al cations in the brucite-like
layers of shigaite are distributed among the layer lattice nodes with a = √3a0 in accordance with
Mn:Al = 2:1 found for this mineral. The observed 3a0 layer periodicity is related to the ordered
distribution of interlayer cation octahedra and sulfate anions. Similar features were observed
for motukoreaite. In this mineral, the non-stoichiometric cation composition of the brucite-like
layers Mg5.6Al3.4 (x = 0.38) is closer to Me2+:Me3+ = 2:1 and therefore a supercell with √3a0
should be expected. Indeed, the refinement has shown that motukoreaite has the same cation
ordering as that in shigaite, whereas interlayer SO42- anions and Na cations coordinated by six
water molecules are distributed with a = 3a0.
In wermlandite, the contents of Al and Fe3+ cations in the brucite-like layers correspond to
x = 0.22. This value is intermediate between x = 0.25 (expected parameter √3a0) and x = 0.20
(expected parameter √5a0). The refinement has shown that the cation ordering in wermlandite
forms a supercell with a = 3a0 and the cation composition of the unit cell corresponds to the
cation ratio Mg:(Al,Fe3+) = 7:2, observed in this mineral.
Recently Chao and Gault36 described a group of new carbonate minerals with the general
formula Me42+Al2(OH)12CO33H2O (Me2+ = Mg2+, Fe2+, Mn2+) (Table 1). Their single crystal
XRD patterns contain superreflections corresponding to a layer hexagonal supercell with a =
2√3a0. Chao and Gault supposed that these superreflections strongly suggest the presence of
cation ordering. They found that the superreflections are weaker for the Mg,Al varieties than
for the Mn,Al and Fe,Al ones. This fact supports the idea about the cation ordering. However,
the actual distribution of the layer cations and interlayer anions in the minerals remains unclear.
Moreover, Arakcheeva et al.37 refined the structure of the Mg4Al2(OH)12CO33H2O single
crystals, which were taken from the same location (Sao Paulo, Brazil) where single crystals
described in reference 36 were found. Initially, Arakcheeva et al. indexed the X-ray reflections
using the unit cell with parameter a = 2√3a0 = 10.56 Å proposed in reference 36. However, h
and k indices for the experimental reflections have only even values indicating that a = √3a0.
Probably, a careful single crystal structure refinement of the minerals described in references
36 and 37 will show that, at least, their isomorphous cations are distributed with a = √3a0 as it
was found in shigaite.
In contrast to minerals mentioned above, cation ordering was not revealed for
desautelsite,45 pyroaurite19 and sjögrenite19 even by single crystal XRD. These minerals have
stoichiometric cation compositions with Me2+:Me 3+ = 3:1 and the isomorphous cations have
quite different scattering powers. Therefore, one may expect that these cations should be
distributed with a = 2a0 (Figure 4.c). Single crystal XRD patterns of these minerals, however,
do not contain even traces of superreflections. This means that, within the average basic unit
cells of desaudelsite, pyroaurite and sjögrenite, Me2+ and Me3+ cations are randomly
distributed.
Thus the analysis of the single crystal XRD studies of LDHs allows us to make some
general conclusions concerning the nature of the layer superperiodicity in their structures. First,
the actual superperiodicity does not always imply the cation ordering because it is determined
by the superposition of the layer cation and interlayer anion order. Second, it is quite likely that
single crystals of LDHs with Me2+:Me3+ = 2:1 are characterized by complete cation ordering
with √3a0, whereas the layer cation order may be absent even in LDHs having strictly
stoichiometric cation composition if Me2+:Me3+ = n > 2. In general, without structural
refinement, even single crystal XRD patterns cannot provide an unambiguous interpretation for
the observed superreflections.
Powder XRD has significantly lower sensitivity to cation-anion ordering in LDHs.
However, if powder XRD patterns contain superreflections, then one may assume that most
crystallites have either the layer cation or interlayer anion or both cation-anion order. Among
natural LDHs there is only one example of a mineral of the composition (Mg4Al2)(OH)12(SO4)
6H2O, whose powder XRD pattern contains a strong 100 superreflection with d(100) = 4.5 Å
corresponding to a supercell with a = √3a0.6 Because Mg and Al have similar scattering powers,
the origin of the superreflection is related to the ordered distribution of interlayer SO42- anions.
It is likely, however, that the S atoms and the layer Al cations are located above/below each
other indicating that Mg and Al cations in the brucite-like layer are distributed with the same
order as the interlayer SO42-.
Nickel and Clark54 found a = √3a0 for carrboydite but the revision of the experimental
XRD pattern has shown that the reflections can be indexed in terms of the unit cell with a0 =
3.02 Å and c0 = 10.34 Å. Supercells found for stichtite and reevesite have not been determined
unambiguously because reflections additional to those of the basic cell may be related to
products of these mineral transformation under X-ray or light action.74 Among synthetic LDHs,
it is also only one example of a sample with cation composition Mg2Ga and a = √3a0 that has
been described in reference 4.
In general, powder XRD of natural and synthetic LDHs, independent of their cation
composition, contain only hkl reflections corresponding to the basic unit cell. Probably,
complete cation ordering depends not only on the Me2+:Me3+ ratio, but also on LDH
crystallization conditions. Conditions providing the growth of LDH single crystals seem to be
more preferable for the cation order than those promoting formation of fine-dispersed LDHs,
even if in both cases, the Me2+:Me3+ = 2:1. Crystallization of fine-dispersed LDHs is likely to
be accompanied by some heterogeneity of individual particles, which can differ from each
other either in order-disorder in cation distribution due to the presence of
Me3+-Me2+-Me2+-Me3+ and Me3+-Me2+-Me3+ cation subsequences or in the deviation from
stoichiometry (Me2+:Me3+ ≥ 2). As it was shown, both factors significantly decrease the
intensity of the diagnostic 100 reflection. Therefore, the absence of the 100 reflection in
powder XRD patterns does not indicate that the studied LDHs are characterized by random
cation distribution - it means only that the long-range cation order is not perfect.
Short-Range Cation Order
The application of spectroscopic methods provides essentially new information concerning

short-range cation order. For example, Hernández-Moreno et al.79 used IR spectra to analyze
cation distribution in LDHs with Me2+/Me3+ equal to 2.0 and 3.0. They found that the OH
stretching vibration bands for the Me2+/Me3+ = 2.0 compounds are more narrow than those for
the Me2+:Me3+ = 3:1 ones. Based on these observations, the authors concluded that octahedral
cation order is only present in the Me2+:Me3+ = 2:1 structures, whereas for those with
Me2+:Me3+ > 2, the brucite-like layers are disordered, although there may be local cation order
resulting from cation segregation. Unfortunately, there are few publications devoted to the IR
study of the local cation order, but even in these papers, the analysis was confined to a
qualitative level.
X-ray absorption spectroscopy (XAS) is another powerful method for the study of
short-range cation order. It probes the local structure around an absorbing atom and provides
excellent conditions to analyze the numbers and types of the cations nearest to the chosen
atoms. Vucelic et al.72 used this technique to determine the effect of Fe content on Fe3+ cation
ordering using three synthetic pyroaurite-like samples with Mg/Fe3+ equal to 2, 3 and 4,
respectively. Note that powder XRD patterns of all the three samples contain sharp and intense
00l and 11l reflections and rather weak and broadened 10l ones. The reflections were indexed in
terms of the basic three-layer unit cells. The most impressive result of this work is that, in all
the specimens, Fe3+ cations have only Mg cations as the nearest neighbors. One has to
emphasize that it is possible to distinguish a relatively low content of Fe3+ in the first cation
shell, certainly as low as 5%. Remarkably, edge-shared Fe3+-Fe3+ octahedra are absent in the
structure with Mg:Fe3+ = 2:1, whereas the XRD pattern of this sample contains only the basic
unit cell reflections. At first sight, this result looks rather confusing because the cation
composition with Mg:Fe3+ = 2:1 and local cation arrangement around Fe3+ cations provide
conditions for the ordered distribution of Mg and Fe3+ with a = √3a0. However, as follows from
the calculations given above, even a small deviation from the ideal Fe3+-Mg-Mg-Fe3+
alternation is accompanied by a dramatic decrease in the 100 superreflection intensity.
NATURAL AND SYNTHETIC LDHS WITH UNUSUAL STRUCTURAL

FEATURES
Coalingite
Mumpton et al.80 were the first to find a mineral of the composition

Mg10Fe2(OH)24CO32H2O in the New Iria, California, named coalingite. Later, coalingite was
described in the Makox Intrusion, Canada, by Jambor.81 In addition, Mumpton et al.80 also
described a variety called coalingite-K, which closely resembled coalingite, but had a
significantly different XRD pattern. These investigations provided information on optical,
XRD, IR and thermal properties of coalingite and coalingite-K. Pastor-Rodríguez and Taylor44
found that the mineral has a hexagonal unit cell with a = 3.12 Å and c = 3*12.47 Å = 37.4 Å and
space group R 3 m. The coalingite structure consists of structural units 12.5 Å thick, each of
which contains two brucite-like layers and an interlayer with CO32- anions and H2O molecules.
The structural units successive along the c axis are shifted by one third of the layer long
diagonal to form the 3R1 polytype. It was assumed that Mg and Fe3+, as well as CO32- and H2O,
are randomly distributed among available structural sites. The two brucite layers in each pair
are packed together as in brucite. Within each of CO3- and H2O-bearing interlayers, the oxygen
atoms are located in the same positions as in the 3R1 hydrotalcite. Thus, the sequence of the
layer and interlayer atoms in the coalingite structure can be denoted, in terms of close packing,
as
AbCAbCC0CaBCaBB0BcABcAA0AbCAbC...
where C0, B0 and A0 are the sites of oxygen atoms of the interlayer CO32- and H2O molecules. If
we assume that the unit cell of each brucite layer has the composition (Mg5/6Fe3+1/6)(OH)2, then
a pair of such layers has (Mg5/3Fe1/3)(OH)4 and the idealized chemical composition of the
coalingite cell should be (Mg5Fe13+)(OH)12(CO32-)1/2·3H2O, in full agreement with the
chemical composition of the mineral. Pastor-Rodríguez and Taylor44 supposed that the main
structural unit of coalingite-K consist of three brucite-like layers separated by CO3 anions and
H2O molecules. The repeat distance along the c axis should be 17.2 Å and the idealized
chemical composition, (Mg16Fe23+)(OH)36(CO3)·2H2O. In the actual structure of coalingite-K,
the 17.2 Å structural units are interstratificated with small amount of the 12.5 Å ones.
Structures with Vacancy-Containing Brucite-Like Layers
If the cation composition of brucite-like layers is confined to divalent cations, then the
surplus layer charge is provided by the layer octahedral vacant sites. In this case, two
tetrahedrally coordinated divalent metal cations are located just above and below the triangular
bases of each vacant octahedron. Such a cation configuration has an excessive positive charge.
Incorporation of anions into the interlayers compensates the layer positive charge and oxygen
atoms of the anions serve to complete the tetrahedral coordination of the interlayer cations
located above and below vacant octahedra. The electrostatic interaction between layers and
anions as well as the hydrogen bonds formed between interlayer anions, water molecules and
layer hydroxyls stabilize this structure. Hydrozincite, [Zn22+]4+[Ζn2 1(OH)6]2-(CO32-) and zinc
hydroxide nitrate [Zn22+]4+[Zn32+ 1(OH)8]2-(NO3-)22- have similar structures with octahedral Zn
cations in the brucite-like layers and tetrahedral Zn cations in the interlayers. Three oxygen
atoms forming upper or lower roofs of the vacant octahedron serve as the base for the
Zn-tetrahedron, whereas the fourth oxygen atom is provided by CO3 or NO3 anions.81-83
Mooreite, lawsonbauerite and torreite also consist of Mg- and Mn2+-bearing brucite-like
layers containing vacant octahedral sites.45,84,85 In mooreite layers, two of the eleven possible
octahedral sites are vacant, and two of the nine sites are vacant in lawsonbauerite and terreyite.
In all the structures, tetrahedrally coordinated Zn cations are located above and below the layer
vacant octahedra. Thus the cation composition of the brucite-like layers and related Zn cations
can be written as
{[Zn42+]8+[(Mg,Mn)92(OH)22]4-}4- -mooreite
{[Zn42+]8+[(Mn,Mg)72(OH)18]4-}4- -lawsoubauerite
{[Zn42+]8+[(Mg,Mn)72(OH)18]4-}4- -torreyite
Note that Mn-rich lawsoubauerite is isostructural to Mg-rich torreyite.

The interlayer composition of these minerals, [SO42-(Mn,Mg)1(OH)2(H2O)4]24- consists of
SO42- anions and Mn,Mg cations octahedrally coordinated to two OH groups and four H2O
molecules. The octahedron is oriented with its two faces parallel to the (001) plane. The two
OH-groups are shared with the Zn tetrahedra on adjacent brucite-like layers, linking the layers.
A detailed structure study of the compounds described was feasible because they are
formed as single crystals. However, among synthetic anion-exchangeable layered compounds
there is a group of layered hydroxyl double salts (HDSs) which are poorly crystallized and have
turbostratic structures.32,86 Therefore, the structural investigation of these materials by powder
XRD is ineffective. Under these conditions, the only way to obtain structural information is to
apply spectroscopic methods, which are sensitive to local structural order-disorder irrespective
of the materials' crystallinity. For example, Choy et al.86 successfully used X-ray absorption
spectroscopy (XAS) for the study of synthetic Ni,Zn hydroxyl double salts,
Ni1-xZn2x(OH)2(CH3CO2)2x nH2O prepared by both hydrothermal and coprecipitation methods.
The main advantage of the method is that it allows determination of the number and the type of
atoms forming the first and the second coordination spheres around absorbing atoms. In
particular, analysis of the Ni and Zn K-edge spectra shows that the brucite layers contain
octahedrally coordinated Ni and vacancies, whereas the Zn cations are located just above and
below the vacant octahedra. The latter cations are coordinated by three oxygen-atoms groups
formed by the vacant octahedra bases and oxygen atoms of the acetate ligands. In full
agreement with the structural model described, it was found that interatomic distances Me-O
and the first coordination numbers are equal to 2.060 Å and 6 for the Ni cations and 1.96 Å and
3.7 for the Zn cation. The structural formulae for the hydrothermally treated and coprecipitated
product can be represented as:
[Zn0.36]0.72+[(Ni0.82)(OH)2]0.36-(CH3CO2)0.300.30-(OH)0.060.06-(H2O)0.91
[Zn0.52]1.04+[(Ni0.76)(OH)2]0.52-(CH3CO2)0.420.42-(OH)0.100.10-(H2O)1.06
LDHs with Silicate Anions in the Interlayers
Schutz and Biloen25 used synthetic (Mg3Al)(OH)8Cl-·nH2O and [Al2Li(OH)6]Cl-·nH2O

compounds to replace interlayer Cl- by negatively charged two-dimensional silicate sheets. To
do this, the Cl-bearing compound was put into a silicate-anion containing solution and kept at
100°C and pH 4-10. Microprobe analysis showed that Cl was completely replaced by
silicon-containing species. Silification of the compounds was accompanied by an increase in co
from 7.97 Å before to 12.0 Å after the treatment. Application of various techniques showed that
the layer structure did not change. The 29Si NMR spectra demonstrated the lack of a Si-O-Al
bond formation. Selected area electron diffraction (SAED) patterns from the treated individual
Mg,Al-bearing microcrystals revealed additional hk0 reflections, which corresponded to layer
periodicity √3a0 ≈ 5.2 Å. Based on these data, Schutz and Biloen25 assumed that the observed
increase in the a parameter is associated with two-dimensional silicate sheets formed in the
interlayers. Indeed, the lateral period of 5.2 Å is the characteristic value for tetrahedral sheets of
layer silicates. The characteristic feature of the XRD pattern of the compound is that it contains
strong 01l reflections with l = 2, 5 and 8.25 This means that the mutual arrangement of the
brucite-like layers in the structure corresponds to the 3R1 polytype with the P-type interlayers.
By analogy with LDHs, one may assume that the brucite-like layers and the interlayer silicate
sheets are connected by hydrogen bonds when oxygen atoms of the tetrahedral apices, as well
as the corresponding Si atoms, are located above or below the nearest layer hydroxyls. In this
case, the location of the tetrahedral sheet within the interlayer determines the arrangement of
these sheets in the following interlayers of the three-layer unit cell. Symbolic notation of the
structure within the basic unit cell with a = a0 and c = 3c0 will be:
AbCCSiCaBBSiBcAASiAbC
where CSi, BSi and ASi are the sites for apices and Si-cations of the interlayer Si tetrahedra.
Mixed-Layer Chrysotile-Hydrotalcite
Drits et al.87 described a new mixed-layer mineral variety whose structural, chemical and
morphological features differ from those of all known mixed-layer phyllosilicates. The mineral
in question was found in stringers and patches of serpentinized peridotites in core samples from
the borehole drilled in the Nizhnemamontov Intrusive (Voronezh Province, Russia). The
sample was studied by a series of physical methods, i.e., high-resolution transmission electron
microscopy, selected-area electron diffraction (SAED), energy-dispersion analysis, powder
XRD and IR spectroscopy. Electron microscopy showed that the sample is composed of tubular
particles of two types: short, thick tubes, represented, as indicated by SAED, by orthochrysotile,
and longer and thinner tubes that were found to belong to the new mineral variety. This mineral
can be described as interstraified chrysotile-hydrotalcite. Its structure consists of regularly
alternating hydrotalcite- and serpentine-like layers; the positive layer charge is compensated by
hydrated interlayer SO42- and Cl- anions. The structural units composing the mineral can be
written as:
Mg5.18Al0.72Fe3+0.1Si4O10(OH)8 1:1 layer

Cl1.38(SO4)0.27Ca0.14 nH2O Interlayer
Mg4.92Al0.73Fe3+0.1Ca0.25O10(OH)12 Brucite-like layer
Regular alternation of the brucite-like (0:1) layers and serpentine-like (1:1) layers leads to
formation of hydrogen bonds between hydroxyl groups of 0:1 layer and basal oxygens in the
tetrahedral sheets of the 1:1 layer.
The authors explain the tubular morphology of individual crystallites by lateral
non-commensurability of the tetrahedral and octahedral sheets in 1:1 layers that causes their
bending and rolling up into tubes. They suppose that this effect is preserved in a packet
consisting of serpentine-like and hydrotalcite-like layer, which leads to the spiral-cylindrical
structure of an individual microcrystal. The latter can be imagined as a long rolled ribbon
formed by a "sandwich" consisting of a serpentine-like layer and a hydrotalcite layer.
CONCLUSION
Review of the literature data devoted to the structural and crystal chemical study of the
natural and synthetic LDHs shows that our knowledge of the actual crystal structure of the
compounds is far from being complete. The main reason is that the interpretation of the
experimental XRD patterns obtained for fine-dispersed LDHs powders is often based on the
so-called "finger's print" approach when the measured reflections spacings are compared with
those published in the literature for a LDH of a similar composition instead of using them for
the determination of the unit-cell parameters. An addition polytype identification of a sample
based on the analysis of the positions but not of the intensities of reflections may lead to a
wrong conclusion. This is the main reason why, until recently, it was generally accepted that
LDHs polytypism was limited only by 2H1 and 3R1 representatives. In fact, analysis of the
reflection intensities in the experimental XRD patterns published in the literature has shown
that the polytype diversity of LDHs is much wider than it was previously assumed.
One of the characteristic features of natural and especially synthetic LDHs, is that their
XRD patterns contain broadened and sometimes asymmetric diffraction maxima whose
positions are shifted from those determined by Bragg's law. These effects are typical for layer
structures containing stacking faults. However, until now the nature of stacking faults, their
contents and distribution patterns observed for LDHs have not been systematically analyzed in
the literature. In this chapter, several examples demonstrate that the mathematical formalism
and computer programs developed for the study of stacking faults in clay minerals can be
successfully applied to LDHs having a defective structure.
Another important crystal chemical problem expected be solved is related with revealing
the factors responsible for order-disorder in distribution of cations and anions in layers and
interlayers of LDHs. To solve this problem, one has to work out approaches providing reliable
determination of long- and short-range ordering in the cation-anion distribution. One of the
most effective ways consist in the study of the same sample by a representative complex of
diffraction and spectroscopic methods, so that the interpretation of the experimental data
observed by these methods is based not on the "finger's print" analysis, but on all the
methodological opportunities available.
REFERENCES
[1] F. Zigan and R. Rothbauer, Neues Jahrb. Miner Monatsh. (1967) 137.
[2] G. W.Brindley and S. Kikkawa, Amer. Mineral. 64 (1979) 836.
[3] C. Barriga, J.M. Fernández, M.A. Ulibarri, F.M. Labajos and V. Rives, J. Solid State
Chem. 124 (1996) 205.
[4] M. Belloto, B. Rebours, O. Clause and J. Lynch, J. Phys.Chem. 100 (1996) 8527.
[5] M. del Arco, P. Malet, R. Trujillano and V. and Rives, Chem. Mater. 11 (1999) 624.
[6] V.A. Drits, T.N. Sokolova, G.V. Sokolova, and V.I. and Cherkashin, Clays Clay Miner. 35
(1987) 401.
[7] H.C.B. Hansen, C.B. Koch and R.M. Taylor, J. Solid State Chem. 113 (1994) 46.
[8] F.M. Labajos, M.D. Sastre, R. Trujillano and V.Rives, J. Mater.Chem. 9 (1999) 1033.
[9] E. López-Salinas, M. García-Sánchez, J.A. Montoya, D.R. Acosta, J.A. Abasolo and I.
Schifter, Langmuir 13 (1997) 4748.
[11] J. Rius and R. Allmann, Z. Kristallog. 168 (1984) 133.
[12] Y. Song and H.-S. Moon, Clay Miner. 33 (1998) 285.
[13] M.C. Gastuche, G. Brown and M.M. Mortland, Clay Miner. 7 (1967) 177.
[15] Pausch, H.-H. Lohse, K. Schörmann and R. Allmann, Clays Clay Miner. 34 (1986) 507.
[16] T.Witzke, Neues Jahrb. Miner Monatsh. (1999) 75.
[17] R.D. Shannon, Acta Cryst. A32 (1976) 751.
[18] G.W. Brindley and C.C. Kao, Phys. Chem. Minerals 10 (1984) 187.
[19] R. Allmann, Neues Jahrb. Miner Monatsh. (1969) 552.
[20] R. Allmann, Neues Jahrb. Miner. Monatsh. (1977) 136.
[21] D.L. Bish, Bull. Mineral. 103 (1980) 170.
[22] S. Korting, Z. Freunde Miner. Geol. 27 (1976) 53.
[24] S. Miyata and A. Okada, Clays Clay Miner. 25 (1977) 14.
[25] Schutz and P. Biloen, J. Solid State Chem. 68 (1987) 360.
[26] A.A. Kashaev, G.D. Feoktistov and S.V. Petrova, Zapisky Vsesouznogo
Mineralogitcheskogo Obchestva 11 (1982) 121 (in Russian).
[27] D.L. Bish and A. Livingstone, Miner. Mag. 44 (1981) 339.
[28] E.H. Nickel and J.E. Wildman, Miner. Mag. 44 (1981) 333.
[29] M.A. Cooper and F.C. Hawthorne, Canadian Mineralogist 34 (1996) 91.
[30] E.H. Nickel, Miner. Mag. 40 (1976) 644.
[31] K. Chibwe and W. Jones, J. Chem. Soc.,Chem. Commun. (1989) 926.
[32] M. Meyn, K. Beneke and G. Lagaly, Inorg. Chem. 29 (1990) 5201.
[33] V. Rives and M.A. Ulibarri, Coordination Chem. Rev. 181 (1999) 61.
[34] R. Allmann and H.P. Jepsen, Neues Jahrb. Miner. Monatsh. (1969) 544.
[35] H.F.W. Taylor, Miner. Mag. 39 (1973) 377.
[36] G.Y. Chao and R.A. Gault, Canadian Mineralogist 35 (1977) 1541.
[37] A.V. Arakcheeva, D.Yu. Pushcharovskii, R.K. Rastsvetaeva, D. Atencio and G.U.
Lubman, Crystallography Reports 41 (1996) 972.
[38] R. Allmann, Acta Crystallogr. 24 (1968) 972.
[39] M.J. Wilson, P.D. Cradwick, M.L. Berrow, W.J. McHardy and J.D. Russel, Miner. Mag.
40 (1976) 447.
[40] J.S. White, E.P. Henderson and B. and Mason, Amer. Mineral. 52 (1967) 1190.
[41] A.V.Tatarinov, A.N. Sapozhnicov, S.G. Prokudin and L.P. Frolova, Zapisky
Vsesouznogo Mineralogitcheskogo Obchestva 14 (1985) 575 (In Russian).
[42] A.S.Bookin, V.I. Cherkashin and V.A. Drits, Clays Clay Miner. 41 (1993) 631.
[43] C.Frondel, Amer. Miner. 26 (1941) 295.
[44] J. Pastor-Rodríguez and H.F.W. Taylor, Miner. Mag. 38 (1971) 286.
[45] J. Dunn, D.R. Peacor and T.D. Palmer, Amer. Mineral. 64 (1979) 127.
[46] D.L. Bish and G.W. Brindley, Amer. Mineral. 62 (1977) 458.
[47] E.H. Nickel, C.E.S. Davis, M. Bussel, P.J. Bridge, J.G. Dunn and R.D. MacDonald, Amer.
Mineral. 62 (1977) 449.
[48] N.A.Lisitzina and V.A. Drits, Litol. Polez. Iskop. 6 (1985) 20 (In Russian).
[49] J.D. Bernal, D.R. Dasgupta and A.L. Mackay, Clay Miner. Bull. 4 (1959) 15.
[50] G. Raade, C.J. Elliott and V.K. Din, Miner. Mag. 49 (1985) 583.
[51] D.W.Kohls and J.L. Rodda, Amer. Mineral. 52 (1967) 1261.
[52] G.W. Brindley, Miner. Mag. 43 (1979) 337.
[53] D.R. Hudson and M. Bussell, Miner. Mag. 44 (1981) 345.
[54] E.H. Nickel and R.M. Clark, Amer. Mineral. 61 (1976) 366.
[55] H.P. Klug and L.E. Alexander, X-Ray diffraction Procedures, 2nd Ed.; Wiley, New York,
1974.
[56] D.M.Moore and R.C. Reynolds, X-Ray Diffraction and the Identification and Analysis
of Clay Minerals; Oxford University Press, Oxford, 1989.
[57] V.A. Drits, C. Tchoubar, G. Besson A.S. Bookin F. Rousseaus B.A. Sakharovand D.
Tchoubar, X-Ray Diffraction by Disordered Lamellar Structures; Springer Verlag, Berlin,
1990.
[58] V.A. Drits and B.A. Sakharov, X-Ray Study of Mixed-Layer Minerals; Nauka, Moscow,
1976 (in Russian).
[59] R.C.Reynolds, NEWMOD, a Computer Program for the Calculation of
One-Dimentional Diffraction Patterns of Mixed-Layered Clays; Reinolds, Hannover,
New Hampshire, 1989.
[60] Sissoko, E.T. Iyagba, R. Sahai and P. Biloen, J. Solid State Chem. 60 (1985) 283.
[61] J. Rius and F. Plana, Neues Jahrb. Miner Monatsh. (1986) 263.
[62] H.M. Rietveld, Acta Cryst. 22 (1967) 151.
[63] H.M. Rietveld, J. Appl. Crystallogr. 2 (1969) 65.
[64] J.E: Post and D.L. Bish, In: Modern Powder Diffraction, D.L. Bish and J.E. Post, Eds,
Mineral. Soc. of America, Reviews in Mineralogy 20 (1989) 277.
[65] H.J. Kuzel, Proc. 5-th Int. Symp. on the Chemistry of Cement. Tokyo, 1968,
Supplementary Paper II-19, 93.
[66] R. Fisher, H.J. Kuzel, and H. Schellorn, Neues Jahrb. Miner Monatsh. (1980) 322.
[67] A.S. Bookin and V.A. Drits, Clays Clay Miner. 41 (1993) 551.
[68] W. Hofmeister and H. von Platen, Cryst. Rev. 3 (1992) 3.
[69] S.W. Bailey, In: Crystal Structures of Clay Minerals and their X-Ray Identification.
G.W. Brindley and G. Brown eds, Miner. Soc., London, 1, 1980.
[70] H. Saalfeld and M. Wedde, Z. Kristallogr. 139 (1974) 129.
[71] Van der Pol, B.L. Mojet, E. van de Ven and E. de Boer, J. Phys. Chem. 98 (1994) 4050.
[72] M. Vucelic, W. Jones, W and G.D. Moggridge, Clays Clay Miner. 45 (1997) 803.
[73] S.A. De Waal and E.A. and Viljoen, Amer. Mineral. 56 (1971) 1077.
[74] A.S. Bookin, V.A. Drits and V.I. Cherkashin, Clays Clay Miner. 41 (1993) 558.
[75] K.A. Rodgers, J.E. Chisholm, R.J. Davis and C.S. Nelson, Miner. Mag. 41 (1977) 389.
[76] G.Mascolo and O. Marino, Miner. Mag. 43 (1980) 619.
[77] R. Allman, R and J.D.H. Donnay, Amer.Mineral. 54 (1969) 296.
[78] R. Allmann and H. Lohse, Neues Jahrb. Miner. Monatsh. (1966) 161.
[79] M.J. Hernández-Moreno, M.A. Ulibarri, J.L. Rendon and C.J. Serna, Phys. Chem.
Minerals 12 (1985) 34.
[80] F.A. Mumpton, H.W. Jaffe and C.S. Thompson, Amer. Mineral. 50 (1965) 1893.
[81] J.L. Jambor, Amer. Mineral. 54 (1969) 437.
[82] S. Ghose, Acta Cryst. 17 (1964) 1051.
[83] W. Stahlin and H.R. Oswald, Acta Cryst. B26 (1970) 860.
[84] R.J. Hill, Acta Cryst. B36 (1980) 1304.
[85] A.H. Treiman and D.R. Peacor, Amer. Mineral. 67 (1982) 1029.
[86] J.-H. Choy, Y.-M. Kwon, K.-S. Han, S.-W.- Song and S.H. Chang, Mater. Lett. 34 (1998)
356.
[87] V.A. Drits, A.I. Gorshkov, A.V. Mokhov and E.V. Pokrovskaya, Litol. Polez. Iskop. 3
(1995) 201 (In Russian).
Chapter 3
COMPUTER MODELLING OF LAYERED

DOUBLE HYDROXIDES
S. P. Newman,† H. C. Greenwell,‡ P. V. Coveney† and W. Jones‡
†
Centre for Computational Science, Queen Mary College, University of London, Mile End,
London, E1 4NS, UK.
‡
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2
1EW, UK.
INTRODUCTION
Computer Modelling as a Technique in Materials Chemistry
As the power and speed of computers increases, so does the range and size of chemical
systems to which computer simulation techniques may be applied. For several years computer
modelling has been used to study biologically-relevant systems such as protein folding and the
structure and dynamics of cell membranes.1-5 For such systems, molecular dynamics computer
simulations in particular have been extensively employed. Colloidal systems, for example the
stability of surfactant micelles in aqueous solution, have also been studied using computer
simulation techniques.6,7
Concurrent with the rapidly advancing power of computers is the growth of the field of
computational modelling applied to extended structures such as those encountered within
materials and solid-state chemistry, reviewed recently by Catlow and co-workers.8-10 The
necessity for computer simulations when working with solid-state materials arises due to
several factors. Many materials do not form satisfactory single crystals, for example, and thus
characterisation is reduced predominantly to powder X-ray diffraction (PXRD) techniques.
Whilst Rietveld refinement can be used in principle to determine structure from powder data,
often the data is not of sufficient quality to allow adequate structure solution. This is
particularly true for disordered systems, such as clays. Defects and surface interfaces present
yet another challenge for solid-state chemists, where mainly microscopy techniques are applied.
Computer simulations may be used in each of these areas to provide insight not available from
the experimental techniques. Many dynamic processes within solid-state structures such as
ionic transport, for example oxygen mobility in superconductors, and processes occurring
102 S. P. Newman, H. C. Greenwell, P. V. Coveney et al.
within microporous host structures may be examined by molecular dynamics computer

simulation techniques, which provide temporal information as well as static structural
information.8-10 Falling into the latter category are materials such as zeolites, which are vitally
important within industry due to the extensive catalytic properties exhibited by the material,
and have thus received much study. Kaszkur et al. have, for example, used a combined
Rietveld refinement and molecular dynamics computer simulation approach to locate the
position of 1,4-dibromobutane in zeolite Y.11 Similarly, Schrimpt and co-workers have
employed molecular dynamics simulations to study the properties (structure, energetics and
diffusion) of aromatic molecules, such as benzene and p- and m-xylene in zeolite Na-Y.12,13
Cheetham and co-workers have also examined adsorption and diffusion processes occurring
within zeolites and other microporous structures using computational simulations.14-20
In recent years, the use of computer modelling techniques to investigate the interlayer
structure and dynamics of layered materials has developed. Skipper and co-workers, for
example, have performed Monte Carlo simulations to investigate the hydration of Li+, Na+ and
K+ montmorillonite cationic clays.21-23 In particular, the influence of the interlayer cation on
clay swelling was studied. This research was driven by its relevance to the oilfield industry.
More recently, Bains et al. have extended this work to model the mechanism of action of
organic clay-swelling inhibitors.24 Molecular dynamics simulations have also been used to
study the adsorption of organic molecules by clays.25 Kelsden et al., for example, calculated the
enthalpy of adsorption of various linear, branched or cyclic hydrocarbons by a model smectite
clay using molecular dynamics simulations.26
In our group, computer simulations have been used to probe the interlayer structure and
dynamics of anionic clays, also known as layered double hydroxides (LDHs). Our motivation
developed from the lack of detailed structural information available for these materials, in particular
where the interlayer anion is organic. In this chapter, we review our computer simulations of LDHs
performed to date. Similar simulations of LDHs performed by other workers are also reviewed
briefly. A variety of interlayer anions, such as carbonate and terephthalate, have been studied and
we describe the type of information, structural and dynamical, available from the simulations of
these systems.
COMPUTER SIMULATION METHODOLOGY

Background
The main computer methods employed for the study of solid-state materials are energy
minimisation, molecular dynamics and Monte Carlo techniques. Each of these methods relies
on the use of relatively simple interatomic potentials. An advantage of these methods is that
they are classically based and, as a consequence, are computationally less expensive than
quantum mechanical methods, which rely on solution of the Schrodinger equation, thus
facilitating the study of systems containing of the order of thousands of atoms (as the power of
computers increases so does the size of system that may be studied). An obvious disadvantage
of the simulation approach is that any property of the materials studied that explicitly relies on
electronic structure - chemical reactivity for example - cannot be modelled.
In energy minimisation methods, the arrangement of minimum potential energy is
determined for a system by adjusting the positions of atoms in the system. Initially the energy
Computer Modelling of Layered Double Hydroxides 103
of the system is evaluated and subsequently minimised, usually in an iterative fashion, with
respect to all relevant variables for the system to give an optimised structure. The kinetic
energy of the atoms, and hence thermal effects, are not considered in such calculations which
are thus known as zero-Kelvin or static-lattice calculations. An obvious disadvantage is the
possibility of trapping in local, as opposed to global, energy minima.
In molecular dynamics, kinetic energy is included explicitly by solving the classical
equations of motion for the system according to the forces present. Molecular dynamics
methods therefore allow the time-evolution of a system at non-zero temperatures to be studied.
In Monte Carlo simulations, an ensemble of probable configurations is generated for the system
over which averages corresponding to system properties are taken. The configurations are
generated by performing a series of random moves, such as translating or rotating a molecule.
If the move lowers the potential energy of the system then the new configuration is accepted
with a probability of unity. If the move increases the potential energy of the system then the
probability of acceptance is weighted by a Boltzmann factor between 0 and 1. In Monte Carlo
simulations, unlike molecular dynamics, there is no temporal relationship between the different
configurations.
In the following sections, our methodology for performing molecular dynamics
simulations of LDHs is outlined. The advantage of molecular dynamics compared with energy
minimisation and Monte Carlo methods is that the dynamical history of the system is known.
Thus dynamical quantities, such as diffusion coefficients, may be calculated using molecular
dynamics in addition to equilibrium (and non-equilibrium) structural properties. All our
simulations have been performed using the Cerius2 software package.27
Molecular Dynamics Simulations
In this section an introduction is given to the method of molecular dynamics computer

simulations. In brief, it is the simulation of the motion of a system of mutually interacting atoms
with respect to the forces that are present.28,29 The forces present are determined from a
potential energy function, V(r), which gives the potential energy of the entire system of N
atoms as a function of their nuclear co-ordinates.
Fi = -∇riV(r)
where ri is the position of the ith atom, and Fi is the total force acting on it as a result of
interactions with the other N-1 atoms of the system. Newton’s equations of motion are then
solved, in an iterative numerical fashion, for the system:
d2ri
Fi = miai = mi
dt2
where mi is the mass, and ai the acceleration, of the ith atom. The value of ri at time t+∆t can be
expanded about ri(t) by a Taylor expansion:
1
ri(t+∆t) = ri(t) + vi(t)∆t + a (t)(∆t)2 + . . .
2 i
which enables the displacement of an atom to be calculated from an initial velocity, vi, and the
acceleration, ai. The initial atomic co-ordinates for a particular system are known and the initial
velocities for a particular temperature are generated from a Maxwell-Boltzmann distribution.
The time-step is then applied several thousand times and the positions and velocities of the
atoms continually updated and stored. For the calculation to be accurate the time-step must be
smaller than the characteristic time of any important process in the system (e.g. the period of an
atomic vibration) and is typically 1 or 2 fs.
The normal procedure in molecular simulations is to assign a forcefield, which contains the
information necessary for calculating the potential energy of the system. A forcefield thus
defines the functional form of V(r), and contains sets of parameters for calculating V(r). The
total potential energy of the system is calculated as a sum of the bonded and non-bonded
interactions present.
Vtotal = Vbonded + Vnon-bonded
The bonded interactions depend on the specific connections (bonds) between atoms of the
system, whereas non-bonded interactions depend only on the distance between atoms of the
system.
Vbonded = Vl + Vθ + Vw + VI
Vnon-bonded = Vvdw + Vq
In general, the bonded interactions consist of bond stretch (Vl), bond-angle bend (Vθ),
dihedral angle torsion (Vw) and inversion terms (VI). The bond stretch term is, for example,
commonly represented by a simple harmonic term:
Vl = Σ kl(l – lo)2
Where lo is the equilibrium bond length, kl is the stretching force constant and the
summation is performed over all bonds present in the system.
Non-bonded interactions generally consist of van der Waals (Vvdw) and electrostatic terms
(Vq). The most common expression for describing the van der Waals interaction between a pair
of atoms i and j is the Lennard-Jones 6-12 potential:
Vvdw = Σ Ai,jrij-12 – Bi,jrij-6
where Ai,j and Bi,j characterise the short-range repulsion and long-range dispersion
interactions, respectively, between a pair of atoms separated by a distance rij. The summation is
performed for all pairs of interacting atoms in the system. The electrostatic interactions are
described according to Coulomb’s law:
Vq = Σ qiqj / 4πεorij
where qi is the partial charge associated with the ith atom and the summation is again performed
for all pairs of interacting atoms in the system. In addition to defining the functional form of the
potential energy function, the forcefield also defines parameters such as force constants,
equilibrium bond lengths and angles, required for the calculation. The precise nature of the
terms and parameters incorporated into the potential energy function thus depends on the
forcefield, and a variety of forcefields are available.
The quality of a given forcefield depends on its parameterisation. This is often achieved by
fitting the variable parameters in the potential energy function to known experimental data for
model compounds. Although accurate, forcefields that are designed for specific applications
(e.g., the TIP3P forcefield for simulations of bulk water)30 normally cannot be applied to
systems other than the one for which the original parameterisation was performed. More robust
forcefields containing generic parameters, however, can be applied to a wider range of systems
but with a reduction in accuracy compared with more specialised forcefields. Choosing the
correct forcefield is thus dependent on the system under investigation and the information
desired from the simulation.
Model Construction
The first stage in preparing a model LDH for computer simulations is construction of the
host framework, i.e., the positively-charged hydroxide layers of the LDH. In this section, the
procedure used for constructing model LDH frameworks with a Mg/Al ratio of 3 or 2 (hereafter
referred to as Mg3Al- and Mg2Al-LDH models) for our most recent simulations is described.
The hydroxide layers of the model LDHs were constructed using atomic coordinates from
the previously-reported crystal structure of hydrotalcite, a naturally-occurring LDH mineral
with the composition [Mg4Al2(OH)12](CO3)·3H2O.31 The structure consists of a rhombohedral
lattice with the hexagonal unit-cell parameters a=3.054, c=22.81 Å; space group R 3 m. The
interlayer carbonate and water molecules were removed and a P1 superlattice created with a
two-layer repeat. Hydroxide layers of size 18.30 x 12.20 Å2 (equivalent to 24 hydrotalcite unit
cells in the ab-plane) or 18.30 x 9.15 Å2 (equivalent to 18 hydrotalcite unit cells in the ab-plane)
were used for simulations of Mg3Al- and Mg2Al-LDH models, respectively. The proportions of
Mg and Al in the hydroxide layers were adjusted explicitly to give the correct Mg/Al ratio in
each case and the distribution of the cations ordered such that the Al atoms did not occupy
adjacent hydroxide octahedra. The initial interlayer spacing (the c-parameter of the simulation
cell) was set initially according to the identity of the interlayer anion used for the simulation.
Atomic charges were initially calculated using the Charge Equilibration Method.32 This method
can be applied only to neutral systems, however; thus the required positive charge of +12 or +9
for the Mg3Al- or Mg2Al-LDH models was subsequently averaged over all atoms in the cell.
The composition of the model LDH frameworks were thus [Mg36Al12(OH)96]12+ or
[Mg24Al12(OH)72]12+.
The second stage in preparation of LDH models for computer simulations is construction
of the interlayer molecules. For our simulations, the initial geometry and atomic charges of the
interlayer anions were calculated using the MOPAC semi-empirical molecular orbital method,
employing the PM3 Hamiltonian approximation.33 For interlayer water, the initial geometry
and atomic charges were taken from the TIP3P specialised water forcefield.30 Molecular
dynamics simulations of bulk water have found that a combination of the Dreiding forcefield,
as used here (Section 2.2.2) with the TIP3P partial charges for water, yields physical properties,
such as density and radial distribution function, in good agreement with experimental values.34
The required number of anions were then placed within the model LDH framework. For
organic molecules, the molecules were generally placed in the framework with their longest
axis oriented in a direction approximately perpendicular to the plane of the hydroxide layers.
Finally, the desired number of water molecules were placed at random in the interlayer of the
models.
Forcefields
An aim of our work was to perform molecular dynamics simulations of model LDHs using
existing forcefields, i.e., not to design a specialised forcefield, parameterised only for LDH
systems. A modified version of the Dreiding forcefield was used, therefore, for all our
simulations. Dreiding is a generic forcefield, designed for application to a wide range of
systems (organic, biological and main-group inorganic molecules) containing a variety of
different atoms.35 The philosophy behind Dreiding is to use general bonded parameters (e.g.
force constants) based on the hybridization states of atoms, rather than the specific combination
of atoms involved in a particular system.
A number of modifications were made to the Dreiding forcefield to tailor it for the LDH
system. Firstly it was necessary to include parameters for Mg, which are not present in the
original Dreiding forcefield. This was achieved by assigning Mg the same parameters as Al (for
which Dreiding does have parameters), with the exception that the equilibrium Mg-O bond
length was set at 2.100Å, which is the mean Mg-O bond length in the crystal structure of
brucite, Mg(OH)2.27 Note that the equilibrium Al-O bond length assigned by Dreiding is
1.697Å. Most of our simulations to date have been performed using this modified version of the
Dreiding forcefield (hereafter referred to as Forcefield I), the results from which are described
in Section 3.1.
Recently, a number of additional modifications have been made to this forcefield. Firstly,
the equilibrium bond length for Al-O was increased to 1.902Å, which is the mean Al-O bond
length in the crystal structure of gibbsite, Al(OH)3.27 This modification was made in order to
counteract the contraction in the ab-plane of the hydroxide layers observed in our previous
simulations of LDHs. Secondly, the harmonic theta form for angle-bend energy terms, E =
1/2K[θ –θeq]2 used in Forcefield I was replaced with a harmonic cosine theta form, E =
1/2C[cosθ – cosθeq]2, where E is the potential energy, K is a force constant, θ is the bond angle,
θeq the equilibrium bond angle and C is given by C = K / (sin θeq )2. We have found that this
modification significantly reduces distortion of the hydroxide octahedra observed during our
earlier molecular dynamics simulations of LDHs using Forcefield I. It should be noted that the
authors of Dreiding recommend use of the harmonic cosine theta form, although the harmonic
theta form is the default used in the Cerius2 implementation of the forcefield, presumably to
reduce computation time. This improved forcefield is hereafter referred to as Forcefield II. The
results obtained using this forcefield are described in Section 3.2.
Simulation Details
Long-range Coulombic interactions and the attractive van der Waals interactions were
computed using the Ewald summation technique. Short-range repulsive van der Waals
interactions were treated with a direct cut-off radius of approximately 7Å. Energy minimisation
was performed on all models prior to the molecular dynamics simulations to reduce strain.
Molecular dynamics simulations were performed in the constant composition,
isothermal-isosbaric (NPT) ensemble at 300K.29 A time-step of 0.001ps was used. Temperature
was maintained using the Hoover thermostat implemented with a relaxation time of 0.1ps and a
cell-mass prefactor of unity.36 The equivalent hydrostatic pressure was set to 105 Pa
(approximately 1 atmosphere). Periodic boundary conditions were applied in three dimensions
so that the simulation cell is effectively repeated infinitely in each direction – each atom in the
cell therefore interacts with its periodic image as well as all the other atoms in the cell.
Generally, the simulations were performed in two stages: firstly equilibration of the system and
secondly data collection of system properties. Whether a system has equilibrated may be
judged by plotting various thermodynamic quantities such as energy or temperature against
time. When equilibration has been reached, these quantities fluctuate around their average
values, which remain constant over time. The total simulation time was generally 40 ps
(equivalent to 40000 time-steps), with the first 30 ps of the simulation required for equilibration.
In certain cases a snapshot of the model was stored every 0.05ps (every 50 time-steps) and the
interlayer spacing of the model averaged over the final 10ps (the average interlayer spacing
from the final 200 snapshots), after it was considered thermal equilibration had been reached.
Furthermore, molecular dynamics simulations were performed for certain models for an
extended time period of 500 ps (0.5 ns). An increased length of the simulation was used to
facilitate extraction of a reliable radial distribution function (RDF) and mean squared
displacement (MSD) for atoms in the system, owing to the improved statistics of longer
simulations. Diffusion coefficients were determined from the calculated MSD.
RESULTS AND DISCUSSION

In this section, selected results from molecular dynamics computer simulations performed in
our group in recent years are described. Generally, models were constructed using the procedure
described above and the simulations performed using the methodology outlined in above. Firstly,
results obtained from simulations employing Forcefield I are described. Secondly, results from
more-recent simulations employing Forcefield II are described.
Forcefield I
Mg3Al-LDHs Containing Carbonate, Nitrate or Chloride
Molecular dynamics simulations have been performed for a model Mg3Al-LDH containing
the inorganic interlayer anions CO32-, NO3- or Cl-.37 The models were constructed as described
previously, with the initial interlayer spacing set to 8.0 Å in each case – a value close to that
observed experimentally for these interlayer anions. A total of 24 water molecules were
included in each of the simulation cells (12 per interlayer) corresponding in each case to 2 water
molecules per Al atom. The same water content was used for each model to facilitate
comparison between the interlayer properties of these LDHs. The empirical formulas of the
models were thus [Mg3Al(OH)8](An-)1/n.2H2O, where A is CO32-, NO3- or Cl-.
The simulations were performed according to the methodology above described and were
divided into two stages. Firstly, molecular dynamics simulations were performed for 40 ps.
Equilibration of the models was judged to have been reached before 30 ps of simulation and the
interlayer spacing was averaged over the final 10 ps of the simulation. Secondly, molecular
dynamics simulations were performed for a period of 500 ps (0.5 ns) using the final atomic
positions from the preliminary 40 ps of simulation as the starting models. The extended
simulations were performed to allow the mean square displacement (MSDs) and diffusion
coefficients (D) of the interlayer anions to be calculated and compared.
Figure 1 shows a snapshot of the simulation cells of the three models, following 40 ps of
molecular dynamics simulation at 300 K. For clarity, only one interlayer of the simulation cell
of each model is displayed. For the model Mg3Al(CO3) LDH the interlayer spacing averaged
over the final 10 ps of the simulation gives a value of 7.30 ± 0.1 Å. This value may be compared
with the experimental value of 7.60 Å reported from single crystal data for a LDH with the
approximate composition [Mg4Al2(OH)12](CO3).3H2O.31 Thus, although similar, the simulated
layer spacing is slightly lower than the value observed from single-crystal X-ray diffraction
data. In agreement with single crystal data, however, the simulation predicts that the carbonate
anions lie midway between, and generally coplanar with, the hydroxide layers of the LDH.
Figure 1. Snapshot of the simulation cells of the Mg3Al(CO3), Mg3Al(NO3), and Mg3Al(Cl) model LDHs,
following 40 ps of molecular dynamics simulation at 300 K. For clarity, only one interlayer of the simulation
cells are presented.
For the model Mg3Al(NO3) LDH, the interlayer spacing averaged over the final 10 ps of
the simulation is 8.61 ± 0.14 Å, which is in good agreement with generally reported
experimental values. An interlayer spacing of 8.34 Å, for example, has been reported for a LDH
with the approximate composition [Mg2.9Al(OH)7.8](NO3)0.83(CO3)0.09.1.4H2O.38 Charge
balancing the model LDH requires twice as many interlayer nitrate anions as carbonate, with
the resulting increase in anion packing density creating greater steric repulsion between the
interlayer anions. The simulation shows (Figure 1(b)) that the nitrate anions therefore tilt away
from co-planarity with the hydroxide layers, presumably to reduce unfavourable intermolecular
interactions between the anions, with a concomitant increase in interlayer spacing compared
with the coplanar carbonate case.
For the model Mg3Al(Cl) LDH, the average interlayer spacing calculated from the final 10
ps is 7.46 ± 0.1 Å which is in reasonable agreement with the experimental value of 7.80 Å
observed for a LDH with the approximate composition [Mg2.2Al(OH)6.4]Cl.2H2O.39 The
chloride ions and water molecules are located in the mid-plane of the interlayer (Figure 1(c)).
Inspection of Figure 1 reveals that significant distortion of the constituent Mg(OH)6 and
Al(OH)6 octahedra of the hydroxide layers occurs during the molecular dynamics simulations.
Moreover, there is a general contraction of the hydroxide layers from their size in the starting
models (constructed from single crystal X-ray diffraction data) during the simulation. For the
carbonate model, for example, the area of the ab-plane for the model following 40 ps of
simulation is 13.5% less than the starting model. Despite distortion of the hydroxide layers,
however, reasonable agreement between the simulated interlayer arrangement of the LDHs and
experimental observations is nevertheless obtained.
The mean square displacements of the interlayer anions, obtained by monitoring the C, N,
or Cl atom displacements as a function of time during 500 ps of molecular dynamics simulation
at 300 K and averaging over all anions and all choices of time origin (t0), are presented in
Figure 2.
MSD = 〈|r(t0 + t) – r(t0)|2〉
The MSD thus calculated reflects the mobility of the interlayer anion during the simulation.
The self-diffusion coefficient of the interlayer anion may be determined from the slope of the
calculated MSD with t using the Einstein relation, which applies only in the limit of infinite t
(compared to the time between collisions of the selected atoms):30-32
2
lim 6Dt = r(t 0 + t) − r (t0 )
t→ ∞
The magnitude of the simulated MSDs indicate that diffusion of the interlayer anions at
300 K is extremely slow, as would be expected. The diffusion coefficients determined from the
slopes are approximately 7x10-8 cm2s-1 for both N and Cl and 1x10-8 cm2s-1 for C. These values
are only rough estimates because the simulated MSDs are too small and non-linear to determine
reliable diffusion coefficients. The results nevertheless demonstrate that the divalent carbonate
anion is less mobile within the interlayer of the model LDH than either the nitrate or chloride
anions (on the time-scale of 0-0.5 ns). In order to evaluate more reliable diffusion coefficients
for the interlayer anions, molecular dynamics simulations for significantly longer time-periods
would be required.
It should be noticed that the potential energy and interlayer spacing of each model
following the extended 500 ps of molecular dynamics simulation were essentially unchanged
compared with the values recorded following the initial 40 ps of molecular dynamics
simulation, thus providing additional confirmation that equilibration was indeed attained
during the initial 40 ps of molecular dynamics simulation.
Figure 2 Simulated MSDs for the (a) carbonate, (b) nitrate and (c) chloride anions obtained from 500 ps of
molecular dynamics simulation at 300 K.
MgAl-LDHs Containing Terephthalate
The first molecular dynamics simulations of LDHs containing terephthalate anions were
performed by Bell et al.40,41 This work demonstrated the ability of the simulations to reproduce
the experimentally observed interlayer spacing for this system. The work was then extended to
study the influence of layer charge and interlayer water content on the interlayer arrangement
of the system.37,42 Here, molecular dynamics simulations were performed for model Mg3Al-
and Mg2Al-LDHs containing interlayer terephthalate anions and varying number of water
molecules (the model LDHs were prepared as described above). The different Mg/Al ratios of
the models allowed the influence of layer charge on the interlayer arrangement of the
organo-LDH to be studied. Furthermore, the influence of water content on the interlayer
arrangement of these model organo-LDHs was simulated by increasing, in intervals of 4, the

number of water molecules included in the simulation cell from 0 up to a maximum of 80. In
the NPT ensemble employed for all the molecular dynamics simulations, the volume of the
system is allowed to vary, enabling the simulation to predict the interlayer spacing for the
specified water content. The total simulation time was generally 40 or 20 ps for the Mg3Al- and
Mg2Al-LDH models, respectively (the longer relaxation time required for the former is due, at
least in part, to the larger size of this simulation cell). In either case, the interlayer spacing for a
particular water content was averaged over the final 10 ps of the molecular dynamics
simulation, after thermal equilibration was considered to have been reached.
Results from the simulations were compared with powder X-ray diffraction and
thermogravimetric measurements performed on synthetic Mg3Al- and Mg2Al-LDHs
containing terephthalate. Different water contents were obtained by hydrating and dehydrating
the synthetic LDHs to different extents. In summary, the experiments revealed that an interlayer
spacing of approximately 14.0 Å is favoured for high layer charge and interlayer water content.
For low layer charge and water content an interlayer spacing of approximately 8.4 Å was
observed. During cycles of dehydration-rehydration, the PXRD data suggested that the 14.0 Å
and 8.4 Å interlayers coexist in varying proportions depending on the layer charge and water
content and in certain cases, a 22.4 Å interstratified phases consisting of a regular alternation of
the component interlayers was identified.
A simulated swelling curve obtained for the model Mg3Al(terephthalate) LDH is presented
in Figure 3, where the error bars (two standard deviations in each direction) represent the
fluctuations about the average interlayer spacing following equilibration. The small size of the
fluctuations is evidence that equilibration has been obtained. The interlayer spacing increases
gradually from approximately 8.5 Å for the model containing no interlayer water molecules, to
approximately 15 Å for the model containing 80 water molecules. The gradual expansion of the
interlayer with increasing water content is accompanied by a gradual change in the orientation
of the terephthalate anions from horizontal to vertical, with respect to the hydroxide layers.
Figure 4 is a snapshot of the model containing 8 water molecules following 40 ps of
molecular dynamics simulation, showing the horizontal orientation of the terephthalate anions.
The water content (3.6 mass%) and interlayer spacing (8.7 Å) of the model are in good
agreement with the measured water content (5.5 mass%) and interlayer spacing (8.4 Å) of the
synthetic Mg3Al(terephthalate) LDH. The final snapshot from the simulation of the model
containing 64 water molecules (Figure 5), shows the terephthalate anions in an approximately
vertical orientation with respect to the hydroxide layers, with the carboxylate groups attached
directly to the hydroxide layers. The majority of the interlayer water molecules form a
monolayer on each of the hydroxide surfaces and are generally excluded from the hydrophobic
midplane of the interlayer formed by the phenyl ring of the anions.
Figure 3. Simulated swelling curve for the model Mg3Al(terephthalate) LDH. The error bars represent the
fluctuations (two standard deviations in each direction) about the average interlayer spacing (over 10 ps),
following equilibration for 30 ps.
Figure 4. Snapshot of the model Mg3Al(terephthalate) LDH containing 8 water molecules (3.6 mass percent),
following 40 ps of molecular dynamics simulation at 300 K.
A simulated swelling curve obtained for the model Mg2Al(terephthalate) LDH is presented
in Figure 6. At first, the interlayer spacing increases gradually with increasing water content,
before levelling off at approximately 14.0 Å for a water content of between 40 and 56
molecules. This water content corresponds approximately to 20 mass%, which is in good
agreement with the experimentally-determined water content for the synthetic LDH with
similar interlayer spacing. For a water content of between 40 and 56 water molecules the
simulations show that the terephthalate anions adopt an approximately vertical orientation with
respect to the hydroxide layers. Fewer water molecules are required to ensure a vertical
orientation of the terephthalate anions in the Mg2Al-LDH compared to the Mg3Al-LDH,
presumably due to the higher layer charge and interlayer anion packing density in the former.
The simulations performed to obtain the swelling curves do not reproduce the
experimentally observed interstratified arrangement for the synthetic LDHs with intermediate
water contents. The observation of the interstratified phase suggests an ordered alternating
sequence of relatively hydrated and dehydrated interlayers with the terephthalate anions in
either a vertical or horizontal orientation, respectively. The canonical aspect (fixed N) and
imposed symmetry (i.e., an equal number of water molecules per interlayer) of the simulations,
however, makes it impossible to predict such situations. Additional molecular dynamics
simulations were performed, therefore, on the Mg2Al-LDH model with an unequal distribution
of the water molecules between the two interlayers of the simulation cell. The results from
these simulations support the experimental interpretation that the interstratified phase consists
of alternating relatively dehydrated and hydrated interlayers.37
Figure 5. Snapshot of the model Mg3Al(terephthalate) LDH containing 64 water molecules (23.2 mass
percent), following 40 ps of molecular dynamics simulation at 300 K.
Figure 6. Simulated swelling curve for the model Mg2Al(terephthalate) LDH. The error bars represent the
fluctuations (two standard deviations in each direction) about the average interlayer spacing (over 10 ps),
following equilibration for 30 ps.
The properties of the interlayer water in the Mg3Al(terephthalate) model with 64 water
molecules and the Mg2Al(terephthalate) LDH with 44 water molecules, were further
investigated using data extracted from extended 0.5 ns molecular dynamics simulations. In
both these models, the terephthalate anions adopt a vertical orientation with respect to the
hydroxide layers and the simulated interlayer spacings are in good agreement with experiment.
As a measure of the local ordering of the interlayer water, the water oxygen-oxygen radial
distribution function (RDF) was calculated for both models. The RDF gives the probability of
finding a pair of atoms separated by a distance r, relative to the probability expected for a
completely random distribution at the same density. The RDFs were calculated for water O-O
pair correlations, averaged over all snapshots from 0 to 0.5 ns, within a single interlayer of the
models (Figure 7).
The calculated water O-O RDFs for the models exhibit the same main features as the
simulated RDF obtained for bulk water by Boek et al.34 The well-defined peak at 2.9 Å (1)
indicates a relatively high degree of structural ordering of the water molecules within the first
coordination shell, probably within a single surface monolayer. A second peak, poorly defined
compared with the first, at 5.7 Å (2) suggests that a second hydration shell also exists.
Figure 7. Water O-O RDF, obtained from 500 ps of molecular dynamics simulation at 300 K, for (a) the model
Mg3Al(TA) LDH containing 64 water molecules and (b) the model Mg2Al(TA) LDH containing 44 water
molecules. The numbers indicate the first and second coordination shells of the water molecules.
The water self-diffusion coefficient, D, was calculated for both models from the gradient of
the simulated MSD of the water oxygen atoms with time (Figure 8). The linear nature of the
MSDs suggests that, for the purpose of calculating D for the water molecules in these models,
500 ps of molecular dynamics simulation is satisfactory, although longer time-scales would be
desirable for more accurate determinations. The values of D obtained (Table 1) are the same
order of magnitude as experimental data obtained using a quasi-elastic neutron scattering (D =
2.47 x 10-7 cm2s-1 for a synthetic Mg2Al(terephthalate) LDH at 50 °C).43 As would be expected
for water constrained between the hydroxide layers of a LDH, the simulated water
self-diffusion coefficients are significantly lower than values obtained from simulations of bulk
water (1.88 x 10-5 cm2s-1 at 300 K, using the Dreiding forcefield and TIP3P water parameters)34
or experimental values obtained for bulk water (2.3 x 10-5 cm2s-1 at 298 K).44
The relative size of D calculated for the two models suggests that the interlayer water
molecules are more mobile in the Mg3Al model compared with the Mg2Al model. This
observation may be understood in terms of the relative charge densities of the layers – the
higher the charge density, the more tightly bound the water molecules.
Figure 8. Calculated MSDs for water in (a) the model Mg3Al(TA) LDH containing 64 water molecules and (b)
the model Mg2Al(TA) LDH containing 44 water molecules, from 500 ps of molecular dynamics simulation at
300 K.
Table 1. Simulated water self-diffusion coefficients
Model D / cm2s-1
Mg3Al(terephthalate), 64 water molecules 4.4 x 10-7
Mg2Al(terephthalate), 44 water molecules 1.1 x 10-7
Forcefield II
MgAl-LDH Containing Carbonate
Figure 9 is a snapshot of a model Mg3Al(CO3) LDH, following 40 ps of molecular

dynamics simulation at 300K, performed using Forcefield II. The starting model used was the
same as that used for the corresponding simulation (Figure 1(a)) performed using Forcefield I.
Comparison of the snapshots from the two 40ps simulations shows that the distortion of the
hydroxide octahedra observed using Forcefield I is significantly reduced when Forcefield II is
used. The difference is due to the manner in which the angle-bend energy terms are treated in
the two forcefields: a harmonic theta term or a harmonic cosine theta term for I and II,
respectively (Section 2.2.2). It is probable that the improved modelling of the hydroxide
octahedra observed using the latter term arises because it yields a zero potential energy gradient
at θ = 180º, whereas the harmonic theta form does not.
Figure 9. Snapshot of the simulation cell of the Mg3Al(CO3) model LDH, following 40 ps of molecular
dynamics simulation at 300 K using Forcefield II.
The average interlayer spacing of the Mg3Al(CO3) LDH model over the final 10 ps of the
simulation using Forcefield II is 7.55 ± 0.1 Å. This is slightly greater than the average interlayer
spacing determined using Forcefield I and in good agreement with single crystal X-ray data for
hydrotalcite.31 As before, the simulation predicts that the carbonate anions lie midway between,
and generally coplanar with, the hydroxide layers of the LDH. In addition to the improved
modelling of the hydroxide octahedra produced by modification of the angle-bend energy term,
there is also less contraction of the hydroxide layers during the simulation with Forcefield II
compared to the simulation with Forcefield I: a 7.2% reduction in the area of the ab-plane from
the starting model to the final model using II, compared to 13.5% with I. This improvement
may be attributed to the modification made to the equilibrium Al-O bond length, i.e., increasing
it from the value assigned by Dreiding of 1.697Å to a value 1.902Å, which is the mean Al-O
bond length in the crystal structure of gibbsite, Al(OH)3. It is clear, therefore, that Forcefield II
represents a significant improvement to Forcefield I for the simulation of LDHs.
MgAl-LDH Containing (S)-phenylalanine and (S)-tyrosine
Forcefield II has been used recently to study the interlayer structure of a model MgAl-LDH
and montmorillonite cationic clay containing the amino acids (S)-phenylalanine and
(S)-tyrosine.45 The fact that amino acids are zwitterionic means that they can be incorporated
into both clay systems with opposite charge. Furthermore, it is important to note that it was
possible to use the same modified version of the Dreiding forcefield (i.e., Forcefield II, with a
modification to the equilibrium Si-O bond-length to tailor it for the cationic clay system) for the
simulations of both clay systems. The models were chosen to replicate an experimental study
performed previously because of the ability of the simulations to provide insight into the
interlayer properties of the LDHs not available from the experimental data.46 Only results from
simulations of the MgAl-LDH systems are discussed here. The models were constructed with
the initial interlayer spacing set at 18.0 Å, and the amino acid anions arranged in a vertical
bilayer-like arrangement.
A snapshot of the simulation cell of a model Mg3Al-LDH containing (S)-phenylalanine,
following 50 ps of molecular dynamics simulation at 300 K is shown in Figure 10. Sixty water
molecules were included in the simulation cell (30 per interlayer), which corresponds to 18.4
mass percent and gives an empirical formula of [Mg3Al(OH)8]((S)-phenylalanine).5H2O.
The average interlayer spacing over the last 10 ps of the simulation is 17.9 ± 0.4 Å, which
is in good agreement with the interlayer spacing of 18.0 Å determined by Fudala et al. for a
synthetic ZnAl(L-phenyalanine) LDH using powder X-ray diffraction.46 The authors do not
report the interlayer water content of the synthetic LDH, which hinders direct comparison
between the experimental and simulation results. As shown above, however, the simulations
reproduce accurately the experimentally-determined correlation between interlayer spacing
and water content for LDHs containing organic anions.
Figure 10. Snapshot of the simulation cell of a model Mg3Al-LDH containing (S)-phenylalanine, following 50
ps of molecular dynamics simulation at 300 K
The snapshot shows that the (S)-phenylalanine molecules retain the bilayer arrangement in
which they were placed initially, with the longest axis of the molecule generally oriented in an
approximately perpendicular direction from the plane of the hydroxide layers. The phenyl rings
of the molecules thus form a hydrophobic region in the mid-plane of the interlayer from which
nearly all of the water molecules are excluded, their preferring instead to form layers close to
the surface of the hydroxide layers. For each (S)-phenylalanine molecule, the closest contact to
the hydroxide layers is made through the oxygen atoms of the carboxylate group, as should be
expected given the positive charge on the layers. The oxygen atoms of the carboxylate groups
and water molecules thus appear to form an oxygen monolayer on the surface of the hydroxide
layers. In this region, a number of close-contacts occur between the water molecules, the
carboxylate groups and the hydroxide surface that are consistent with the existence
hydrogen-bond interactions (Figure 11). The hydrogen-bond, H…O, distance is typically 2.2 Å
with variable O-H…O angle, where the hydrogen-bond donor is a surface OH group and the
acceptor is an O atom belonging to a water molecule or carboxylate group. The amine group is
also involved in what might be considered hydrogen-bond interactions with water molecules,
although generally not with the hydroxide surface.
Figure 11. Possible hydrogen-bond interactions (broken lines) in a model Mg3Al-LDH containing
(S)-phenylalanine, following 50 ps of molecular dynamics simulation at 300 K. The criteria for hydrogen-bond
assignment are that the maximum H-A distance is 2.5 Å and the minimum D-H…A angle is 90º, where D and A
are hydrogen-bond donors or acceptors, respectively. Here, N and O are allowed to act as either donor or
acceptors, whereas C is allowed to act as neither.
The relative orientation of the interlayer anions is displayed in Figure 12. The view is along
[001] with only the phenyl ring of the anions in one interlayer of the model displayed. The
separation between the anions is typically 6Å, as indicated by the selected centroid-centroid
distances. Furthermore, an edge-to-face orientation is generally preferred, rather than a
face-to-face orientation, possibly indicative of weak but directional C-H...π hydrogen bonding.
(π-electron density is of course not accounted for in classically-based simulations. Any
interaction is simply coulombic between a H atom with a positive partial charge and the C
atoms in the phenyl ring bearing negative partial charges).47
Figure 12. View along [001] of model Mg3Al-LDH containing (S)-phenylalanine anions following 50 ps of
molecular dynamics simulation at 300 K. Only the phenyl ring of the anions in one interlayer of the model is
displayed (4 simulation cells in the ab-plane are displayed). Centroids of the phenyl rings are indicated in black.
Distances are in Å. Two short C-H...π contacts are also indicated (the C-H...centroid angles are 140.8 and
173.4º for the 4.06 and 2.96 Å contacts, respectively).
A snapshot of the simulation cell for the model Mg3Al-LDH containing (S)-tyrosine,
following 50 ps of molecular dynamics simulation at 300 K is shown in Figure 13. Sixty water
molecules were included in the simulation cell (30 per interlayer), which corresponds to 17.8
mass percent and gives an empirical formula of [Mg3Al(OH)8]((S)-tyrosine).5H2O. Again, the
mean simulation-cell parameters in the ab-plane are within five percent of the initial values.
The average interlayer spacing over the last 10 ps of the simulation is 18.0 ± 0.2 Å, which is
slightly larger than the interlayer spacing of 17.5 Å determined by Fudala et al. for a synthetic
Zn3Al-LDH containing L-tyrosine using powder X-ray diffraction.46 Presumably, this small
difference may be attributed to a small difference between the water content of the model and
real systems. The geometrical arrangement of the cell is generally comparable to the
(S)-phenylalanine example, the only significant difference being additional hydrogen-bond
type interactions between water molecules and the OH group belonging to (S)-tyrosine.
OTHER LDH SIMULATIONS

Fogg et al. have recently used energy minimisation methods to rationalise the structure of
anhydrous LiAl-LDHs containing Cl-, Br- or NO3-, anions.48 In this work, energy minimisation
was achieved using the Extensible System Force Field, ESFF within the Insight II software
package.49 The simulations showed that the calculated lowest-energy structures were in good
agreement with the structures determined experimentally using synchrotron X-ray and neutron
diffraction Rietveld refinement methods.50 In addition, the same energy minimisation
methodology was utilised to make predictions of the interlayer structure of LiAl-LDHs
containing SO42-, CO32-, and oxalate (C2O4-) anions, for which the structures had not been
determined previously.
Figure 13. Snapshot of the simulation cell of a model Mg3Al-LDH containing (S)-tyrosine, following 50 ps of
molecular dynamics simulation at 300 K.
Modelling of the structure and dynamics of the interlayer Cl- anions and water molecules in
hydrocalumite, [Ca2Al(OH)6]Cl.2H2O, has been performed recently by Kalinichev et al.51
Hydrocalumite, also known as Friedel’s salt, differs from most hydrotalcite-like LDHs in that it
has an ordered Ca and Al distribution in the hydroxide layer and a relatively well-ordered Cl-
and water structure in the interlayer. The structure has been characterised by single crystal
X-ray diffraction and the interlayer order is due to coordination of the water molecules to Ca in
the hydroxide layer.52
The system was investigated in the temperature range from –100 to 300 oC using
isothermal-isobaric molecular dynamics simulations, with interactions modelled using a
modified version of the augmented ionic consistent valence forcefield (CVFF) within
Cerius2.27 Good agreement was obtained between the simulated models and the single-crystal
structure, which suggests that the parameterisation of the forcefield is well suited to simulations
of LDHs. In addition, the simulations were used to probe the dynamics of anions and water
molecules in the interlayer and on the hydroxide surface. The surface phenomena were
modelled by separating the interlayer surfaces with a layer of water (20 Å thick) to prevent
interaction between them. To extract dynamical information, the simulations were performed
for a time period of 100 ps and results compared favourably with 35Cl NMR data for
hydrocalumite.53
CONCLUDING REMARKS
Computer simulations, based on relatively simple models and simulation procedures, are
an effective tool for investigating the interlayer structure of LDHs. They can provide detailed
insight into the interlayer properties of the LDH not available from experimental measurements.
Due to the inherent structural disorder and generally low crystallinity of LDHs, complete
structure determination using single crystal or powder X-ray diffraction is rarely possible, for
example. Structure elucidation is then normally reduced to inferring the interlayer arrangement
of the clay from the interlayer separation, which may be obtained from powder X-ray data.
Computer simulations, however, provide a method of predicting the interlayer structure, and
thus studying interactions between the host layers and the interlayer molecules. Dynamical
information about the interlayer species may also be obtained if molecular dynamics
simulations are employed.
In general, results from simulations to date are in good agreement with those of experiment
and suggest that further modelling of these materials would be beneficial. The simulations have
helped to clarify various aspects of the experimental work and are a valuable adjunct for the
interpretation of experimental data. In the future, we hope to extend our modelling of LDHs to
investigate chemical reactions that may occur in the interlayer (such as in situ polymerization)54
or on the surface of LDHs. Such investigations require the use of electronic structure-based
calculations and will be computationally more expensive than the simulations described
previously in this chapter.
REFERENCES
1. J. M. Goodfellow, Ed. Molecular Dynamics: Applications in Molecular Biology, The
Macmillan Press Ltd., London, 1991.
2. Q. Zhong, Q. Jiang, P. B. Moore, D. M. Newns and M. L. Klein, Biophys. J. 74 (1998) 3.
3. Q. Zhong, T. Husslein, P. B. Moore, D. M. Newns, P. Pattnaik and M. L. Klein, FEBS

Letters 434 (1998) 265.
4. D. J. Tobias, K. Tu and M. L. Klein, Curr. Opin. Colloid Interface Sci. 2 (1997) 15.
5. J. A. McCammon, B. R. Gelin and M. Karplus, Nature 267 (1977) 585.
6. N. Quirke, Curr. Opin. Colloid Interface Sci. 2 (1997) 231.
7. J.-B. Maillet, V. Lachet, and P. V. Coveney, Phys. Chem. Chem. Phys. 1 (1999) 5277.
8. C. R. A. Catlow, Modelling of Structure and Reactivity in Zeolites, Academic Press,
London, 1992.
9. C. R. A. Catlow, R. G. Belland J. D. Gale, J. Mater. Chem. 6 (1996) 781.
10. C. R. A. Catlow, L. Ackermann, R. G. Bell, F. Corà, D. H. Gay, M. A. Nygren, J. C. Pereira,
G. Sastre, B. Slater and P. E. Sinclair, Faraday Discuss. 106 (1997) 1.
11. Z. A. Kaszkur, R. H. Jones, D. Waller, C. R. A. Catlow and J. M. Thomas, J. Phys. Chem.
97 (1993) 426.
12. G. Schrimpf, B. Tavitian and D. Espinat, J. Phys. Chem. 99 (1995) 10932.
13. H. Klein, H. Fuess and G. Schrimpf, J. Phys. Chem. 100 (1996) 11101.
14. S. Yashonath, J. M. Thomas, A. K. Nowak and A. K. Cheetham, Nature 331 (1988) 601.
15. S. D. Pickett, A. K. Nowak, J. M. Thomas, B. K. Peterson, J. F. P. Swift, A. K. Cheetham,
C. J. J. den Ouden, B. Smit and M. F. M. Post, J. Phys. Chem. 94 (1990) 1233.
16. J. D. Gale and A. K. Cheetham, Zeolites 12 (1992) 674.
17. A. K. Nowak, C. J. J. den Ouden, S. D. Pickett, B. Smit, A. K. Cheetham, M. F. M. Post
and J. M. Thomas, J. Phys. Chem. 95 (1991) 848.
18. L. M. Bull, N. J. Henson, A. K. Cheetham, J. M. Newsam and S. J. Heyes, J. Phys. Chem.
97 (1993) 11776.
19. S. M. Auerbach, N. J. Henson, A. K. Cheetham and H. I. Metiu, J. Phys. Chem. 99 (1995)
10600.
20. N. J.Henson, A. K. Cheetham and J. D. Gale, Chem. Mater. 8 (1996) 664.
21. E. S. Boek, P. V. Coveney and N. T. Skipper, J. Am. Chem. Soc. 117 (1995) 12608.
22. E. S. Boek, P. V. Coveney and N. T. Skipper, Langmuir 11 (1995) 4629.
23. A. V. C. De Siqueira, N. T. Skipper, P. V. Coveney and E. S. Boek, Mol. Phys. 92 (1997) 1.
24. A. S. Bains, E. S. Boek, P. V. Coveney, S. J. Williams and M. V. Akbar, Mol. Sim. in press,
2000.
25. B. J. Teppen, C.-H. Yu, D. M. Miller and L.Schäfer, J. Comput. Chem. 19 (1998) 144.
26. G. L. Keldsen, J. B. Nicholas, K. A. Carrado and R. E. Winans, J. Phys. Chem. 98 (1994)
279.
27. Cerius2 version 4.2, Molecular Simulations, Inc., San Diego, USA., 1999.
28. J. M. Haile, Molecular Dynamics Simulation: Elementary Methods, John Wiley & Sons,
Inc., New York, 1992.
29. M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids, Oxford Science
Publications, Oxford, 1994.
30. W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Imrey and M. L. Klein, J. Chem.
Phys. 79 (1983) 926.
31. R. Allman and H. P. Jepsen, Neus. Jahrb. Miner. Monatsh. 12 (1969) 544.
32. A. K. Rappé and W. A. Goddard III, J. Phys. Chem. 95 (1991) 3358.
33. J. P. Stewart, MOPAC version 6.0, QCPE No. 455, Department of Chemistry, Indiana
University, 1990.
34. E. S. Boek, P. V. Coveney, S. J. Williams and A. Bains, Mol. Simul. 18 (1996) 145.
35. S. L. Mayo, B. D. Olafson and W. A. Goddard III, J. Phys. Chem. 94 (1990) 8897.
36. W. H. Hoover, Phys. Rev. A 31 (1985) 1695.
37. S. P. Newman, Ph.D. Thesis, University of Cambridge, 1999.
38. S. Miyata, Clays Clay Miner. 23 (1975) 369.
39. V. R. L. Constantino and T. J. Pinnavaia, Inorg. Chem. 34 (1995) 883.
40. M. Aicken, I. S. Bell, P. V. Coveney and W. Jones, Adv. Mater. 9 (1997) 496.
41. I. S. Bell, F. Kooli, W. Jones and P. V. Coveney, Mater. Res. Soc. Proc. 453 (1996) 73.
42. S. P. Newman, S. J. Williams, P. V. Coveney and W. Jones, J. Phys. Chem. B 102 (1998)
6710.
43. W. W. Kagunya, J. Phys. Chem. 100 (1996) 327.
44. R. Mills, J. Phys. Chem. 77 (1973) 685.
45. S. P. Newman, T. Di Cristina, P. V. Coveney and W. Jones, J. Mater. Chem. submitted,
2000.
46. A. Fudala, I. Pálinkó and I. Kiricsi, Inorg. Chem. 38 (1999) 4653.
47. G. R. Desiraju and T. Steiner, Weak Hydrogen Bond in Structural Chemistry and Biology,
Oxford University Press, New York, 1999.
48. A. M. Fogg, A. L. Rohl, G. M. Parkinson and D. O’Hare, Chem. Mater. 11 (1999) 1194.
49. Insight II, Molecular Simulations, Inc., San Diego, USA., 1999.
50. A. V. Besserguenev, A.M. Fogg, S. J. Price, R. J. Francis, D. O’Hare, V. P. Isupov and B. P.
Tolochko, Chem. Mater. 9 (1997) 241.
51. A. G. Kalinichev, R. J. Kirkpatrick and R. T. Cygan, Amer. Mineral. 85 (2000) 1046.
52. A. Terzis, S. Fillippakis, H.-J. Kuzel and H. Burzlaff, Z. Kristallograph. 181 (1987) 29.
53. R. J. Kirkpatrick, P. Yu, X. Hou and Y. Kim, Amer. Miner. 84 (1999) 1186.
54. S. Stackhouse, P. V. Coveney and E. Sandré, in preparation, 2000.
Chapter 4
STUDY OF LAYERED DOUBLE HYDROXIDES BY

THERMAL METHODS
Vicente Rives
Departamento de Química Inorgánica, Universidad de Salamanca,
37008-Salamanca (Spain)
fax: +34 923 29 45 74; e-mail: vrives@usal.es
INTRODUCTION
Layered double hydroxides (LDHs) constitute the counterpart of the long time known
cationic clays; they are formed by positively charged layers, with balancing anions and water
molecules in the interlayers. The most widely known LDHs contain M+2 and M+3 cations in the
layers,1-5 but other systems containing M+/M+3 6 or even M+2/M+4 and M+2/M+3/M+4 7-10 are also
known. They are commonly known also as “hydrotalcite-like” materials, as the mineral
hydrotalcite, first discovered in Sweden around 1842, is a hydroxycarbonate of Mg and Al with
this structure which occurs in nature in foliated and contorted plates. Its formula is
[Mg6Al2(OH)16](CO3) · 4 H2O although it is usually written as [Mg0.75Al0.25(OH)2]
(CO3)0.125 · 0.5 H2O to emphasize its relationship to brucite, Mg(OH)2. As with cationic clays,
the interlayer anions can be easily exchanged, although exchange of carbonate is rather
difficult,11 so anionic exchange representing an alternative way for synthesis of new
hydrotalcites. Also as cationic clays, hydrotalcites can be pillared with polynuclear
anions,3,5,12-15 including metal-containing oxometalates or coordination compounds.
Less stable than cationic clays, LDHs undergo collapsing of their structure upon heating
even at rather moderate temperatures, finally leading to crystalline, three-dimensional phases
which precise nature depends on several factors. Moreover, the calcined product shows
commonly the ability to recover the original layered structure upon equilibration with moisted
air or when immersed in aqueous solutions cotaining anions,16-19 and this method has been used
in some cases as an alternative route to prepare new LDHs.
Finally, it should be noted that one of the most interesting features of LDHs is their role as
precursors for heterogeneous catalysts,2 which catalytic performance strongly depends on the
method followed during thermal decomposition from the original LDH to the final mixture of
metallic oxides.
128 Vicente Rives
Although thermal decomposition of LDHs ultimately leads to formation of mixed oxides,

we can distinguish several situations, depending on the atmosphere (oxidizing or non-oxidizing)
surrounding the sample during decomposition, the presence of oxidizable (or reducible) cations
in the brucite-like layers, and the nature of the interlayer anion. For these reasons, this review
has been divided into four sections, each one dealing with: (i) LDHs with volatile, i.e., non
permanent (carbonate, nitrate, sulphate, chloride, etc.) inorganic anions in the interlayer space;
(ii) LDHs with interlayer organic anions; (iii) LDHs with non volatile, metal-containing,
interlayer anions, i.e., oxometalates or anionic coordination compounds, and (iv) LDHs with
reducible cations in the layers or constituting the interlayer anions. With this classification we
hope to facilitate understanding of the different processes taking place during thermal treatment
of LDHs.
LAYERED DOUBLE HYDROXIDES WITH VOLATILE,

INORGANIC ANIONS
Carbonate-LDHs with Non-transition Metal Cations
For obvious reasons, most of the studies carried out on thermal decomposition of LDHs
refer to the use of synthetic hydrotalcite itself, [Mg0.75Al0.25(OH)2](CO3)0.125 · 0.5 H2O, (Mg:Al
molar ratio = 3:1 or with other Mg/Al rations).
In one of the pioneering papers on a Mg-Al-CO3 LDH, Miyata reported1 three thermal
transitions, which precise properties (i.e., temperature and intensity) depend on the aluminum
content in the LDH. These three features occur at ca. 280, 400, and 450 °C, according to the
DTA (differential thermal analysis) traces, and were attributed to loss of interlayer water, of
structural hydroxyl groups (as H2O), and of interlayer carbonate (as CO2), respectively. These
results have been also reported by Yun and Pinnavaia upon a detailed study of water content in
Mg,Al-CO3 LDHs.20
Reichle et al.21 reported that CO2 evolution starts already at 300 °C, water vapour and CO2
escaping through fines pores generated at the brucite-like layers, thus accounting for the
increase in specific surface area observed for these medium-temperature calcined samples;
actually, an increase in the specific surface area, directly related to the presence of such pores,
has been reported as the Al (and the carbonate) content increases.22
Typical Differential Scanning Calorimetry (DSC) and TG/DTG (Thermogravimetric/
Differential Thermogravimetric analyses) curves for a Mg-Al-CO3 LDH (Mg:Al:2:1) are given
in Fig. 1.23 In these case, two peaks are recorded in the DSC curve, which positions fit
remarkably well with those in the DTG curve (indicating that they correspond to weigth-loss
processes): peak II at ca. 220 °C, and peak III with two components at 330 °C (IIIa), and 380 °C
(IIIb). However, if the sample had been previously equilibrated with water vapour at room
temperature for 70 h, an additional peak (peak I) is recorded below 100 °C; this picture
coincides with the early work of Miyata.1 The precise position and intensity of peak I depends
on the specific sample tested, while the positions and intensities of peaks II and III remain
rather unchanged. Similar results have been reported by other authors24,25 for Mg-Al-CO3
LDHs.
Study of Layered Double Hydroxides by Thermal Methods 129
Meanwhile, Powder X-ray diffraction (PXRD) shows that the position of the (003)
diffraction peak (which spacing coincides with the sheet-sheet distance, perpendicular to the
sheet plane) remains almost unchanged in either intensity or position until ca. 150 °C; above
this temperature a gradual decrease of d(003) is observed,23-25 with a rapid fall to ca. 6.6 Å at ca.
200 °C. When the calcination temperature is further increased, mostly amorphous materials are
formed; close to 500 °C crystallization of highly disordered MgO is observed, although the
lattice parameters are smaller than for pure MgO, probably due to inclusion of Al+3 in the MgO
lattice forming a solid solution; finally, well crystallized MgO is formed, together with
MgAl2O4 spinel, when the solid is calcined at 1000 °C or above, Fig. 2.
Figure 1.-(a) Differential scanning calorimetry (DSC), (b) thermal gravimetric analysis (TG), and (c)
differential thermogravimetric analysis (DTG) for a “dry” Mg,Al CO3 LDH treated at 105 °C in air for 18 h.
Reprinted from L. Pesic, S. Salipurovic, V. Markovic, D Vucelic, W. Kagunya and W. Jones, J. Mater. Chem., 2
(1992) 1069, Thermal characteristics of a synthetic hydrotalcite-like material, J. Materials Chem. 2 (1992)
1069-1073, © 1992, with permission from the Royal Society of Chemistry.
Kanezaki has recently reported26-29 a detailed high-temperature PXRD study of the phases
formed during thermal decomposition of Mg,Al-CO3 LDHs with different Mg:Al ratios,
concluding that the metastable phase formed at ca. 200 °C, accounting for the interlayer space
of 6.6 Å, corresponds to a decarbonated LDH, through reaction between carbonate ions and
water molecules in the interlayer space, leading to CO2 evolution and formation of a layered
130 Vicente Rives
material with interlayer hydroxyl anions (the natural material is known as meixnerite, and it has
been also synthetized). However, this conclusion should be rejected, as mass spectrometric
analysis of gases evolved during thermal decomposition23,30-32 has shown that peak II
corresponds to removal of water (and only 1% of total carbon evolved up to 550 °C23), while
peak II corresponds to evolution of both CO2 and H2O, Fig. 3; actually, splitting of this peak,
probably because of its double origin, is observed clearly in some cases. Recent results33 by
temperature programmed desorption (TPD) have confirmed the sequence above given for gases
evolved during calcination of different hydrotalcite-like materials, Fig. 3. Neutron diffraction
and inelastic neutron-scattering studies have confirmed also that lattice water is expelled after
heat treatment at ca. 210 °C.34
Figure 2.-Powder X-ray diffraction diagrams (radiation Cu K ) for a Mg,Al-CO3 LDH calcined in air at the
temperatures given (°C). Reprinted from F. M. Labajos, V. Rives and M. A. Ulibarri, Effect of hydrothermal
and thermal treatments on the physicochemical properties of Mg-Al hydrotalcite-like materials, J. Mater. Sci.,
27 (1992) 1546-1552, © 1992, by kind permission from Kluwer Academy Publishers.
There seems to be a general agreement among different authors about the chemical origin
of the thermal effects detected, and which can summarized as follows:
Removal of Adsorbed Water.
This process takes place between room temperature and ca. 100 °C, is absent in samples
dried after synthesis, and is only observed in the case of samples previously equilibrated with
water vapour for prolongued periods of time. The heat involved in this process has been
calculated23 as ∆H = 43±7 kJ mol-1, slightly higher than that normally expected during
evaporation (ca. 40 kJ mol-1), thus being likely that the water is condensed and not simply
physisorbed. Drying at 105 °C is enough to remove most of this water, but exposure to ambient
conditions (even during handling of the sample) is enough for an external partial rehydration of
the sample, thus giving rise to re-adsorption of water, the process being reversible. Water
molecules in the interlayer are hydrogen bonded to interlayer carbonate ions, thus accounting
for the splitting of the ν3 band of this anion into two bands at 1400-1383 and 1369-1364
cm-1.25,35
Figure 3.-(left) Mass spectrometric analysis of gases evolved during thermal decomposition of a Mg,Al-CO3
LDH, reprinted from V. Rives, Comment on “Direct observation of a metastable solid phase of
Mg/Al/CO3-layered double hydroxide by means of high-temperature in situ powder XRD and DTA/TG” Inorg.
Chem., 38 (1998) 406-407, © 1998, with permission from the American Chemical Society; (b) temperature
programmed desorption profiles of gases evolved during thermal decomposition of a Ni,Al-CO3 LDH
(takovite), reprinted from P. Bera, M. Rajamathi, M. S. Hegde, P. V. Kamath, Thermal behaviour of hydroxides,
hydroxysalts and hydrotalcites, Bull. Mater. Sci. (India) 23 (2000) 141-145, © 2000, with permission from the
Indian Academy of Sciences.
Removal of Interlayer Water Molecules.
Early work by Miyata proposed interlayer water is responsible for the weight loss around
220 °C.1,36 According to Stanimirova et al.,35 two consecutive stages can be distinguished: (i)
First, up to 140-180 °C, the interlayer is dehydrated, but this process has no effect on the
interlayer space, d(003) being ca. 7.8 Å, as carbonate ions remain parallel to the layers, acting
as a sort of chemically-unbonded pillars; in such a situation, the thickness of a carbonate ion
and of a water molecule would be the same, and so removal of the latter would not modify the
interlayer spacing. (ii) Secondly, up to 240-260 °C, the fully dehydrated phase is formed. The
132 Vicente Rives
measured enthalpy change (∆H=55±2 kJ mol-1) for dehydration23 is close to that expected for
physisorbed water. IR bands observed in the νOH region after removal of water in vacuo24 are
close to those reported in the literature for Mg37,38 and Al39,40 oxides. The d(003) spacing
decreases from ca. 7.60 Å to 6.60 Å. This decrease from ca. 7.8 to 6.6 Å does not leave room
enough in the interlayer to accomodate carbonate ions (diameter close to 3.0 Å, and interlayer
space only 1.8 Å, from a interlayer spacing of 6.6 Å and a brucite-like sheet width of 4.8 Å41),
and it has been explained35 assuming a “grafting” of the carbonate ions to the brucite-like layers,
a process already described by other authors for LDHs containing chromate or dichromate as
interlayer anions.42-44 Such a grafting requires substitution of hydroxyl groups (from the parent
layers) by oxide groups (from the carbonate ions) in the corners of some of the [M(OH)6]
octahedra in the layers. Evidence for partial removal of OH groups comes also from 1H
MAS-NMR measurements.24 The PXRD results, on the other hand, indicate also, in addition to
the shift of the d(003) peak from 7.8 to 6.6 Å, a broadening of such a peak, indicating that,
despite layered, the structure becomes partially disordered.45 Accordingly, the 27Al MAS-NMR
spectrum of a sample calcined at 250 °C displays a six coordinated Al peak much broader
(FWHM = 860 Hz) at δ ca. 8.8, than for the uncalcined sample (370 Hz at δ 9.1),19 together
with a weak peak at δ 76, which intensity indicates that at this temperature ca. 25% of Al ions
have migrated to tetrahedral positions; such Oh → Td migration has been also reported to occur
when heating is performed in vacuo.24 Appearance of tetrahedrally coordinated Al (previously
suggested by Belloto et al. from XPS measurements46) has been reported at temperatures as low
as 200 °C30 or even 100 °C;47 the presence of five-coordinated Al species is not, however,
confirmed by these studies, although their presence has been claimed during decomposition of
Zn,Al-CO3 LDHs.48 However, it has been also pointed out47 that the heating rate somewhat
controls the crystallinity degree if intermediate species (amorphous at large heating rates, but
with similar MAS-NMR spectra to that of the parent material at low heating rate).
Decarbonation and Dehydroxylation.
These two processes account together for the weight loss recorded up to ca. 450-500 °C.
The weight loss is, however, usually recorded as a single effect, although the derivative curve
(DTG) is asymmetric, suggesting two consecutive processes; similar features can be observed
in the DTA traces. So, dehydroxylation of OH bound to Al has been claimed1,16 as the origin of
a peak at 305-320 °C, while the peak at 375-400 °C has been attributed to dehydroxylation of
OH bound to Mg and the main CO2 evolution.31-33 After calcination at 350 °C the PXRD
pattern shows only broad peaks roughly coincident with those of MgO, the shift (decrease)
from the tabulated values being assigned45 to formation of a non-stoichiometric spinel
containing Al3+ ions (the main diffraction peaks of the MgAl2O4 spinel coincide with those of
periclase, MgO), or, alternatively, to formation of a solid solution of Al3+ ions in the MgO
lattice.16 Above 800 °C, however, the MgO lattice parameter increases until reaching a value
close to that for pure MgO.31 It should be noted that, despite the role of carbonate is to balance
the excess in positive charge of the layers because of the Mg2+/Al3+ substitution, LDHs with the
same Mg/Al ratio, but with large specific surface area, release more CO2 up to 350 °C,
indicating that some CO2 should be also adsorbed on the external surface of the crystallites and
is thereof released at a rather low temperature, 150-250 °C.31,32 Hibino et al.31 have shown that
in samples with large Al content (the minimum Mg:Al ratio is 2:1 to avoid edge-sharing
Al(OH)6 octahedra49), CO2 evolution is observed even at 900 °C; these authors claim that
during collapsing of the structure, some carbonate remains trapped inside the decomposed
material, thus hindering complete decarbonation, which takes place only when Al3+ migrates to
form MgAl2O4 spinel. For lower Al3+ content, such a process would not be observed.
In addition to weight loss and MS-GC analysis of evolved gases,23,30-33 dehydroxylation
has been also concluded from 1H MAS-NMR spectra; both the intensity and the second
moment (S2) of the NMR line become weaker as the calcination temperature increases, the
decrease in S2 accounting for longer H-H distances24 as the dehydroxylation proceeds. With
respecto to the evolution of the layers during calcination at high temperature, the 27Al
MAS-NMR spectra indicate that the percentage of tetrahedral Al3+ ions increases with the
calcination temperature,19,50 while two distinct signals due to octahedral Al3+ species develop
(the band broadens and shifts to higher δ values). Finally, calcination at 1000 °C leads to
development of PXRD peaks ascribed to MgO and MgAl2O4 spinel; however, the 3Q 13Al
MAS-NMR spectra display sharper peaks (more symmetric environment of the Al3+ ions),
corresponding to two four-coordinated Al3+ species and probably two six-coordinated Al3+
species; it should be noted that the percentage of tetrahedral Al3+ species decreases from 750 °C
upwards.
When alternative synthetic routes are followed, for sol-gel synthetized Mg,Al-CO3 LDHs
it has been found51 that those prepared with Al triacetylacetonate were more stable (i.e. the
structure collapses at higher temperature) than those prepared with Al trisecbutoxide, probably
because of a poor hydrolysis of this last compound: combustion of the unhydrolyzed organic
residue would favour destruction of the layered structure.
Quantitative analysis of TG traces can be used to determine the amount of water molecules
in the interlayer space of LDHs, so completing chemical analysis data usually reported for the
layer cations and, in many cases, for the interlayer anion. For example, assuming a Mg,Al-CO3
LDH, the final product after high temperature (e. g., 1000 °C) calcination is a mixture of MgO
and Al2O3 or MgO and Mg2Al2O4 (differences being no relevant for weight loss calculation).
The maximum amount of interlayer water can be calculated through simple structural
reasonings: the size of a carbonate anion can be assumed to be three times that of a hydroxyl
group, and the sizes of a hydroxyl group and a water molecules can be assumed to be equal. For
a close-packing situation, the number of “spheres” in the interlayer (carbonate, nC, and water,
nW) would be equal to the number of “spheres” (hydroxyl groups, nO) in the layers, i.e., per
formula of hydrotalcite nO = 2 = nC/3 + nW. If the nature and amount of interlayer anion nC is
known (well from elemental chemical analysis, or simply assuming a single anion
electrically-balancing trivalent cations in the layers), calculation of interlayer water can be
straightforward carried out. However, the experimental value is usually lower than the
maximum value calculated, as restriction arise in order to attain favourable orientations to
maximize hydrogen bonding of water molecules with interlayer carbonate and even with layer
hydroxyl groups.
It should be mentioned, however, that in some cases it is difficult to distinguish the precise
nature of the interlayer anion, even when carbonate was present during synthesis, as repeated
washings of the precipitated solids with distilled water to eliminate counterions in the starting
salts may give rise to formation of hydrogen-carbonate species:23
CO32- + H2O → OH- + HCO3-

134 Vicente Rives
A parallel study by infrared spectroscopy or other spectroscopic techniques is then

necessary to distinguish the nature of the interlayer anion.
In addition to the studies discussed so far, involving exclusively LDHs with Mg and Al in
the brucite-like layers, many other studies have been reported on systems possesing different
cations.
Due to the similar chemical properties between Al and Ga, LDHs containing Mg and Ga
have been also studied. Although according to Aramendía et al., the thermal decomposition
patterns of Mg,Ga-CO3 hydrotalcites follow the same trends as those observed for the
Mg,Al-CO3 LDH,52,53 differences have been reported by López-Salinas et al.,54 depending on
the Mg/Ga ratio, Fig. 4. Dehydration is completed at lower temperatures (and the
corresponding DTA peak shifts in the same direction) as the Mg/Ga ratio increases (229 °C for
Mg/Ga=4.3, but 175 °C for Mg/Ga=12.9). Also, larger amounts of interlayer water exist as well,
in agreement with larger space availability as the Mg/Ga ratio increases; the dehydration
enthalpy also increases with the Mg/Ga ratio, and so difficulty in dehydration is mainly related
to diffusional barriers. The result is similar to that previously reported by Mascolo et al.55 for
LDHs with different Mg/Al ratios.
With respect to the second weight loss (dehydroxylation plus decarbonation), it extends in
a narrower temperature range, approaching the curve recorded for Mg(OH)2, as the Mg/Ga ratio
increases, and this effect has been related to the decreasing concentration of polar Mg-O-Ga
sites as the Mg/Ga ratio increases, the solid residue thus interacting more weakly with the
evolved gases. The corresponding DTA peak is rather narrow in all cases and does not shift
significantly for different Mg/Ga ratios. The increase in the enthalpy associated to this DTA
peak when the Mg/Ga ratio increases has been tentatively attributed by these authors54 to the
lower energy demand to break a Ga-OH bond than to break a Mg-OH bond, although the
reported values are not too different, 352±40 and 357±12 kJ/mol, respectively.56
Figure 4.-Effect of the Mg/Ga molar ratio on DTA (left) and TG (right) patterns of Mg,Ga-CO3 LDHs. Mg/Ga=
(a) 1.8, (b) 2.9; (c) 4.3; (d) 5.3; (e) 7.7; (f) 12.9; (g) Mg(OH)2. Horizontal bars in the right plot indicate range of
stability. Reprinted from E. López-Salinas, E. Torres-García and M. García-Sánchez, Thermal behavior of
hydrotalcite-like [Mg1-xGax(OH)2](CO3)x/2 · mH2O as a function of gallium content, J. Phys. Chem. Solids
58 (1997) 919-925, © 1997, with permission from Elsevier Science.
Some studies have been also reported on LDHs containing La3+, Y3+, Zr4+ or Sn4+.57-60
However, in all cases, the simultaneous presence of Al3+ seems to be essential to stabilize the
layered structure, probably because of the distortions originated by the large differences in
ionic radii between these cations and Mg2+ or Al3+. As a consequence, formation of unidentified
amorphous Zr and Mg salts (hydroxides and hydroxycarbonates) in Mg,Al,Zr-CO3 LDHs,59 or
crystallization of side products, such as MgSn(OH)6 in Mg,Al,Sn-CO3 60 has been reported; in
other cases, the observed effect is a decrease of crystallinity, i.e., a broadening of the diffraction
peaks.58,60 In all these cases, the first effect in the DTA traces shifts towards lower temperature
as the amount of Mn+ cation is increased (M = Sn, Zr, Y). Probably, the poor crystallinity
favours decomposition of the layered structure at a lower temperature than for a Mg,Al-CO3
LDH or, alternatively, the incorporation of these cations with a lower charge-to-size ratio
facilitates the decomposition process due to the weakening of the interaction between the
brucite-like layers and the interlayer.
Carbonate-LDHs with Transition Metal Cations in the Layers
Due to the close stability of transition metal cations in different oxidation states, the
thermal decomposition patterns of these LDHs change deeply from those above commented if,
during calcination, additional red-ox processes occur simultaneously. Under these
circumstances, the curves recorded will become modified if the analysis is performed in
oxidizing (air or oxygen) or inert (N2, He, Ar) atmospheres.
Fig. 5 shows the DTA and TG patterns for a NiV-CO3 LDH recorded in O2 and in N2.61 The
first DTA peak, due to dehydration, is similar in both cases, while the second effect is much
weaker when the analysis is performed in O2 and shows a rather expected intensity when
recorded in N2. During calcination in air, V3+ ions are oxidized, an exothermic process which
presumably takes place in the same temperature range as the endothermic removal of water and
CO2; consequently, both effects become almost completely cancelled.62 Correspondingly, the
weight loss recorded in the TG analysis is larger when the analysis is performed in N2 than in O2
(28.2% vs. 23.6 %, respectively, of the original weight of this Ni,V-CO3 sample): calcination of
a Ni,V-CO3 LDH will lead to the formation of NiO and V2O3 (or solids related to these) if V3+
ions are not oxidized during calcination (i.e., in N2), but NiO and V2O5 in oxygen, thus
accounting for the larger weight in oxygen of the final solid. Similar results had been
previously reported for Co-containing hydrotalcites.63 Even in some cases, depending on the
amount of heat released during oxidation, the amount of heat released due to oxidation equals,
or even overcomes the heat demand due to decarbonation and dehydroxylation, thus giving rise
to a flat trace64,65 or a net exothermic effect in this temperature range.63 Actually, thermal
decomposition studies of Mg,Co,Al-CO3 LDHs have shown66 that the DTG peak
corresponding to the second weight loss (dehydroxylation plus decarbonation) is recorded as a
sharp signal for Mg-free solids, but with several shoulders in the high temperature side when
the Mg content is increased (and that of Co consequently decreased), evidencing a lower
release of heat due to a lower concentration of oxidizable Co2+ ions. Moreover, mass
spectrometric monitoring of gases evolved during decomposition of these samples containing
both carbonate and nitrate in the interlayer66 have shown formation of NO, but only traces of
NO2, probably because a larger oxygen demand by oxidizable Co2+ ions, similarly to previous
results with Ni,Mg,Al-CO3,NO3 LDHs,67 NO being always released at higher temperatures
136 Vicente Rives
than CO2. However, the overall process also depends on the atmosphere during synthesis,
which may lead to formation of Co3+-containing LDHs,68,69 which calcination in air would
release a lower amount of heat, due to oxidation, than in the case of LDHs containing
exclusively Co2+ in the layers.
Figure 5.-DTA curves of a Ni,V-CO3 LDH recorded in nitrogen or in oxygen.61
LDHs with Other Interlayer Inorganic Anions
Thermograms recorded for LDHs with partially chloride-substituted carbonate are rather
similar to those of samples containing exclusively carbonate, with only a minor influence on
the total weight loss recorded, but shifting the second endothermic DTA peak 15-35 °C towards
higher temperatures,70,71 while dehydroxylation occurs at lower temperatures than for those
LDHs containing carbonate or nitrate.72 However, Velu et al.48 have reported a complex
decomposition pattern for a Zn,Al-CO3,Cl LDH, both for removal of interlayer water (with
several overlapped DTG minima below 300 °C) and HCl/Cl2 loss at 450-600 °C. For
nitrate-containing LDHs, evolution of NO2 and NO was observed at 250 and 390 °C,48 while for
samples containing sulphate a weight loss recorded at a rather high temperature, 850 °C,48 has
been attributed to complete decomposition of SO42- in the interlayer into gaseous SO3.73 Broadly
speaking, LDHs with vaporizable anions (carbonate, nitrate) decompose at lower temperatures
than those with non-vaporizable (SO42-, Cl-) anions. The activation energies calculated for the
thermal decomposition are larger for divalent containing LDHs than for those containing
monovalent anions (carbonate > sulphate >> chloride > nitrate), which has been attributed to a
stronger binding force between the divalent anion and the basic layer;48 it should be also noticed
the poor ability of nitrate to act as a ligand. Formation of pentacoordinated Al species,
characterized by a signal at δ ca. 50 ppm, similar to that existing (δ ca. 30 ppm) in ρ-alumina
(formed by thermal decomposition of gibbsite30) upon calcination at 500 °C, has been reported
for sulphate and carbonate-containing Zn,Al-LDHs,48 probably due to the ability of these
anions to form bridged bidentate species.
Ramos et al. 74 have prepared LDHs by a sol-gel method starting from Mg ethoxide and
different Al sources (nitrate, sulphate and chloride), finding the incorporation of the
Al-balancing anion in the interlayer (but chloride/carbonate competition when starting from
AlCl3); in their thermal analysis traces, these solids show endothermic peaks due to removal of
water and hydroxyl groups, but also a sharp exothermic effect at 435-515 °C due to combustion
of unhydrolyzed ethoxide species75 which partially cancels the endothermic effects due to
removal of interlayer anions and layer hydroxyl groups. However, Yamaguchi et al.76 have
reported DTA traces without such an exothermic peak, but only the expected endothermic
effects close to 270 and 470 °C, for Mg,Al-CO3 LDHs prepared from magnesium methoxide
and aluminium isopropoxide; probably, the drying treatment at 80 °C under vacuum had
completely removed any traces of unreacted alkoxides.
Chisem et al.77 have reported DTG traces for a Li,Al-CO3 LDH with increasing amounts of
nitrate, introduced by ionic exchange under acidic conditions (pH=1). From a complex DTG
peak for the original sample at ca. 200-300 °C, sharp minima at ca. 100, 250, and 550 °C
develop for the sample exchanged for 72 h. MS analysis of evolved gases during
decomposition shows the steady decrease in the intensity of the peak at m/e=44 (CO2+) due to
carbonate decomposition, and the progressive increase in the intensity of the peak at m/e=30
(NO+), due to nitrate decomposition. The presence of three CO2 signals (ca. 280, 330, and 700
°C) and three NO signals (ca. 390, 500, and 590 °C) has been attributed to two different
situations: formation of interstratified layers (ones containing nitrate and the others containing
carbonate), in agreement with Weber et al.,78 or association of the anion with either the
interlayer region or with Li+ or Al3+ cations.
The Mg/Al ratio, and thus, the concentration of interlayer anions, has an effect on the
thermal stability of the layered structure, at least when nitrate is the interlayer anion. So,
Vansant et al.79 have reported an increase in the position of the DTG peak due to
dehydroxylation and nitrate removal, shifting from ca. 350 °C (Mg/Al=4.44) to ca. 460 °C
(Mg/Al=2.05); the temperature was 360-390 °C for Mg(OH)2 and Al(OH)3; as this wide range
(350-460 °C) cannot be attributed to dehydroxylation, these authors conclude that it is a
consequence of the increased layer charge, which helds more tenaciously the nitrates as the
Mg/Al ratio decreases.
The preparation of a LiAl2(OH)7 · 2 H2O LDH by hydrothermal reaction between hydrated
alumina gel and LiOH has been reported by Nayak et al.80 Although total weight loss is in
agreement with literature values,81 the sequence of losses differs, and a sharp, intense
endothermic DTA peak due to dehydration is followed by a weight loss, up to 500 °C, due to
dehydroxylation. It should be noted that small weight losses up to 1143 °C are due to
evaporation of Li2O. Such a process is hardly expected in other types of LDHs containing Mg,
Zn, Al, ..., which form the corresponding oxides upon calcination, possessing high evaporation
temperatures.
138 Vicente Rives
LAYERED DOUBLE HYDROXIDES WITH ORGANIC ANIONS

Neutral organic species have been often used for swelling of layered materials to favour
access of large anions into the interlayer space by ion exchange.18,82-84 Hybrid organic-inorganic
compounds formed by LDHs with intercalated organic anions have been also prepared. These
materials usually show larger d-spacings than the carbonate-form, and deep changes in the IR
spectra can be also seen. The thermal decomposition traces usually display, in addition to
effects due to dehydration (lower concentration of interlayer water is sometimes observed, due
to hydrophobicity of the organic anions), and dehydroxylation, some other due to combustion
of the organic anion, but interesting features are usually observed at lower temperatures.
Besse et al. have reported the intercalation of oxalate (=ox)85 and succinate and tartrate86
into several LDHs. Oxalate-containing Zn,Al LDHs (d=7.78 Å) were obtained and, under
similar synthesis routes, Zn,Al LDHs with intercalated [Al(ox)3]3- anions (d=9.91 Å) were also
prepared,85 although a similar spacing had been previously attributed by Lagaly et al.87 to the
presence of tilted oxalate anions. Thermal decomposition leads to formation of ZnO and
ZnAl2O4 in both cases, without CO evolution (also reported by Lagaly et al.87), as observed
during thermal decomposition of metal oxalates. Maximum H2O evolution is observed at ca.
220 and 320 °C for the 7.78 Å phase, but at 180 and 380 °C for the 9.91 Å phase.
Correspondingly, CO2 evolution from the first phase was similar to that observed for carbonate
Zn,Al LDH, while for the latter, sharp CO2 evolutions were observed at ca. 400 and 500 °C.
These authors have also reported Zn,Al and Zn,Cr LDHs intercalated with succinate and
tartrate.86 Calcination at 150 °C leads to contraction of the interlayer distance, although the IR
spectra of the 150 °C-calcined materials are essentially identical to those of the untreated solids,
indicating that the organic molecules are not grafted onto the layer; moreover, the analogies
between calcined tartrate and succinate LDHs also discard any sort of condensation reaction
during contraction. This is due to a stereochemical rearrangement around the central C-C bond
without bond breaking, as confirmed by 12C CP-MAS NMR spectroscopy, which permits the
organic anion to act as a bridge attached to both adjacent layers via hydrogen bond, cancelling
rehydration of the calcined solids. Removal of interlayer water, up to 250-300 °C, is followed
by a strong exothermic DTA effect due to decomposition (combustion) of the organic anions.
Intercalation of amino acids is important as these molecules being amphoteric, they can be
protonated to cations, to be intercalated in cationic clays, or deprotonated to anions, able to
intercalate into LDHs. Kiricsi et al. have reported the intercalation of deprotonated
L-tyrosine88,89 and L-phenylalanine89 into a Zn,Al LDH (It should be noted that these authors
report a d-spacing of 8.9 Å, instead of the common value of ca. 7.8 Å for the reference
Zn,Al-carbonate LDH studied, despite the IR spectra indicate a low water content, and the
amino acids were intercalated by anion exchange at pH=8 starting from the carbonate LDH).
The DTG (no TG nor DTA curves are given in these papers) show three minima due to
desorption of physisorbed water at ca. 100 °C, followed by loss of chemisorbed (crystal) water
(ca. 210 °C for the original LDH and for the organic-intercalated materials) and
dehydroxylation (300 °C for the LDH and 270 °C for the organic-intercalated LDHs), followed
finally by collapsing at ca. 400 °C; unfortunately, no quantitative information is given about the
chemical composition of the intercalated nor the original LDHs, nor the recorded weight losses.
Intercalation of poly(styrene sulphonate) (PSS) into Mg,Al and Zn,Al LDHs has been
reported by Oriakhi et al.90 These nanocomposites, with ca. 1 polymer repeat per 3-metal
segment in the LDH structures, show d-spacings compatible with a bilayer of PSS between the
LDH sheets. Upon calcination, the Mg,Al derivative losses ca. 15% of the initial weight up to
100 °C (water removal). A plateau up to ca. 300 °C indicates that the dehydrated species is
rather stable and remains white (i.e., the polymer has not carbonized). Degradation starts at ca.
400 °C (as for Na-PSS), rendering a black solid; the weight loss (23%) between 300-500 °C is
ascribed to dehydroxylation and decomposition of the polymer, as shown also by DSC, with an
endothermic and an exothermic effect, respectively, in this temperature range. A sharp weight
loss at ca. 800 °C (750 °C for Na-PSS) is ascribed to oxidative elimination of the carbonaceous
residue generated during initial polymer degradation, forming a white solid. Quite surprisingly,
this last weight loss is not observed for the Zn,Al derivative (Zn/Al molar ratio =3). These
authors claim that the early appearance (400 °C) of ZnO particles during decomposition of this
LDH favours decomposition of the polymer in a single step. Alternatively, a larger
thermodynamic stability of the Mg,Al-polymer nanocomposite would delay its decomposition
to higher temperatures even in the presence of metal oxides, as previously reported by
Kuwahara et al. for p-toluensulphonate intercalated LDHs.91
Intercalation of alkyl sulphates and similar organic anions has been studied by several
authors,92-94 leading to layered compounds with one or two layers of organic anions in the
interlayer space of the LDH; it has been also observed a reorientation of these molecules after
several treatments. Clearfield et al. have reported94 a study of Ni,Al and Mg,Al LDHs
intercalated with dodecyl sulphate; although simultaneous crystallization of the corresponding
sodium salt has been also observed, these authors report a precise analysis of the decomposition
steps of these compounds. After dehydration up to 180 °C, evolution of C12H24 has been
observed, together with formation of HCl (from incomplete Cl-/dodecyl sulphate exchange)
and SO3 at high temperatures.
Carlino et al.95 have prepared Mg,Al LDHs intercalated with phenylphosphonic acid, by
melting of the acid intimately mixed with the LDH at 187 °C (this rather unusual method to
prepare intercalates has been also applied for cationic clays96,97); consequently, the endothermic
DTA effect due to water removal is considerable weaker, as most of the water should be
removed during the synthesis; decomposition of the guest molecule takes place at ca. 550 °C,
together with dehydroxylation of the layers. However, Vansant et al.98 have found a lack of
weight loss between 300-550 °C for a Mg,Al phenylphosphonic LDH with Mg/Al=4, as a
consequence of the formation of a layered metal phenylphosphonate and transformation of the
LDH structure; on the contrary, for low Mg/Al values (2), phenylphosphonate becomes
intercalated; Zn/Al substitution can partially solve this problem, but a biphasic material (metal
phosphonate, and phosphonate-intercalated LDH) is still formed.
It is known that intercalation of carbon in smectite clays increases their
thermostability;99,100 Hibino et al.101 have studied the thermal stability of LDHs containing
carbonate and carbon clusters. Directly synthetized Mg,Al LDHs with malonate, glutarate,
pimelate, and phthalate were calcined (air or inert atmosphere) up to constant weight (500-600
°C) and then the organic anions carbonized, the material re-converted to a LDH (forming a
“carbon-LDH complex”) in a sodium carbonate solution. DTA curves showed endothermic
effects at 180 and 410 °C, but at 210, 320, and 375 °C for the carbonate analogue, i.e., the
carbon-LDH complex collapses 90 °C above the carbonate analogue, thus suggesting that the
carbon clusters should be between the layers, hampering sintering; the layer structure is
maintained up to the temperature of maximum decarbonation (as checked by PXRD), which is
favoured to occur in a narrower temperature range (as experimentally observed), the CO2
140 Vicente Rives
molecules then “escaping” in between the layers, instead of through the layers, as reported for
carbon-free LDHs.21
This method has been used by Schwarz et al. to prepare carbon particles:102 1,5-naphtalene
disulphonate intercalated in a Mg, Al LDH was carbonized at 650 °C in N2 in situ and extracted
(water and HCl to dissolve the inorganic matrix); aromatization by condensation of the
intercalated molecules occurs at lower temperature than for the pure sodium salt, forming
microporous carbons with a rather heterogeneous micropore structure.
Calcination of Mg,Al LDHs reconstructed from formerly calcined LDHs containing
organic anions (malonate, glutarate, and pimelate) yields a spinel phase at 400 °C, while
temperatures as high as 900 °C are required to crystallize spinel from a reconstructed LDH
prepared through calcination of a carbonate-LDH precursor.103
The thermal decomposition patterns of LDHs with intercalated coordination compounds
containing organic ligands follow trends similar to those depicted by the LDHs discussed in
this section. As an example, Fig. 6 shows the TG and DTA curves of a Mg,Al-[Cu(EDTA)]
complex in tercalated in a Mg,Al LDH.104
Figure 6.-DTA and TG curves for a Mg,Al LDH intercalated with [CuEDTA] complex.104
LAYERED DOUBLE HYDROXIDES WITH PERMANENT

INORGANIC ANIONS
We will discuss here the literature data on LDHs containing interlayer anions such as
phosphate, borate, and silicate, and anionic coordination complexes; the behaviour of
sulphate-containing LDHs has been discussed above.
One of the reported potential applications of LDHs with the hydrotalcite structure is their
use as adsorbents of intestinal phosphate.105 With this aim, Hayashi et al.106 have studied the
progressive chloride/phosphate anionic substitution in Mg,Al LDHs. During thermal

decomposition in nitrogen a steady change in the DTA curves was observed, Fig. 7, as the
concentration of interlayer phosphate was increased: First, the endothermic effect due to
evolution of physisorbed and interlayer water, recorded as a single peak at ca. 130 °C for the
chloride form of the solid, splits into two well defined peaks at 90 °C (physisorbed water) and
234 °C (interlayer water); the total amount of water increases with the phosphate content,
probably because of swelling of the layers (from 7.8 Å for the chloride form to 8.4 Å for the
fully exchanged sample). Secondly, the peaks at 367 and 437°C weaken, the former disappears
and a new peak develops at 337 °C in the chloride-free sample; these authors conclude that the
peaks at 337 and 437 °C should correspond to water removal, and that at 367 °C to elimination
of interlayer chloride. Obviously, as phosphorous is not removed during calcination, the
recorded total weight losses between 250 and 500 °C decrease with the increase in phosphate
content.
Figure 7.-DTA curves of original and phosphate-loaded Mg,Al-Cl LDH. The amount of phosphate loading was
as follows: A (0%), B (6%), C (37%), D (49%), E (57%), F (65%), G (74%), and K (100%). Reprinted from A.
Ookubo, K. Ooi, F. Tani and H. Hayashi, Phase transition of Cl-intercalated hydrotalcite-like compound during
ion exchange with phosphate, Langmuir 10 (1994) 407-411, © 1994, with permission from the American
Chemical Society.
The thermal evolution of LDHs containing borate or silicate prepared by ion exchange of a
nitrate precursor has been reported. 107 The layered structure of the borate form is preserved
above the temperature found for decomposition of the nitrate form (Mg/Al=2), and
142 Vicente Rives
decomposition takes place through several consecutive steps until an amorphous material is
obtained at ca. 500 °C; crystallization of Mg2B2O5 (together with a small amount of alumina),
identified by PXRD, takes place at 700 °C, giving rise to a sharp, clear exothermic peak in the
DTA trace. However, decomposition of the silicate analogue (prepared using aqueous sodium
silicate as precursor) yields mostly amorphous solids even at 300 °C, which undergo
crystallization to MgSiO3 at 900 °C, also identified by a sharp, intense exothermic peak in the
DTA curve, without the simultaneous crystallization of MgO. It should be noted that the
crystalline compound formed at high temperature is, however, Mg2SiO4 when the silicate
precursor was [N(CH3)4]8Si8O20 · x H2O 108 or tetraethyl ortosilicate,109 probably due to the
formation of interlayer silicates with different polymerization degrees in one case or another.
The thermal decomposition of a Mg,Al LDH containing [Fe(C2O4)3]3- anions in the
interlayer is rather different from that corresponding to the potassium salt of this complex, or to
the carbonate form of the LDH;110 the thermogravimetric curve corresponds to a “Type V”
multistage decomposition;111 interlayer water is removed ca. 100 °C above the temperature
recorded for the carbonate analogue, and a sharp endothermic effect at 300 °C seems to have
the same origin as a peak recorded at 265 °C in the DTA curve of K3[Fe(C2O4)3] · 3 H2O
(dehydrated at 100 °C), forming CO2, Fe2O3 and K2C2O4; this means that the complex becomes
stabilized in the interlayer space (decomposition takes place 35 °C above the temperature it
takes place for the pure complex); dehydroxylation (and evolution of unexchanged carbonate)
finishes at 500 °C.
As expected, the weight loss recorded during thermal decomposition of a Mg,Al LDH
containing intercalated [Fe(CN)6]3- anions112 is smaller than for the corresponding nitrate or
carbonate analogue; however, contrary to the behaviour observed for the nitrate form
possessing different Mg/Al ratios,80 for which the DTG peak shifted to larger values as the
Mg/Al ratio was decreased (see above), now it happened at 410±10 °C, whichever the Mg/Al
ratio.80 A small weight loss at 250-325 °C, which increased with the [Fe(CN)6]3- loading, has
been related80 to partial decomposition of the interlayer anion. This conclusion is supported by
IR spectroscopy measurements, which show a shift of the ν(C-N) band from 2215 cm-1,
characteristic of [Fe(CN)6]3- species, for the original sample, to 2050 cm-1, characteristic of
[Fe(CN)6]4-, upon heating in nitrogen at 325 °C, the band decreasing its intensity at 450 °C and
finally disappearing at 500 °C; actually, (CN)x species were identified by GC-IR analysis in the
gases evolved between 250-350 °C. Such a red-ox process has been also reported to occur in
other LDHs even without heating.113-118
Calcination of LDHs containing oxoanions in the interlayer has been reported to involve
some sort of grafting of the anion to the brucite-like layers, probably by a OH (from the
layer)/O (from the oxoanion) substitution.42-44 These processes should modify the thermal
properties, and, moreover, the stability of the layered material. The effect has been studied in
detail by several authors.42-44,73,119,120 Besse et al.120 have reported a study of chromate and
dichromate grafting to takovite (a Ni,Al carbonate LDH) upon mild calcination. The systems
containing these anions collapse at temperatures close to 450 °C, well above those reported for
chloride-containing takovite; below this temperature, a smooth decrease in the basal spacing is
observed, contraction being larger than the expected one for simply removal of interlayer water
molecules. Water molecules are released at higher temperatures than for Cl-LDH, probably
because hydrogen bonding to “hard” oxide anions (from chromate and dichromate) is stronger
than to “soft” chloride anions. Moreover, once the interlayer water molecules have been
eliminated, further water evolution arises from the grafting process itself, leading to two DTG
minima around 200 °C in the case of a Ni,Al-chromate LDH,120 but only a single peak for the
dichromate analogue, for which grafting took place at the early stages of heating (below 100
°C). Finally, water evolution formed through condensation of hydroxyl groups not involved in
the grafting process accounts for an additional weight loss centered around 380-440 °C.
Decavanadate-containing LDHs have been also extensively studied. Upon calcination,
vanadates of the metal cations originally existing in the brucite-like layers are generally formed,
but if these cations are oxidizable, interesting differences arise: calcination in air of LDHs
containing interlayer carbonate and Cr3+ in the layers leads to formation of chromate-like
species at intermediate calcination temperatures,121-127 probably favoured by interlayer
carbonate,124 and which presence has been evidenced by XANES spectroscopy in some
cases.125,126 This oxidation process gives rise to an exothermic effect at 335 °C (Co, Cr LDH126)
or 435 °C (Zn, Cr LDH125), but is absent when the analysis is recorded in nitrogen, thus
confirming that it corresponds to an oxidation process. Quite surprisingly, this effect is also
absent when the interlayer anion is decavanadate, which also inhibits the Co2+ → Co3+
oxidation126 observed in air in the Co,Cr-carbonate LDH, also confirmed by XANES
spectroscopy. Depolymerization of decavanadate follows trends similar to those reported by
Twu and Dutta128 for a Mg,Al-decavanadate LDH, but the crystalline species formed differ in
the presence or in the absence of decavanadate: while CoIICoIIICrO4 spinel is formed at 650 °C
from the Co,Cr-carbonate precursor, CoIICr2O4 and Co2V2O7 are formed from the decavanadate
analogue.126 Starting from Zn,Cr-decavanadate, ZnV2O6 is formed at 400 °C, transforming to
Zn2V2O7 at 750 °C, together with ZnCr2O4.125 Although the role of carbonate to favour these
oxidation processes cannot be ignored, the thermodynamic stability of the mixed oxides formed
under different reaction conditions (in the presence or absence of decavanadate) should be also
be considered to understand these differences.
In the absence of such oxidizable cations, the thermal decomposition of LDHs containing
vanadate, molybdate or polyoxometalates (Keggin, Dawson, and Finke type) proceeds, as
expected, in two steps, dehydration and dehydroxylation, obviously without removal of the
anion,12,84,129-135 although in many cases exothermic effects due to crystallization of anhydrous
oxides are observed at high temperatures. In the case of decavanadate intercalates, additional
weight losses or DTA effects are recorded, due to depolymerization of the interlayer
anions,128,136-138 as concluded from FT-IR and XAS spectroscopy studies; changes in spacing due
to this depolymerization is not, however, conclusive about the nature of the species formed.
THE SPECIAL CASE OF REDUCTION

In the previous sections of this chapter we have discussed the effect of heating under
oxidizing or inert atmospheres on the structure and chemical changes of several LDHs. In the
case of LDHs containing reducible (transition metal) cations, a study of their thermal
decomposition in a reducing atmosphere is worthwhile to be carried out, due to the potential
role of these LDHs and their decomposition products as catalysts for different reactions.
Temperature-programmed reduction (TPR), well in the chromatographic or the
thermogravimetric fashion, has been applied for these purpouses. In the first case, the weight
loss recorded in a thermogravimetric analysis under H2 atmosphere (usually combined with GC
or MS analysis of the gases evolved) corresponding to a process depicted as:
144 Vicente Rives
MOn + (n-p) H2 → MOp + (n-p) H2O
(p could be equal to zero) is quantified and related to the decrease in the average oxidation state
of the metal cation. In the second case, gas chromatographic analysis of a H2/Ar mixture which
passes through the solid being heated at a linear heating rate is used to quantify hydrogen
consumption during reduction. Results are equivalent, although the analysis is not as
straightforward as it could seem, due to processes (e.g., dehydration, dehydroxylation,
vaporization of volatile anions, phase changes, etc.) occuring in the same temperature range as
reduction proceeds. The oxidation state of the metal in the final solid residue can be inferred
from tabulated thermodynamic values. Finally, reduction can affect not only to layer cations,
but also to interlayer metal-containing anions (e. g., decavanadate), and reduction of carbonate
cannot be excluded if CO2 is not evolved before CO32- is reduced. The TPR analysis of a
Mg,Al-carbonate LDH indicates that Mg2+ and Al3+ are not reduced even at 800 °C, and that
carbonate is evolved before being reduced to coke or methane.139 Nor Cr3+ in Mg,Cr-carbonate
LDH not V3+ in Ni,V-carbonate62 are reduced under these conditions.139 However, Ni2+ is
quantitatively reduced to Ni0 in Ni,Al-carbonate and Ni,Cr-carbonate LDHs, Fig. 8, although
the reduction patterns are different (a sharper peak is recorded for the Ni,Al carbonate LDH),
probably because when reduction starts (ca. 325 °C) the LDH is partially decomposed and
reduction of Ni2+ species proceeds through different routes.
Figure 8.-Temperature-programmed reduction (TPR) profiles of LDHs: (a) Mg,Al-CO3; (b) Mg,Cr-CO3; (c)
Ni,Al-CO3; (d) Ni,Cr-carbonate. Reprinted from V. Rives, M. A. Ulibarri and A. Montero, Application of
temperature-programmed reduction to the characterization of anionic clays, Appl. Clay Sci., 10 (1995) 83-93,
©1995, with permission from Elsevier Science.
As mentioned above,127 when a Ni,Cr-carbonate LDH is calcined at increasing

temperatures, formation of chromate-like species is detected at intermediate calcination
temperatures. Their reduction takes place in a narrow temperature range at ca. 250 °C , i.e., at
lower temperature than reduction of Ni2+ ions, and the integrated area of the low-temperature
reduction peak can be used to calculate the average oxidation state of Cr ions, taking into
account that their final oxidation state should be 3+,139 Fig. 9.
Mg,Al,Fe-carbonate LDHs have been also studied using TPR techniques,140 and it has been
found that the onset temperature for Fe3+ reduction (close to 425 °C) decreases as the Fe/Al
ratio increases, the reduction profile being similar to those reported for reduction of small Fe2O3
particles,141,142 probably because these particles have already been formed when reduction
starts.
When two reducible cations exist, the behaviour observed is different to that for systems
where these cations are separated. So, although Co3O4 and Fe2O3 are quantitatively reduced to
Co0 and Fe0, respectively, under TPR conditions,65,143 with maximum reduction rates at 276 and
337 °C (for Co3O4) and 527 °C (Fe3O4), the TPR profile of a Co,Fe-carbonate LDH shows a
single reduction maximum at 383-423 °C, which integrated area coincides with the sum of that
expected for Co2+ → Co0 and Fe3+ → Fe0 reduction processes. It has been previously reported
that reduction of two metals supported on the same support takes place simultaneously, despite
the fact that they are reduced at different temperatures when present alone.144 It has been
claimed65 that hydrogen can be dissociatively adsorbed on reduced cobalt particles, with further
spillover of hydrogen atoms, thus lowering the reduction temperature of nearby iron oxide
particles. A similar effect has been also reported for a Ni,Fe-carbonate LDH,145 which TPR
profile shows a single reduction maximum at 347 °C, despite Ni2+ in Ni,Al-carbonate is reduced
at 391 °C139 and Fe3+ in a Zn,Al,Fe-carbonate LDH is reduced at 380 °C.146 Reduction of
supported Ni-Fe catalysts147 and mixed oxides prepared by calcination of Ni,Fe-carbonate
LDHs also show a similar behaviour, the onset for reduction decreasing as the Ni (more
reducible) content was increased.148 It is generally observed that the temperature for reduction
of a previously calcined LDH is larger than that required for reduction of the fresh, uncalcined
LDH, due to the strong interaction between the oxides formed.
Figure 9.-TPR profiles for a Ni,Cr-CO3 LDH previously calcined in air at the temperatures (K) given.
Reprinted from V. Rives, M. A. Ulibarri and A. Montero, Application of temperature-programmed reduction to
the characterization of anionic clays, Appl. Clay Sci., 10 (1995) 83-93, ©1995, with permission from Elsevier
Science.
146 Vicente Rives
When the interlayer anion is also reducible, additional reduction maxima are sometimes
recorded. Coq et al. have studied the catalytic properties of mixed oxides containing Ni and/or
Co together with Mg and Al, prepared from LDH precursors. These authors have used nitrate
LDHs, and so, during TPR analysis, reduction of nitrate, in addition to that of Ni and/or Co, is
observed. TPR analysis of Ni,Mg,Al LDHs in the nitrate form exhibits,67,149 a rather broad
reduction maximum centered around 500-550 °C, which broadness and position shifts if the
LDH has been previously calcined. The hydrogen consumption corresponding to this peak
roughly coincides with the value expected for Ni2+ → Ni0 reduction. However, for the original
LDH and after calcination up to 250 °C, an additional, sharp, reduction maximum is also
observed at ca. 300 °C. Mass spectrometric analysis of gases evolved around 300 °C shows the
presence of NO (m/e=30), but NO2 (m/e=46) was hardly detected, as it is probably also reduced.
An increase in the relative concentrations of Mg and/or Al in the layers gives rise to a decrease
in the reducibility of Ni2+,149-151 while the presence of interlayer chloride increases such a
reducibility.72
Similar effects have been also reported for Co,Mg,Al LDHs in the nitrate form.66 In this
case, the low temperature reduction peak, at ca. 250 °C, is sharp and very intense at low Co
contents, but weakens and shows a broad shoulder on the high temperature side as the Co
content is increased; in all cases, a second reduction maximum is recorded at ca. 850 °C,
suggesting that, at least, two different types of Co cations exist, one reducing at 250 °C and
another at 850 °C; in addition, the sharp maximum should corresponds mainly to reduction of
interlayer nitrate anions, as concluded also from MS analysis of gases evolved (NO peak at
m/e=30).
Finally, these authors have also reported on LDHs containing Co, Ni, Mg, Al with the
simultaneous presence of nitrate and carbonate in the interlayer.152 The behaviour of these
samples seems to be the superposition of those shown by Ni,Mg,Al67,72,149 and Co,Mg,Al,66 i.e.,
reduction of nitrate around 250 °C (where reduction of Co species also takes place), and
reduction of Ni and other type of Co species at ca. 800 °C. As in the other studies, the H2
consumption of the calcined samples (where interlayer anions have been already removed)
coincides with the amount calculated for total reduction of Ni and Co to the metallic state,
while for samples calcined up to 250 °C (where interlayer nitrate still exists) the H2/(Co+Ni)
ratio reaches values up to 1.57 (1. 0 expected for reduction of Ni and Co only).
LDHs with interlayer nitrate and carbonate (simultaneously) containing Cu2+ ions in the
layers together with Al3+, have been also studied by TPR.153 NO evolution by MS (i.e., nitrate
reeduction) is observed at ca. 225 °C, in rather good agreement with the results above
mentioned for nitrate LDHs containing Ni or Co, and Cu2+ reduction starts immediately after
NO evolution; for high Cu contents, reduction of Cu2+ takes place simultaneously to CO2
evolution (below the temperature at which CO2 evolution is observed under an oxidizing
atmosphere), probably because bidentate Cu2+ carbonates are formed via grafting in the sample,
which must cleave with the reduction of Cu2+ to metallic copper. On the other hand, for low
Cu/Al ratios the reduction of Cu2+ takes place at higher temperatures, because there is a greater
interaction between Cu2+ and alumina.
CONCLUSIONS
Thermal properties of layered double hydroxides depend on the precise chemical
composition of the sample, and on the atmosphere during heating. Mixed, mostly amorphous,
oxides are generally formed at intermediate calcination temperatures, crystallization of mixed
oxides being observed as the calcination temperature is increased. Combined
decomposition/oxidation processes can be also observed when oxidizable cations exist in the
parent compound, well in the brucite-like layers, or in the interlayer anion. Under a reducing
atmosphere cations are easily reduced to the metallic state, depending on the thermodynamic
stability of their different oxides. The techniques used (DTA, TG/DTG,TPR) permit also the
identification of temperature ranges where thermally stable species can be identified.
ACKNOWLEDGMENTS
Financial support from DGICYT (grant PB96-1307-C03-01), DGI-MCyT (grant
MAT2000-1148-C02-01) and Junta de Castilla y León (Consejería de Educación y Cultura,
grant SA45/96) is greatly acknowledged.
REFERENCES
2. F. Cavani, F. Trifirò and A. Vaccari, Catal. Today 11 (1991) 173.
3. A. de Roy, C. Forano, K. El Malki and J. P. Besse, in “Expanded Clays and other
Microporous Solids, Synthesis of Microporous Materials”, eds. M. L. Occelli and H.
Robson, van Nostrand Reinhold, New York, 1992, chapter 7, p. 108.
4. F. Trifirò and A. Vaccari, in “Comprehensive Supramolecular Chemistry. Volume 7.
Solid-State Supramolecular Chemistry: Two- and Three-Dimensional Inorganic
Networks”, eds. J. L. Atwood, J. E. D. Davies, D. D. MacNicol, F. Vögtle, J.-M. Lehn, G.
Alberti and T. Bein, Pergamon, Oxford, 1996, p. 251.
5. V. Rives and M. A. Ulibarri, Coord. Chem. Rev. 181 (1999) 61.
6. C. J. Serna, J. L. Rendón, J. E. Iglesias, Clays Clay Miner. 10 (1982) 180.
7. R. M. Taylor, Clay Miner. 19 (1984) 591.
8. S. Velu, V. Ramaswamy, A. Ramani, B. M. Chanda, S. Sivansaker, J. Chem. Soc., Chem.
Comm. (1997) 2107.
9. S. Velu, S. P. Sabde, N Shah and S. Sivasanker, Chem. Mater. 10 (1998) 3451.
10. S. Velu, K. Suzuki, M. Okazaki, T. Osaki, S. Tomura and F. Ohashi, Chem. Mater. 11
(1999) 2163.
12. M. A. Drezdzon, ACS Symp. Ser. 437 (1990) 140.
13. A. Clearfield, M. Kuchenmeister, J. Wang and K. Wade, Stud. Surface Sci. Catal. 69
(1991) 485.
14. A. Clearfield, in “Multifunctional Mesoporous Solids”, eds. C. A. C. Sequeira and M. J.
Hudson, Kluwer, Amsterdam, 1993, p. 159.
148 Vicente Rives
15. K. Ohtsuka, Chem. Mater. 9 (1997) 2039.

16. T. Sato, K. Kato, T. Endo and M. Shimada, Reactivity Solids 2 (1986) 253.
17. K. Chibwe and W. Jones, J. Chem. Soc., Chem. Comm. (1989) 926.
18. T. Kwon and T. J. Pinnavaia, Chem. Mater 1 (1989), 381.
19. J. Rocha, M. del Arco, V. Rives and M. A. Ulibarri, J. Mater. Chem. 9 (1999) 2499.
20. S. K. Yun and T. J. Pinnavaia, Chem. Mater. 7 (1995) 348.
21. W. T. Reichle, S. Y. Yang and D. S. Everhard, J. Catal. 101 (1986) 352.
22. J. I. Di Cosimo, V. K. Diez, M. Xu, E. Iglesia and C. R. Apesteguía, J. Catal. 178 (1998)
499.
23. L. Pesic, S. Salipurovic, V. Markovic, D Vucelic, W. Kagunya and W. Jones, J. Mater.
Chem. 2 (1992) 1069.
24. F. Rey, V. Fornés and J. M. Rojo, J. Chem. Soc., Faraday Trans. 88 (1992) 2233.
25. F. M. Labajos, V. Rives and M. A. Ulibarri, J. Mater. Sci. 27 (1992) 1546.
26. E. Kanezaki, J. Mater. Sci. Lett. 17 (1998) 371.
27. E. Kanezaki, Solid State Ionics 106 (1998) 279.
28. E. Kanezaki, Mater. Res. Bull. 33 (1998) 773.
29. E. Kanezaki, Inorg. Chem. 37 (1998) 2588.
30. K. J. D. MacKenzie, E. J. Meinhold, B. L. Sherriff and Z. Xu, J. Mater. Chem. 3 (1993)
1263.
31. T. Hibino, Y. Yamashita, K. Kosuge and A Tsunashima, Clays Clay Miner. 43 (1995) 427.
32. V. Rives, Inorg. Chem. 38 (1998) 406.
33. P. Bera, M. Rajamathi, M. S. Hegde, P. V. Kamath, Bull. Mater. Sci. (India) 23 (2000) 141.
34. W. Kagunya, P. K. Dutta and Z. Lei, Physica B 234-236 (1997) 910.
35. Ts. Stanimirova, I. Vergilov, G. Kirov and N. Petrova, J. Mater. Sci. 34 (1999) 4153.
36. S. Miyata and A. Okada, Clays Clay Miner. 25 (1977) 14.
37. M. Che, C. Naccache and B. Imelik, J. Catal. 24 (1972) 328.
38. V. C. Farmer, “The Infrared Spectra of Minerals”, Mineralogical Society, Monograph 4,
London, 1974.
39. P. O. Scokart and P. G. Rouxhet, J. Colloid Interface Sci. 86 (1982) 96.
40. H. Knözinger and P. Ratnasamy, Catal. Rev.- Sci. Eng. 17 (1978) 31.
41. J. R. Smyth and D. L. Bish, “Crystal Structures and Cation Sites of the Rock-forming
Minerals”, Allen and Unwin, London, 1988, p. 69.
42. K. El Malki, A. de Roy, J. P. Besse, Eur. J. Solid State Inorg. Chem. 26 (1989) 339.
43. C. Depège, C. Forano, A. de Roy, J. P. Besse, Mol. Cryst. Liq. Cryst. 244 (1994) 161.
44. L. Bigey, C. Depège, A. de Roy, J. P. Besse, J. Phys. IV France C2, 7 (1997) 949.
45. D. Tichit, M. N. Bennani, F. Figueras and J. R. Ruiz, Langmuir 14 (1998) 2086.
46. M. Belloto, B. Rebours, O Clause, J Lynch, D. Bazin and E. Elkaim, J. Phys. Chem. 100
(1996) 8535.
47. M. J. Hudson, S. Carlino and D. C. Apperley, J. Mater. Chem. 5 (1995) 323.
48. S. Velu, V. Ramkumar, A. Narayanan and C. S. Swamy, J. Mater. Sci. 32 (1997) 957.
49. G. W. Brindley and S. Kikkawa, Am. Mineral. 64 (1979) 836.
50. A. Béres, I. Pálinkó, J.-C. Bertrand, J. B. Nagy and I. Kiricsi, J. Molecular Structure
410-411 (1997) 13.
51. T. López, E. Ramos, P. Bosch, M. Asomoza and R. Gómez, Mater. Lett. 30 (1997) 279.
52. M. A. Aramendía, Y. Avilés, J. A. Benítez, V. Borau, C. Jiménez, J. M. Marinas, J. R. Ruiz
and F. J. Urbano, Microporous Mesoporous Mater. 29 (1999) 319.
53. M. A. Aramendía, Y. Avilés, V. Borau, J. M. Luque, J. M. Marinas, J. R. Ruiz and F. J.

Urbano, J. Mater. Chem. 9 (1999) 1603.
54. E. López-Salinas, E. Torres-García and M. García-Sánchez, J. Phys. Chem. Solids 58
(1997) 919.
55. G. Mascolo and O. Marino, Miner. Mag. 43 (1980) 619.
56. J. B. Pedley and E. M. Marshall, J. Phys. Chem. Ref. Data 12 (1984) 967.
57. B. C. Lippens, P. Fransen, J. G. van Ommen, R. Wijngaarden, H. Bosch, J. R. H. Ross,
Solid State Ionics 16 (1985) 275.
58. J. M. Fernández, C. Barriga, M. A. Ulibarri, F. M. Labajos and V. Rives, Chem. Mater. 9
(1997) 312.
59. S. Velu, D. P. Sabde, N. Shah and S. Sivasanker, Chem. Mater. 10 (1998) 3451.
(1999) 2163.
61. M. D. Sastre, M. Sc. Thesis, University of Salamanca, Spain (1997).
62. F. M. Labajos, M. D. Sastre, R. Trujillano and V. Rives, J. Mater. Chem. 9 (1999) 1033.
63. M. A. Ulibarri, J. M. Fernández, F. M. Labajos and V. Rives, Chem. Mater. 3 (1991) 626.
64. J. T. Kloprogge and R. L. Frost, Appl. Catal. A: General 184 (1999) 61.
65. M. del Arco, R. Trujillano and V. Rives, J. Mater. Chem. 8 (1998) 761.
66. S. Ribet, D. Tichit, B. Coq, B. Ducourant and F. Morato, J. Solid State Chem. 142 (1999)
382.
67. D. Tichit, F. Medina, B. Coq and R. Dutartre, Appl. Catal., A:General 159 (1997) 241.
68. H. C. Zeng, Z. P. Xu and M. Qian, Chem. Mater. 10 (1998) 2277.
69. Z. P. Xu and H. C. Zeng, J. Mater. Chem. 8 (1998) 2499.
70. D. Tichit, M. H. Lhouty, A. Guida, B. H. Chiche, F. Figueras, A. Auroux, D. Bartalini and
E. Garrone, J. Catal. 151 (1995) 50.
71. J. Sánchez Valente, F. Figueras, M. Gravelle, P. Kumbhar, J. López and J. P. Besse, J.
Catal. 189 (2000) 370.
72. O. Lebedeva, D. Tichit and B. Coq, Appl. Catal. A: General 183 (1999) 61.
73. V. R. L. Constantino and T. J. Pinnavaia, Inorg. Chem. 34 (1995) 883.
74. E. Ramos, T. López, P. Bosch, M. Asomoza and R. Gómez, J. Sol-Gel Sci. Technol. 8
(1997) 437.
75. T. López, P. Bosch, M. Asomoza, R. Gómez and E. Ramos, Mater. Lett. 31 (1997) 311.
76. O. Yamaguchi, H. Taguchi, Y. Miyata, M. Yoshinaka and K. Shimizu, Polyhedron 6 (1987)
1587.
77. I. C. Chisem, S. D. Cosgrove and W. Jones, J. Thermal Anal. 50 (1997) 757.
78. R. S. Weber, P. Gallezot, F. Lefebvre and S. L. Suib, Microporous Mater. 1 (1993) 223.
79. H. Nijs, M. de Bock and E. F. Vansant, Microporous Mesoporous Mater. 30 (1999) 243.
80. M. Nayak, T. R. N. Kutty, V. Jayaraman and G. Periaswamy, J. Mater. Chem. 7 (1997)
2131.
81. K. R. Poeppelmeier and S. J. Hwu, Inorg. Chem. 26 (1987) 3297.
82. T. Kwon, G. A. Rsigdinos and T. J. Pinnavaia, J. Am. Chem. Soc. 110 (1988) 3653.
83. M. A. Drezdzon, Inorg. Chem. 27 (1988) 4628.
84. M. A.Ulibarri, F. M. Labajos, V. Rives, R. Trujillano, W. Kagunya and W. Jones, Inorg.
Chem. 33 (1994) 2592.
85. V. Prevot, C. Forano and J. P. Besse, J. Mater. Chem. 9 (1999) 155.
86. V. Prevot, C. Forano and J. P. Besse, Inorg. Chem. 37 (1998) 4293.
150 Vicente Rives
87. M. Meyn, K Beneke and G. Lagaly, Inorg. Chem. 29 (1990) 5201.

88. A. Fudala, I. Pálinkó, B. Htivnák and I. Kiricsi, J. Thermal Anal. Calorimetry 56 (1999)
317.
90. C. O. Oriakhi, I. V. Farr and M. M. Lerner; Clays Clay Miner. 45 (1997) 194.
91. T. Kuwahara, O. Onitsuka, H. Tagaya, J. Kadokawa and K. Chiba, J. Incl. Phenom. Mol.
Recogn. Chem. 18 (1994) 59.
92. H. Kopka, K. Beneke and G. Lagaly, J. Coll. Interface Sci. 123 (1988) 427.
93. M. Meyn, K. Beneke and G. Lagaly, Inorg. Chem. 29 (1990) 5201.
94. A. Clearfield, M. Kieke, J. Kwan, J. L. Colon and R. C. Wang, J. Inclusion Phenom.
Molec. Recognition Chem. 11 (1991) 361.
95. S. Carlino, M. J. Hudson, S. W. Husain and J. A. Knowles, Solid State Ionics 84 (1996)
117.
96. J. Bujdák and H. Slosiariková, Appl. Clay Sci. 7 (1992) 263.
97. C. del Hoyo, V. Rives and M. A. Vicente, Clays Clay Miner. 44 (1996) 1996.
98. H. Nijs, A. Clearfield and E. F. Vansant, Microporous Mesoporous Mater. 23 (1998) 97.
99. A. Oya, Y. Omata and S. Otani, J. Mater. Sci. 20 (1985) 255.
100. A. Oya, H. Mita, Y. Tosaka and S. Otani, Appl. Clay Sci. 5 (1990) 13.
101. T. Hibino, K. Kosuge and A. Tsunashima, Clays Clay Miner. 44 (1996) 151 (corrections in
ibid. 44 (1996) 851).
102. K. Putyera, T. J. Bandosz, J. Jagieo and J. A. Schwarz, Carbon 34 (1996) 1559.
103. T. Hibino and A. Tsunashima, Clays Clay Miner. 45 (1997) 842.
104. M. J. Flores, C. Barriga, J. M. Fernández, M. A. Ulibarri and V. Rives, unpublished
results.
105. A. Ookubo, K. Ooi and H. Hayashi, J. Pharmaceutical Sci. 81 (1992) 1139.
106. A. Ookubo, K. Ooi, F. Tani and H. Hayashi, Langmuir 10 (1994) 407.
107. M. del Arco, S. Gutiérrez, C. Martín, V. Rives and J. Rocha, J. Solid State Chem. 151
(2000) 272.
108. C. A. Fyfe, G. Fu and H. Grondey, Mater. Res. Soc. Symp. Proc. 346 (1994) 907.
109. S. Gutiérrez, M. Sc. Thesis, Universidad de Salamanca, Spain (1999).
110. S. Carlino and M. J. Hudson, Solid State Ionics 110 (1998) 153.
111. M. E. Brown, “Introduction to Thermal Analysis”, Chapman and Hall, London, 1988,
Chapters 1 and 2.
112. J. M. Fernández, M. A. Ulibarri, F. M. Labajos and V. Rives, J. Mater. Chem. 8 (1998)
2507.
113. H. A. Larsen and H. G. Drickamer, J. Phys. Chem. 47 (1967) 2591.
114. F. A. P. Cavalcanti, A. Schutz and P. Biloen, in “Preparation of Catalysts IV”, B. Delmon,
P. Grange, P. A. Jacobs and G. poncelet, eds., Elsevier, Amsterdam (1987), p. 165.
115. K. A. Carrado, A. Kostapapas and S. L. Suib, Solid State Ionics 26 (1988) 77.
116. S. Idemura, E. Suzuki and Y. Ono, Clays Clay Miner. 37 (1989) 553.
117. H. C. B. Hansen and C. B. Koch, Clays Clay Miner. 42 (1994) 170.
118. M. J. Holgado, V. Rives, M. S. Sanromán and P. Malet, Solid State Ionics 92 (1996) 273.
119. C. Forano, A. de Roy, C. Depége, M. Khaldi, F. Z. El Métoui and J. P. Besse, in “Synthesis
of porous materials: zeolites, clays and nanostructures”, eds. M. L. Occelli and H.
Kessler, Marcel Dekker, New York, 1996.
120. F. Malherbe, L. Bigey, C. Forano, A. de Roy and J. P. Besse, J. Chem. Soc., Dalton Trans.
(1999) 3831.
121. G. del Piero, M. di Conca, F. Trifirò and A. Vaccari, in “Reactivity of solids”, eds. P. Barret
and L. Dufour, Elsevier, Amsterdam, 1985, p. 1029.
122. S. Gusi, F. Pizzoli, F. Trifirò, A. Vaccari and G. del Piero, Stud. Surface Sci. Catal. 31
(1987) 753.
123. T. Sato, H. Fujita, T. Endo and M. Shimada, Reactivity Solids 5 (1988) 219.
124. K. Fuda, K. Suda and T. Matsunaga, Chem. Lett. (1993) 1479.
125. M. del Arco, V. Rives, R. Trujillano and P. Malet, J. Mater. Chem. 6 (1996) 1419.
126. M. del Arco, M. V. G. Galiano, V. Rives, R. Trujillano and P. Malet, Inorg. Chem. 35 (1996)
6362.
127. F. M. Labajos and V. Rives, Inorg. Chem. 35 (1996) 5313.
128. J. Twu and P. K. Dutta, J. Catal. 124 (1990) 503.
129. J. Wang, Y. Tian, R.-C. Wang, J. L. Colón and A. Clearfield, Mat. Res. Soc. Symp. Proc.
233 (1991) 63.
130. E. López Salinas and Y. Ono, Bull. Chem. Soc. Jpn. 65 (1992) 2465.
131. J. Wang, Y. Tian, R.-C. Wang and A. Clearfield, Chem. Mater. 4 (1992) 1276.
132. T. Kwon and T. J. Pinnavaia, J. Molecular Catal. 74 (1992) 23.
133. J. D. Wang, G. Serrette, Y. Tian and A. Clearfield, Appl. Clay Sci. 10 (1995) 103.
134. S. K. Yun, V. R. L. Constantino and T. J. Pinnavaia, Microporous Mater. 4 (1995) 21.
135. S. K. Yun and T. J. Pinnavaia, Inorg. Chem. 35 (1996) 6853.
136. E. López Salinas and Y. Ono, Bull. Chem. Soc. Jpn. 65 (1992) 2465
137. C. Barriga, W. Jones, P. Malet, V. Rives and M. A. Ulibarri, Inorg. Chem. 37 (1998) 1812.
138. H. Nijs, M. de Bock and E. F. Vansant, J. Porous Mater. 6 (1999) 101.
139. V. Rives, M. A. Ulibarri and A. Montero, Appl. Clay Sci. 10 (1995) 83.
140. S. M. Auer, J.-D. Grunwaldt, R. A. Köppel and A. Baiker, J. Molecular Catal. A:
Chemical 139 (1999) 305.
141. R. Brown, M. E. Cooper and D. A. Whan, Appl. Catal. 3 (1982) 177.
142. O. J. Wimmers, P. Arnoldy and J. A. Moulijn, J. Phys. Chem. 90 (1986) 1331.
143. D. Lazarov, V. Rives, R. Klissurska, I. Mitov and D: Klissurski, Mater. Lett. 27 (1996)
129.
144. S. Kacimi and D. Duprez, Stud. Surface Sci. Catal. 71 (1991) 581.
145. M. del Arco, P. Malet, R. Trujillano and V. Rives, Chem. Mater. 11 (1999) 624.
146. C. Barriga, F. Kooli, V. Rives and M. A. Ulibarri, in “Synthesis of porous materials:
zeolites, clays and nanostructures”, eds. M. L. Occelli and H. Kessler, Marcel Dekker,
New York, 1996, p. 661.
147. E. E. Unmuth, L. H. Schwartz and J. B. Butt, J. Catal. 61 (1980) 242.
148. M. Tu, J. Shen and Y. Chen, Thermochim. Acta 302 (1997) 117.
149. F. Medina, R. Dutartre, D. Tichit, B. Coq, N. T. Dung, P. Salagre and J. E. Sueiras, J.
Molecular Catal. A: General 119(1997) 201.
150. A. Vaccari and M. Gazzano, Stud. Surface Sci. Catal. 91 (1995) 893.
151. N. T. Dung, D. Tichit, B. H. Chiche and B. Coq, Appl. Catal. A: General 169 (1998) 179.
152. B. Coq, D. Tichit and S. Ribet, J. Catal. 189 (2000) 117.
153. A. Alejandre, F. Medina, P. Salagre, X. Correig and J. E. Sueiras, Chem. Mater. 11 (1999)
939.
Chapter 5
INFRARED AND RAMAN SPECTROSCOPIC STUDIES

OF LAYERED DOUBLE HYDROXIDES (LDHS)
J. T. Kloprogge and R. L. Frost

Centre for Instrumental and Developmental Chemistry, Queensland University of
Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001, Australia
INTRODUCTION
Clays are an important group of minerals that are heavily used by various industries. They
are commonly found in nature and can be used to produce a range of versatile materials.1
Hydrotalcites (HTs) or layered double hydroxides (LDHs) are in the literature also described as
anionic clays, due to their layered structure with a charge opposite to that of cationic clays, like
smectites, consisting of negatively charged alumino-silicate layers with cations in the interlayer
space to balance the negative charge. Hydrotalcites found in nature are known as the
pyroaurite-sjögrenite group. Layered double hydroxides form an important group of
compounds, which are simple and inexpensive to synthesise under low temperature and
pressure conditions.
The first structural formulae for hydrotalcite was proposed in 1915 by Manasse,2 who also
recognised that the carbonate ions present in the interlayer are an essential part of the structure
of the hydrotalcite. Further developments in the unravelling of the hydrotalcite mineral
structure occurred in the 1930’s, when Aminoff and Brome3 recognised the existence of two
polytypes of hydrotalcites with rhombohedral and hexagonal symmetry. However, it was not
until 1941 that Frondel4 clarified the structural and chemical relationships between the several
minerals within the hydrotalcite group and their real constituents.
The first hydrotalcites were already synthesised by Feitknecht in the 1930’s with the
reaction of dilute solutions of metal ions with bases, which yielded small quantities of the
hydrotalcite mineral.5 In the early 1940’s, Feitknecht synthesised a large number of HT
compounds, assigning them a structure with intercalated hydroxide layers.6,7 For a long time,
however, these materials were mainly the objects of mineralogical studies, and it was not until
after the 1970’s that their industrial applications became of interest. The applications of HT
materials have become numerous and important in unexpected fields. Prior to the 1970’s,
Brindley and Kikkawa,8 Taylor,9 Reichle,10,12 and in particular Miyata and his group13,14 have
154 J.T. Kloprogge and R.L. Frost
investigated the synthetic aspects of these materials. Miyata,15,16 Ross and Kodama,17 and
Bish18 examined the general properties of these anionic clays.
The structure of hydrotalcite can be visualised as positively charged OH-layers comparable
to those in brucite [Mg(OH)2] in which a part of the Mg2+ is substituted by a trivalent metal like
Al3+ separated by charge compensating, mostly hydrated, anions between the OH-layers. In
hydrotalcites a range of compositions are possible of the type [M2+1-xM3+x(OH)2][An-]x/n.yH2O,
where M2+ and M3+ are the di- and trivalent cations in the octahedral sites within the OH-layers
with x normally between 0.17 and 0.33. An- is an exchangeable anion. It is important that the
ionic radii of the M2+ and M3+ do not vary more than 30 % in size, e.g. 0.65 Å for Mg2+ and 0.45
Å for Al3+ and the solubility products S1 and S2 of M2+(OH)2 and M2+CO32- must satisfy 0 <
pS1-pS2 < 10, where pS1 is the negative logarithm of the solubility product of M2+(OH)2 and
pS2 of M2+CO3.19
The structure of hydrotalcite can accommodate a large variety of cations including
combinations such as Ni2+/Al3+, Ni2+/Mn3+, Zn2+/Cr3+,Cu2+/Cr3+, Mg2+/Cr3+, Co2+/Cr3+,
Mg2+/Fe3+.20-27 Even ions, e. g. Cu2+, which are otherwise too large, have been reported to be
incorporated in the hydrotalcite structure although only in small amounts.19,27 However, such
ions usually give rise to preferential precipitation of malachite-like phases, because of the
Jahn-Teller effect for these ions (d9), the formation of distorted octahedral structures is
favoured.28 The number of counterbalancing anions or anionic complexes is essentially
unlimited provided that the anion does not form a complex with the cations in the octahedral
sheets during the formation.29 Therefore, the variety possible in both the cationic and anionic
composition offers the possibility to prepare tailor-made materials for specific applications,
such as basic catalysts, as a precursor for the preparation of mixed metal oxidic catalysts,
absorbents, as for other specific powder properties such as filler, UV-radiation stabiliser,
chloride scavenger and thermal stabiliser.30
INFRARED AND RAMAN SPECTROSCOPY

Spectroscopy and especially infrared spectroscopy has been a widely used technique in the
industry for the structural and compositional analysis of organic, organometallic, metalorganic,
inorganic and polymeric materials, in addition to quality control of raw materials and
commercial products. In general, it can be said that spectroscopic techniques are concerned
with the interaction between radiation of some sort and matter, using radiation with an energy
or wavelength appropriate to the distance and time scales relevant to the microscopic study of
atoms, molecules and solids. In this regard a large number of radiation types can be used
including electromagnetic radiation, elementary particles, nuclei, ions and ultrasonic waves.
Infrared and Raman spectroscopy are vibrational spectroscopic techniques and will be
discussed in more details in the next paragraphs. Those readers who are interested in a more
fundamental approach of vibrational spectroscopy and vibrational spectroscopy of minerals are
referred to a number of good quality publications.31-39 Vibrational spectroscopy involves the
use of light to probe the vibrational behaviour of molecular systems, usually via absorption,
emission or light scattering experiments. For molecules and crystals, the vibrational energy
involved ranges from approximately 0 to 60 kJ/mol, equivalent to 0-5000 cm-1 (according to
Infrared and Raman Spectroscopic Studies of Layered Double Hydroxides… 155
the relation between frequency ν, wavelength λ and wavenumber ν in cm-1: λ = c/ν and ν =
ν/c).
Both infrared and Raman spectroscopy give rise to a set of absorption or scattering peaks as
a function of the energy forming a vibrational spectrum. Individual peaks in the spectrum
correspond to energies of vibrational transitions within the sample or, in other words, to the
frequencies of the vibrational modes. Since a vibrational spectrum is dependent on the
interatomic forces in a molecule or crystal, it is a very sensitive probe of the microscopical
structure and bonding within the molecule or crystal. Therefore, the positions, symmetries and
relative intensities of the observed peaks in a spectrum and any changes in these peaks with
changes in variables such as temperature, pressure and composition, will provide useful
structural information of the sample.
A classical mechanical model can be used as a first approximation for the description of the
vibrations of molecules and crystals. In this case nuclei are assumed to be point masses and the
interatomic interactions (both bonding and repulsive interactions) by springs. Now, atoms are
allowed to undergo small vibrational displacements around their equilibrium positions and
their equations of motion are analysed in terms of Newtonian mechanics. If the springs are
assumed ideal, the restoring force is directly proportional to the displacement (Hooke’s law),
then the vibrational motion is harmonic or sinusoidal in time. The proportionality constant,
which relates the restoring force to the vibrational displacement, is termed the force constant of
the spring. Solution of the equations of motion for the system allows a set of vibrational
frequencies to be identified. Each frequency corresponds to a particular atomic displacement
pattern, known as a normal mode of vibration. However, although this classical model
describes most of the basic features of vibrational motion, it cannot explain all the details. For a
more detailed understanding, a quantum mechanical model has been developed based on
Schrödinger’s wave equation. In the light of this chapter it goes too far to give all the details of
this model, but in general it can be summarised as follows. In a vibrational spectroscopic
experiment the system will undergo a transition between vibrational levels with different
quantum numbers and light is absorbed or emitted with an energy (∆E = hν) corresponding to
the separation between the levels, which is generally in the order of 0-60 kJ/mol.
INFRARED AND NEAR-INFRARED SPECTROSCOPY

Conventional infrared spectroscopy relies on the dispersion of an infrared beam via a
grating into its monochromatic components and slowly scanning through the entire spectral
region of interest. When a sample is placed in the beam, various wavelengths of infrared
radiation will be absorbed by the sample corresponding to the energies of the possible
vibrational transitions in the molecule or crystal and the remaining signals are recorded as an
absorption spectrum. A major disadvantage of this technique is that every point of the spectrum
has to be recorded separately, which makes it a relatively inefficient.
Fourier-transform spectroscopy offers the possibility to simultaneous and almost
instantaneous recording of the whole spectrum. The basic principle behind this technique relies
on interferometry applying a Michelson (and to a lesser extent Genzel) interferometer. A
Fourier-transform infrared (FTIR) spectrometer consists of a standard infrared radiation source,
collimation mirrors, a beam splitter, a fixed mirror and a moving mirror. The light from the
infrared source is passed through the beam splitter, which directs 50 % of the incident intensity
to the fixed mirror and the other 50 % to the moving mirror. The two beams are recombined at
the beam splitter, so that reconstructive or destructive interference can occur, depending on the
position of the moving mirror to the fixed mirror. The result is an interferogram plotted as light
intensity versus time. For a pure single frequency source, such as a laser as used in FT-Raman
spectroscopy, the result is a pure sine wave.
A sample that absorbs infrared radiation will modify the interferogram according to the
wavelengths absorbed. Thus all the absorption information is contained within a single
interferogram. The mathematics of the Fourier transformation will result in a “single beam”
spectrum of intensity versus wavenumber (or wavelength). One has to take into account that
such a “single beam” spectrum represents a combination of the source and beam splitter
characteristics combined with any absorbances of the air inside the spectrometer such as water
vapour and carbon dioxide. Purging the instrument with dry air can diminish the amount of
water vapour, but a large absorbance of the carbon dioxide will be observed. To correct for this
effect, a “reference” spectrum is taken of the system without the sample before the sample
spectrum is obtained, followed by rationing the sample spectrum to the “reference” or “blank”
spectrum. An important advantage of the FTIR spectroscopy is the ability to increase the signal
to noise ratio by averaging a large number of scans in a relatively short period of time. The
signal to noise ratio improves as the square root of the number of scans taken. In practice, the
interferograms are signal-averaged before a single Fourier transform is done.
Near-infrared (NIR) spectroscopy is also known as “proton” infrared spectroscopy, as it
covers the spectral region in which all the overtone and combination bands of vibrations
involving hydrogen appear. The NIR spectral region has been defined by Kaye40,41 to extend
from 700 to 3500 nm (14285 to 2860 cm-1). The only fundamental vibrations in the NIR region
between 4000 and 10000 cm-1 are those associated with hydrogen atoms existing in hydroxyl
groups or water in the case of minerals and inorganic compounds like LDHs. Rossman42
reported average band positions for hydroxyl and water in the NIR region around 4200 cm-1 as
being due to M-OH motions, 5200 cm-1 as the H2O combination mode (bending + stretching)
and around 7100 cm-1 as the first OH stretching overtone. This means that NIR spectroscopy is
a very suitable technique to study compounds such as LDHs, which contain both water and OH
groups in their structure, to obtain more information about the local environments involved.
INFRARED EMISSION SPECTROSCOPY

The technique of measurement of discrete vibrational frequencies emitted by thermally
excited molecules is known as Fourier transform Infrared Emission Spectroscopy (FTIR ES or
simply IES).43-45 One of the major advantages of Infrared emission spectroscopy is that no real
sample preparation is involved ,as long as the particles are smaller than 1 µm. The great
advantage of the IES technique is that the heated sample acts as a source of the infrared
radiation and so no separate IR source is required as with normal FTIR spectroscopy. The
technique is particularly useful for the study of thermally induced changes such as dehydration,
dehydroxylation, decarbonisation, desorption and phase changes of thin films and
monolayers,46,47 organic compounds including polymers,48,49 and inorganic materials,50-54
including natural and synthetic minerals.55-60 The major advantages of IES are that the samples
are measured in situ at elevated temperatures. Further, the technique removes the difficulties of
heating the sample to elevated temperatures and quenching before measurement, as IES
measures the surface phenomena as it is actually taking place.
Normally when using dispersive infrared spectroscopy, the infrared beam is split into two
beams, one the reference beam and one for the measuring beam. The resultant absorbance is the
negative logarithm of the ratio of the intensities of the measured to reference intensities. In a
Fourier transform instrument the background is measured as a single beam and the measured
spectrum rationed to this background spectrum. In Fourier transform infrared emission
spectroscopy, the emission spectrum is actually this single beam reference or background
spectrum, modified by the instrument response function. Emission spectra are obtained by
rationing the emission of the sample to that of a reference, usually a black body source, which
emits a continuum of radiation according to Planck’s law. Real samples will always emit less
energy than that of the blackbody. Consequently, for any given temperature, the ratio of the
energy emitted by the sample to that of the blackbody at any given wavelength is the emissivity.
RAMAN SPECTROSCOPY
Raman spectroscopy is a relative old technique and was based on theoretical grounds
already predicted in 1923. Sir C.V. Raman was, in 1928, the first who experimentally showed
the existence of inelastic lightscattering. This effect became known as the “Raman effect”.
When light hits a molecule, a part of the light will be dispersed with the same wavelength as the
initial light. This effect is known as elastic or Rayleigh scattering. A much smaller part,
however, will show a shift in wavelength (approximately 10-6 of the initial light) due to the
interaction between the vibrating molecules and the incoming photons. The Raman effect
creates a shift in both positive and negative direction compared to the initial wavelength of the
incoming light. These shifts are known as Stokes and anti-Stokes lines. Raman scattering is
thus mainly determined by the structure of a molecule, which can as well be a mineral. Raman
spectroscopy is very sensitive for the symmetry of minerals and is very suitable for the
determination of molecular vibrations of symmetric molecules. Raman spectroscopy can be
seen as complementary to infrared spectroscopy and both are quite often used together. The
major difference between these two techniques is mainly found in the fact that Raman
spectroscopy depends on changes in polarisability of molecules, whereas infrared spectroscopy
depends on changes in dipole moments of molecules.61 Raman microscopy combines the use of
an optical microscope with conventional Raman spectroscopy. The laser beam used as a
lightsource gives a very small spotsize on the mineral surface of less than 1 µm in diameter,
making it possible to analyse even very small crystals without damaging them.62
FACTOR GROUP ANALYSIS

In order to get a useful interpretation of the vibrational spectra of the LDHs it is necessary
to apply a full factor group analysis. The vibrational modes of the hydroxyl groups in the LDH
layers can be interpreted on the basis of the brucite [Mg(OH)2] structure from which the LDH
structure is derived, by partial replacement of the M2+ cation by a M3+ cation. Both have a
hexagonal symmetry with one formula unit per primitive cell. This leads to a space group D3d
with z =3/8.63,64 The whole vibrational representation including optically active modes will
then be:
Γν = 10 A1g + 5 A2g + 15 Eg + 5 A1u + 10 A2u + 15 Eu
The infrared active modes are thus represented by ΓνIR = 10 A2u + 15 Eu and the Raman
active modes by ΓνR = 10 A1g + 15 Eg. The remaining modes are not infrared or Raman active.
Modes A1g and A2u represent the OH-stretching modes, Eg and Eu the corresponding librational
modes, and A1g(T), A2u(T), Eg(T) and Eu(T) the translational lattice modes.64 A similar factor group
analysis has to be applied for the interlayer anionic groups in the LDH structure. Based on the
crystal structure of LDHs, one can expect various OH-modes as each OH-group in the LDH
layer is bonded to three metal cations. Therefore, one can theoretically expect an overlap of
bands belonging to 3M2+-OH, 2M2+M3+-OH, M2+2M3+-OH and 3M3+-OH, resulting in one
broad band. However, based on the possible range of M2+-M3+ substitutions, the last band will
not be observed and the M2+2M3+-OH will be very weak.65,66
THE HYDROXIDE LAYERS

Mg/Al-LDH
Some of the first infrared spectra of synthetic Mg/Al-HTs were published in 1965 by
Mumpton et al.67 and by Ross and Kodama in 1967.17 Although the bands are broad, a band can
clearly be recognised around 3480 cm-1 with a shoulder around 3000 cm-1. Both bands were
incorrectly interpreted as being water-stretching vibrations. Koritnig and Süsse68 described in
1975 a new type of LDH named meixnerite with a chemical composition of
Mg6Al2(OH)18.4H2O, and compared it with hydrotalcite from Snarum and a material prepared
according to the method of Feitknecht.6,7 A strong band was observed around 3470 cm-1 for all
three samples together with two other bands around 670 and 865 cm-1, but no assignment was
made.
Numerous later studies have reported the infrared hydroxyl-modes, and some have been
summarised in Table 1a. In general, a broad band can be recognised, sometimes with a
recognisable shoulder around 3000-3300 cm-1 (Fig. 1). This strong band results from an
overlapping of two, and possibly even three, OH-stretching vibrations and a stretching
vibration due to interlayer water. Another possibility has been proposed by Lutz,73 who pointed
out that brucite-type hydroxides possess relatively strong side peaks due to combination
vibrations of librational or lattice modes. The shoulder is believed to be due to the interaction
between hydroxyls and the interlayer carbonate. Châtelet et al.,69 however, report a shoulder
around 3050 cm-1, which they ascribe to what they call “solvation water molecules” highly
condensed into the microporosity. The replacement of Mg2+ by Al3+ with its higher charge and
smaller ionic radius in the brucite-like layers results in a stronger hydrogen bond,63 with a
shorter O-H bond in LDH than in brucite, due to an increased electrostatic attraction within
each layer.64 This effect is detected in the infrared spectra by a shift of the main OH-stretching
band from ca. 3570-3555 cm-1 for brucite to approximately 3450 cm-1 for the Mg/Al-LDH.
A similar shift can be observed for the lattice translation modes in the low frequency region
of Mg/Al-LDH in comparison to brucite.64 Roughly below 650 cm-1 the lattice translational
modes can be observed, while between ca. 700 and 1000 cm-1, broad and intense bands due to
librational modes of the hydroxyl groups and water can be seen. The band around 450 cm-1 has
been ascribed to a condensed [AlO6]3- group or as single Al-O bonds.72 In many spectra
reported in the literature a broad complex band is observed with components around 600-650
cm-1 with64-66,71,72 or without69,70 a separately recognisable band around 555 cm-1. This part of
the spectrum is complicated, as on the bands due to Al-O and Mg-O the carbonate band ν4(E’)
can be superimposed around 680 cm-1.63 Controversy exists about the interpretation of the band
around 870 cm-1. Moroz and Arkhipenko,63 Kloprogge and Frost65 and Hickey et al.66 have
ascribed this band to the ν2(A”2) mode of the interlayer carbonate, while Kagunya et al.64
assigned the band around 856 cm-1 as the Eu(R)(OH) mode for LDHs with not only carbonate,
but also with nitrate and hydroxyls as the interlayer anions. Due to the broadness of the bands in
this region, both explanations may well be correct and actually an overlap of both bands might
be observed. In contrast to the above interpretations, Valcheva-Traykova et al.72 assigned a
shoulder at 850 cm-1 as being typical for boehmite. However, no boehmite was observed in
their X-ray diffraction patterns, although they claim to observe small amounts in the Scanning
Electron Microscope without description how they recognised the boehmite as a separate
phase.
Kagunya et al.64 noted, based on their study of Mg/Al-LDHs with various interlayer anions
such as CO3, NO3 and OH, that the energies of the librational and lattice modes do not differ
significantly as a function of the interlayer anion. This implies that the dipoles of the hydroxyl
groups in the LDH layers are not affected by the interaction with the interlayer anions. However,
as Table 1a shows, quite a large range of frequencies have been reported by various authors for
Mg/Al-LDHs containing similar and different anions.
In contrast to the numerous infrared spectra that have been reported, the number of Raman
spectra is only very limited. This is partly caused by the fact that in most cases quite a strong
fluorescence background is observed, obscuring the Raman signals of the LDH. Table 1b gives
an overview of the bands associated with the hydroxide layers of Mg/Al-LDH. The
OH-stretching modes are weak but sharper than the corresponding modes in the infrared
spectra. Two bands assigned to the Eg(T) and Eg(R) modes around 695 and 1061 cm-1 by Kagunya
et al.64 are very close to the ν4(E’) and ν1(A’1) modes of the interlayer carbonate around 680 and
1063 cm-1 63 and may therefore very well overlap. Kloprogge and Frost65 reported a sharp band
at 1061 cm-1 with a broader and much weaker overlapping band around 1053 cm-1, but they
were unable to show two bands around 680-695 cm-1. The two bands around 476 and 552 cm-1
have been assigned as hydroxyl groups associated with mainly Al, but which are also
influenced probably by one Mg in its coordination. The band at 476 cm-1 is only Raman active,
while the band at 552 cm-1 has an equivalent mode in the infrared spectrum around 553 cm-1. It
is unclear at the moment the origin of the band around 979 cm-1 in their spectrum.
Table 1. Frequencies (cm-1) and assignments of the hydroxide layer modes of the types M-OH and M-O in the infrared spectra of Mg/Al-layered
double hydroxides in comparison to brucite Mg(OH)2.
(a) Infrared spectra

brucite [67] [18] [69] [70] 1 [71] [72] [64] 1 [65] assignment
- CO3 CO3 CO3 NO3, SO4, Cl CO3 CO3 CO3, NO3, OH CO3 Interlayer anion present
3570 2700-4000 3597 A2u ν1(OH-HOH) or “Mg/Al”-OH
3480 3470 3421 3392-3422 3441 3440-3478 3467 A2u ν2(OH-HOH) or ”Al”-OH
998 985 950 960-945 939 νsym. anion or νdef. Al-OH
865 799 853-830 874 850 2 857-856 870 Eu(OH) or ν2 CO32-
680 670 651 668 671 663 686-663 635 Eu(OH) or “Mg”-OH translation
455 na na 616-584 556 555 553-550 553 A2u(T) or “Al”-OH translation
365 na na 426-419 451 451 448-440 Eu(T)
1
range due to variation in interlayer anion
2
850 cm-1 interpreted as boehmite, 1020 cm-1 as gibbsite
(b) Raman spectra

[63] [64] [65] assignment
3560 3572 3580 A1g(OH) or “Mg/Al”-OH
3460 3454 3454 A1g(OH-HOH) or “Al”-OH
3358
1061 1053 Eg(R)(OH)
979
695 694 Eg(T) or ν4(E’) CO3
557 552 Eg(T)
483 476 A1g(T)
393 388 A1g(T)
307 303 Acoustic overtone
Figure 1 Infrared spectra of LDHs containing Cu, Ni, Mg and Co as the divalent cation. Indicated are the the
hydroxyl modes related to either hydroxyl groups in the LDH structure or interlayer water.
Replacement of Mg by Other di- and Monovalent Metals in M2+/Al-LDH
The infrared spectra from hydrotalcites with Mg partly or completely replaced by Zn have
been briefly reported.74,75 Kooli et al.75 indicated that the addition of Zn in the Mg/Al
hydrotalcite composition resulted in a slight shift of the OH-stretching mode towards higher
frequency, together with the ν3 mode of the interlayer carbonate. However, detailed
descriptions of the influence of different cations on the IR spectra, especially on the lattice
region, of hydrotalcite have not been given by these authors.
Recently, Kloprogge and coworkers have systematically studied the infrared and Raman
spectra of LDHs with increasing Mg/Zn ratios, Table 2.76 The shift towards higher frequencies
with the incorporation of Zn in the LDH structure was not observed in this study. In addition,
two new bands were observed in the Raman spectra in the low frequency region around 450 and
495 cm-1 with only one corresponding band in the infrared spectrum around 445 cm-1. These
bands are similar to the bands observed around 460 and 520 cm-1 in the infrared spectrum of
hydrozincite.77
The Zn/Al-LDH variety has been synthesised and characterised by vibrational
spectroscopic methods by Hickey et al.78 as a continuation of the study by Kloprogge et al.76 on
Mg/Zn/Al-LDHs. Barriga et al.79 reported the infrared spectrum of Zn/Al-LDH with a broad
band due to OH-stretching modes around 3435-3445 cm-1. However, the low frequency region
was not described in detail, but the pattern reported seems to be similar to those of
Mg/Al-LDHs. Hickey et al.78 observed a slight shift up to 15 cm-1 towards lower frequencies
for the bands below 1000 cm-1 compared to similar bands for Mg/Al-LDH. This is in contrast
with earlier findings of Kooli et al.75 but it does agree with the results reported by Kloprogge et
al.76
Table 2. FT-IR and FT-Raman band positions of hydrotalcite with composition Mg4Zn2Al2(OH)16CO3.nH2O compared to similar bands in related
minerals and suggested interpretation.
FT-IR bands FT-Raman FT-Raman bands FT-Raman bands FT-Raman IR natural Suggested assignment
(cm-1) bands (cm-1) (cm-1) (cm-1) bands (cm-1) hydrozincite [64,76]
hydrotalcite hydrotalcite hydrotalcite hydrotalcite hydrotalcite 2[Zn5(CO3)2(OH)6]
Mg/Zn/Al Mg/Zn/Al Mg/Zn/Al 4/2/2 Mg/Zn/Al 2/4/2 Mg/Zn/Al [77]
4/2/2 6/0/2 0/6/2
445 452 443 460 “Zn”-OH translation
476 476 477 465 A1g(T) or “Al/Mg”-OH translation
496 494 495 520 A1g(T) or “Zn”-OH translation
559 552 548 550 549 Eg(T) or “Al/Mg”-OH translation
616 “Al/Mg”-OH translation
771 Eg(T) or “Al”-OH translation or ν4(E’) CO3
955 979 979 981 980 960
“Al/Zn”-OH deformation
1033 Eg(R)(OH) or “Al”-OH deformation
3358 3362 3365 3360 3300 A1g(OH-?) or M-OH1 stretch
3471 3454 3444 3445 3444 A1g(OH-HOH) or M-OH2 stretch
3580 3562 3535 3559 A1g(OH) or M-OH3 stretch
An interesting precursor for industrial catalysts is obtained when the Zn/Al-LDH is

modified by the incorporation of divalent copper. Thermal transformation of this material leads
to catalytically active mixed metal oxides for relatively low temperature synthesis of methanol
or methanol-higher alcohol mixtures from syngas (CO + CO2 + H2 in variable proportions)80-82
and the Fischer-Tropsch synthesis of hydrocarbons.83 The infrared spectra for LDHs with
Cu:Zn:Al ratios of 38.0:38.0:24.0 and 34.5:34.5:31.0 reported by Trifirò et al.84 show very
broad bands without much detail. A strong broad band is observed around 3400-3500 cm-1,
while in the low frequency region no clear bands can be distinguished. Kooli et al.75 reported
that upon the incorporation of small amounts of Cu the OH-stretching modes remain near 3450
cm-1, but a shift towards 3400 cm-1 is observed when the Cu/Zn ratio becomes higher than 6. In
general, their spectrum reveals a broadening of all bands and a loss of details in the region
below 800 cm-1 compared to the spectra of the Zn/Al- and Mg/Zn/Al-LDHs. Morpurgo et al.85
even go a step further and incorporated small amounts of Co, up to 15 atom%, in the
Zn/Cu/Al-LDH. They did not report the infrared of Raman spectra, but they did report the
near-infrared spectra in the region between 5000 and 30000 cm-1. A broad band is observed
around 12500 cm-1, which is attributed to the envelope of the transition for Cu2+ in a distorted
octahedral coordination. The incorporation of Co resulted in the formation of a weak band
around 20000 cm-1 assigned to Co2+ in octahedral coordination. The two bands corresponding
to the 4T1g → 4T2g transition of octahedral Co2+ around 8300 cm-1 and to the dz2 → dx2-y2
transition of distorted octahedral Cu2+ around 8000 cm-1 are very weak and could not be
separately distinguished.
Cobalt plays an important role in heterogeneous catalysis and therefore it is not surprising
that Co/Al-LDHs have been synthesised as precursors for the preparation of mixed metal oxide
catalysts for Fischer-Tropsch reactions.86-89 Fig. 1 shows the infrared spectrum of a Co/Al-LDH.
Kannan and Swamy86 described a broad band around 3440 cm-1, which they assigned as H2O
stretching mode instead of overlapping M-OH stretching modes (Table 3). In the low frequency
region they attributed the 785 and 602 cm-1 bands to the Co-Al-OH stretching and bending
modes, respectively. The other bands were not assigned other than as lattice vibrations of the
cations. In a later paper they showed the effect of increasing the Co/Al ratio.90 Increasing the
Co/Al ratio from 2 to 2.6 and 3.1 resulted in a shift from 3414 to 3436 and 3453 cm-1,
respectively. At the same time, they observed an increase in bandwidth from 280 cm-1 to 380
cm-1 for this broad band. Hydrothermal treatment at 110°C for 2 days significantly decreased
the bandwidth by 100 to 200 cm-1 but no significant shift in the position. The infrared spectrum
of Co/Al-LDH and subsequent band component analysis reported by Kloprogge et al.65
revealed much more details and some significant differences, especially in the low frequency
region. These authors65 observed two bands around 925 and 861 cm-1 in agreement with the
infrared spectra of other LDHs, which were not observed by Kannan and Swamy.86 In addition,
the bands around 733 and 588 cm-1 are strongly shifted towards lower wavenumbers compared
to the corresponding bands reported by Kannan and Swamy86 around 785 and 602 cm-1.
Kloprogge et al.65 were unable to measure the corresponding Raman spectrum due to strong
fluorescence.
Takovite forms one of the most important LDH variations, in which Mg2+ is fully replaced
by Ni2+. Takovite and other transition metal LDHs are used as precursors for the preparation of
heterogeneous catalysts, sensors and as electrodes for alkaline secondary batteries and fuel
cells.91-98 Heat treatment under reducing conditions converts the takovite in a Ni/Al2O3 catalyst
for methanation of CO, Fischer-Tropsch reactions and steam reforming of methane. Bish and
Brindley99 described the infrared spectra of some naturally occurring takovites including
material from the type locality Takovo. The OH-stretching modes associated with the
hydroxide layers were shown as a broad band around 3400 cm-1. From the low frequency
region they only mentioned that the bands could be attributed to cation-oxygen vibrations.
Other papers were mainly focussed on synthetic takovites. Hernández-Moreno et al.100 and
Kannan et al.101 showed that increasing the amount of Ni from a ratio Ni/Al 2 to 3 resulted in a
shift of the OH-stretching band from approximately 3420/3450 to 3500 cm-1. This can be
ascribed to the changes in electrostatic interaction between the hydroxide layer and the
interlayer, which has its effect on the hydrogen bonding. Kloprogge et al.65 observed in their
band component analysis of the hydroxyl-stretching region a weak band around 3697 cm-1 in
addition to the major band around 3570 cm-1 (Table 3). This high-wavenumber band was
interpreted as an OH-stretching mode of a hydroxyl group bonded to both Al and Ni in adjacent
octahedral sharing the hydroxyl group. In the low frequency region minor shifts are observed
with increasing nickel content, together with a broadening of the bands due to a possible
decrease in the cation ordering.100 Ehlsissen et al.102 reported a broad band around 3500 cm-1
plus two lattice vibrations at 480 and 520 cm-1. The very low crystallinity of their material
resulted in a spectrum with very broad bands masking other bands in the low frequency region
observed by others.65,100 Both Raman microscope and FT-Raman spectra have not been
reported so far basically due to the problems with fluorescence and heating resulting in a huge
thermal band in the FT-Raman spectrum even at low laser power (30-35 mW). A clearly
green-colored material as takovite lends itself to a study of the UV-VIS spectra. Labajos et
al.103 showed two double bands at 740 and 645 nm and at 410 and 378 nm together with a weak
band around 275-300 nm. The weak band around 275-300 nm was interpreted as being due to
charge transfer processes. These bands were assigned according to the Tanabe-Sugano energy
level diagram for a d8 configuration in an octahedral geometry.104 Two spin-allowed transitions
3
A2g(F) → 3T1g(F) and 3A2g(F) → 3T1g(P) were assigned to the bands at 740 and 378 nm,
respectively, while the bands at 645 and 410 nm were assigned to the spin-forbidden transitions
3
A2g(F) → 1Eg(D) and 3A2g(F) → 1T2g(D).
Table 3. FT-IR band positions of the vibrational modes associated with the hydroxide layers of
LDHs with varying monovalent and divalent cations.
Mg [65] Zn [78] Co [65] Co [86] Ni [65] /cm-1 Ni2 [100] Ni [102] Li [108]
/cm-1 /cm-1 /cm-1 /cm-1 /cm-1 /cm-1 /cm-1
3697
3597 3573 3570
3467 3468 3474 3440 3420 3450 3400
939 942 925 913 995 900
870* 868* 861* 846*
759 785 785 753 755
739 733
635 620
590 588 602 597 620 600 ± 630
553 552 548 549 558 560 560 545
523 ± 475
450 430 424 435 425 390
*possible overlap with ν4 CO3
A naturally occurring mineral related to takovite is known as carrboydite named after the
Carr Boyd Rocks nickel mine, West Australia.105 The most important differences are the partial
substitution of Ni by Cu and CO3 by SO4 in the interlayer region, and a composition of
(Ni,Cu)14Al9(SO4,CO3)6(OH)43.7H2O is now accepted. The structure is however different from
hydrotalcite-type minerals such as takovite and is probably more related to nickel
hydroaluminate, which consists of sheets containing three layers of hydroxyl groups between
which two layers of cations are sandwiched. In the case of carrboydite it was assumed that the
charged anions would be accommodated largely in the double-layered sheets containing the
cations and not in the interlayer. The interlayer is basically filled with only water molecules.
The infrared spectrum shows a very broad and strong OH-stretching band around 3400 cm-1 in
which no details can be distinguished. Nickel and Clarke did not give any interpretation of the
low-frequency region containing various cation-anion interactions. However, from the figure in
their article, bands can be recognised around 380, 540, 600, 720, 840, 1000, 1120, 1180 and
1240 cm-1. Some of these bands represent carbonate and sulfate modes.
A special type of LDH is formed when the divalent cation is replaced by a monovalent
cation, as in the case of lithium dialuminate [LiAl2(OH)6]2CO3. Here the presence of lithium
cations in the aluminium hydroxide sheets like in gibbsite or bayerite resulting in positively
charged sheets compensated by interlayer anions such as hydroxyls or carbonate giving a
hydrotalcite-type structure.106,107 Infrared spectra have been reported by Sissoko et al. for the
sulfate equivalent [Li Al2(OH)6]2SO4 and Perrota et al. for lithium dialuminate formed as a thin
film on aluminium film and powder after reaction with lithium hydroxide or carbonate
solutions.108,109 The broad OH-stretching mode is observed around 3400 cm-1, while low
frequency bands can be identified around 900, 755, 630, 545, 475 and 390 cm-1, Table 3.108
Sissoko et al. also reported a band at 235 cm-1, which they ascribed to be associated with Li-O,
as this band strongly diminished in intensity upon leaching of the Li from the hydrotalcite-like
structure. The exact band positions cannot easily be identified in the spectra reported by Perrota
et al.,109 as the bands are broad and overlapping. In addition, the spectra show mixtures of the
starting Al-sheet plus the LDH component and small amounts of bayerite. Dutta and Puri110
reported the Raman spectrum with lattice modes νOAlO at 362, 402, 532 and 555 cm-1, νOAlO at
380 and 460 cm-1 and νOAl at 602 and 752 cm-1. These assignments were shown to be consistent
with vibrational data of LiAl-LDH synthesised in D2O. For the deuterated sample Raman bands
were observed for νOAlO around 353 and 526 cm-1, νOAlO around 460 cm-1 and νOAl at 593 and
740 cm-1. No equivalent bands were observed in the deuterated spectrum for the bands around
460, 402 and 555 cm-1 in the original Raman spectrum. Two weak bands around 880 and 1030
cm-1 were attributed to OH-bending modes. The OH-stretching region was characterised by
broad bands around 32450 and 3484 cm-1 together with a sharper band at 3590 cm-1.
Deuteration resulted in a shift of these bands to 2398, 2440 and 2651 cm-1, respectively. In
contrast to all other papers on LDHs and their infrared spectra, the first two OH-stretching
bands in the Raman spectrum were interpreted as being due to intercalated water in the
interlayer, while the sharp band was assigned to OH-groups of the LDH bonded to the
interlayer chlorine anion.
Replacement of Al by Other Trivalent Metals in Mg/M3+-LDH
Ga is an interesting substitution as it is very comparable to Al in terms of behaviour and

size. It is well known from pillared clays111 and zeolites112,113 that Ga has a significant influence
on their catalytic activity and selectivity compared to Al and similar differences can be
expected for LDHs in which Al3+ is replaced by Ga3+. Ga-containing LDHs are potential
catalyst precursors in the dehydrogenation and aromatisation reactions of light olefins.114-116 In
addition, this substitution is expected to have an effect on their vibrational and NMR spectra.
Aramendía et al.117 reported the synthesis of Mg/Ga- and Mg/Al,Ga-LDHs. However, the FTIR
spectra only reveal a very broad band between 3800 and 2700 cm-1 together with broad bands
corresponding to the interlayer carbonate modes. The incorporation of Ga seems to result in a
broadening of the OH-stretching band around 3700 cm-1. Bands between 450 and 650 cm-1 are
claimed to correspond to vibrations of the oxides MgO, Al2O3 and Ga2O3, but these vibrations
are not shown nor are their positions quoted. Rousselot et al.118 synthesised mixed
Mg/Al,Ga-LDHs. Again a broad band is observed around 3500 cm-1 and a broad band is
present around 680 cm-1. The lower wavenumber bands were not further specified as being due
to lattice vibrations such as Al-O, Ga-O, Mg-O and Al-O-Ga without giving band positions.
A naturally occurring LDH in which Al3+ is replaced by Fe3+ is known as coalingite,
Mg10Fe2(CO3)(OH)24.2H2O.119 The infrared spectrum is rather similar to that of hydrotalcite,
with a strong OH-stretching mode around 3450 cm-1. The carbonate modes around 1430 cm-1
are broad and only a very weak band can be recognised around 870 cm-1, which might be either
Eu(OH) or ν2 CO32-. Other bands cannot be recognised in the low frequency region. Fernández
et al.120 prepared the synthetic analogue as well as a hydrotalcite in which only a part of the Al3+
was substituted by Fe3+. A broad band is observed around 3500 cm-1 due to the stretching
modes of the hydroxyl groups from the hydroxide layers and from the interlayer water
molecules. In the region below 1000 cm-1 differences in relative intensities were observed for
several bands due to the presence of different amounts of Al3+ and Fe3+ in the LDH structure.
Increasing the trivalent iron content from [Mg0.74Fe0.11Al0.15(OH)2][CO3].0.70H2O to
[Mg0.75Fe0.25(OH)2][CO3]0.13.
0.61H2O resulted in a split of the 440 cm-1 band into a band at 380 cm-1 plus a shoulder around
450 cm-1. At the same time a broad band around 625 cm-1 with a very weak shoulder is split into
two clearly distinguishable bands around 625 and 720 cm-1. A second shoulder around 875 cm-1
becomes invisible in the figure presented in this paper. The UV-VIS spectrum of the
aluminium-free LDH exhibited a broad absorption centred around 400 nm with another sharp
absorption near 300 nm. It was pointed out by the authors that because Mg2+ has a d0
configuration and Fe3+ a d5 high-spin configuration, due to weak field oxide ligands the
absorptions should be due to charge transfer processes from the (hydr)oxide ligands to the Fe3+
ions.
The same group of scientists around Rives also prepared LDHs with other trivalent metals
such as Cr3+, V3+ and Y3+. The OH-stretching mode of the hydrogen-bonded hydroxyl groups,
both from the layers and interlayer water molecules, are observed to shift from 3410 to 3448
and 3472-3480 cm-1 for LDHs containing Cr, Y+Al and V as the trivalent cation,
respectively.121-123 For the Y-containing Mg/Al-LDH two relatively broad bands were reported
in the low frequency region at 605 and 412 cm-1, which were attributed to lattice vibrations of
possibly Mg-O, Al-O, Y-O, Mg-O-Al, etc. without further specification.121 The V-containing
sample revealed lattice vibrations around 395, 510, 709 and 960 cm-1,122 which agrees quite
well with the A2u(T) mode for Mg/Al-LDH around 448 cm-1 and the Eu(OH) mode around 686
cm-1.64 A band comparable to the 960 cm-1 band was observed by Kloprogge et al.65 for
Mg/Al-LDH at 979 cm-1. For the Mg/Cr-LDH also the UV-VIS spectrum was reported with
broad bands around 225, 400 and 570 nm with a shoulder around 690 nm.123 The absorptions
around 570 and 400 nm were ascribed to the transitions 4A2g(F) → 4T2g(F) and 4A2g(F) →
4
T1g(F), respectively. The band around 225 nm was interpreted as being due to charge transfer.
The broadness of the bands can be explained, at least partially, by the lowering of the symmetry
of the Cr3+ in the octahedra in the brucite-like layers compared to that of Cr(H2O)63+. The
shoulder around 690 nm was explained by the spin-forbidden transition
4
A2g(F) → 2Eg.
Desautelsite is a naturally occurring orange-coloured LDH in which the trivalent cation is

basically Mn3+. Hansen and Taylor124 reported on the synthesis of desautelsite by aerial
oxidation of a suspension of freshly prepared manganese(II) carbonate in a magnesium nitrate
solution at a fixed pH. The presence of Mn2+ and Mn4+ cannot be excluded in this synthesis and
these can very well be incorporated in the LDH structure. In contrast, Fernández et al.125
reported a coprecipitation method followed by washing and drying at 60°C without aerial
oxidation resulting in only partial oxidation of Mn2+ to Mn3+ in the LDH hydroxide layers.
They found that under these conditions more than 80 % of the manganese was oxidised to Mn3+.
The infrared spectra of the Mg/Mn-LDHs reported by both groups show some significant
differences. The OH-stretching band is represented by a single broad band around 3420 cm-1 in
the spectrum measured by Fernández et al.,125 while Hansen and Taylor124 showed a similar
band around 3430 cm-1 but with a clear shoulder near 3560 cm-1 which may be due to surface
water on the outside of the crystals. Also in the low frequency region there are some significant
differences. The 955 cm-1 band125 is comparable to the band observed around 979 cm-1 for
Mg/Al-LDH,65 but this band was not observed by Hansen and Taylor.124 The 864 cm-1 band was
interpreted by Hansen and Taylor as being due to a MnCO3 impurity, but on this position also
the interlayer carbonate ν2 has been observed in other LDHs. The broad band around 625 cm-1
reported by Fernández et al.125 seems to have a shoulder around 685 cm-1, which can be
ascribed to the ν4 interlayer carbonate mode. This band is comparable to the very sharp band at
619 cm-1 reported by Hansen and Taylor,124 although they show a clear split between the 619
and 684 cm-1 bands in their infrared spectrum. The interpretation of the differences is far from
being straightforward, especially because one of the spectra contains impurities such as MnCO3
and nitrate salts.124
Other Combinations di- and Trivalent Metals in LDHs
Well-known Ni/Fe containing naturally occurring layered hydroxide materials related to

hydrotalcite and carrboydite are reevesite [Ni6Fe2(CO3)(OH)16.4H2O], honessite
[Ni6Fe2(SO4)(OH)16.4H2O] and hydrohonessite [Ni6Fe2(SO4)(OH)16.7H2O].126,127 These three
minerals are quite often found as mixtures and are difficult to separate for single mineral
analysis. The spectra are very similar as might be expected based on the fact that for honessite
and hydrohonessite only the amount of water is different. Both are characterised by a broad
OH-stretching mode around 3400 cm-1 plus a weak band around 480 cm-1 in the low frequency
region, which can be assigned as a lattice vibration. Two weak shoulders can be recognised
around 720 and 760 cm-1, which are comparable to bands observed around 739 and 785 cm-1 for
Zn/Al-LDH by Hickey et al.78 The infrared spectrum for synthetic hydrohonessite126 was
shown to be very similar to that of natural honessite as published by Bish and Livingstone.127
Del Arco et al.128 reported the infrared spectrum of synthetic reevesite with a broad band
between roughly 4000 and 3000 cm-1 due to the OH-stretching modes of hydroxyl groups in the
hydroxide sheets linked to Ni and/or Fe and of interlayer water molecules. In the low frequency
region bands can be observed around 385, 500 and 770 cm-1 with shoulders around 615 and 960
cm-1. No further assignment was made than that these bands are other modes of bicarbonate and
vibrations implying M-O, M-O-M and O-M-O in the hydroxide sheets with M either Ni2+ or
Fe3+.
Several other papers have dealt with a combination of Ni2+ withother di- and trivalent
metals including Zn2+, Fe3+, Cr3+, V3+ and Mn3+ in order to prepare new types of catalyst
precursors. Barriga et al.129 described the synthesis of Ni/Mn(III)-LDH prepared via a similar
route as was used for the synthesis of Mg/Mn(III)-LDH,125 using coprecipitation during which
partial oxidation of the initial Mn2+ to Mn3+ took place. In addition to the usual OH-stretching
band around 3420 cm-1 due to the overlapping modes of the hydroxyl groups in the brucite-like
sheets and the interlayer water molecules, clearly recognisable lattice vibrations were reported
around 384, 563 and 731 cm-1. Labajos et al.130 reported the infrared spectra of Ni/V3+-LDHs
with Ni/V ratios of 2.54 and 4.35. Replacement of Mn by V resulted in a shift of the broad
OH-stretching band from 3420 to 3435 cm-1. The interpretation of the low frequency region
containing basically the lattice vibrational modes is even more complicated in this case as the
atomic weights of Ni and V are rather similar. However, increasing the Ni/V ratio gives some
significant changes in the low frequency region (Table 4). The two peaks around 520 and 525
cm-1 merge into one broad band around 522 cm-1 with increasing V content. Also the two bands
around 677 and 776 cm-1 merge into a single band with a maximum shifted towards lower
wavenumbers to 732 cm-1. At the same time, the shoulder around 843 cm-1 becomes a clearly
recognisable band with increasing V content.
For nickel catalysts to be active and selective for most reactions, a high dispersion of the
metallic phase is required. It has been shown that for coke formation during acetylene
hydrogenation three-atom clusters on the surface of the catalysts are needed.131 Therefore, coke
formation can be diminished through what has been called “geometrical isolation of the surface
nickel atoms” by incorporation of zinc in the alumina carrier forming a spinel-type phase.132
From this point of view, Monzón et al.133 have attempted to synthesise a three-metal-LDH
containing Zn2+, Ni2+ and Al3+, which were even further modified by the addition of Cr3+ or
Fe3+ to influence the catalytic activity and selectivity. The infrared spectra of the Zn/Cr/Al- and
the Ni/Zn/Cr/Al-LDHs are very similar. The same is true for the combinations Zn/Fe/Al and
Ni/Zn/Fe/Al. However, the incorporation of either Cr or Fe resulted in some minor changes in
the low frequency region, where the Cr-containing samples show a single broad band in the
infrared spectrum around 475 cm-1, which splits up in two bands at 475 and 440 cm-1 for the
Fe-containing samples. For all samples, a broad OH-stretching band was observed around 3400
cm-1. UV-VIS spectroscopy revealed bands around 575 and 410 nm for octahedrally
coordinated Cr3+, which agrees well with other UV-VIS data reported for Mg/Cr-LDH123 with
broad bands around 400 and 570 nm associated with the transitions 4A2g(F) → 4T2g(F) and
4
A2g(F) → 4T1g(F), respectively. Incorporation of Fe3+ in the LDH structure gave a broad band
between 250 and 500 nm associated with charge transfer processes between the oxide ions and
Fe3+.120 Bands around 375, 635 and 730 nm were assigned to the presence of octahedral Ni2+ in
the hydroxide sheets of the LDH structure. Takovite, Ni/Al-hydrotalcite, however, was shown
to have four bands at 378, 410, 645 and 740 cm-1 103 instead of the three observed for the
Ni-containing samples reported by Monzón et al.133 No explanation was given by these authors
other than that these three bands are due to spin-orbit coupling. Labajos and Rives123 reported
two bands for octahedrally coordinated Ni2+ in Ni/Cr-LDH around 746 and 385 nm and for
octahedrally coordinated Cr3+ around 685, 580 and 415 nm.
In a previous paragraph the infrared spectroscopy of LDHs has been described in which
Mg2+ was replaced by Co2+.65,86-90 In these cases it was assumed that Co was only present in the
divalent state, while Al constitutes the trivalent part of the charged hydroxide sheets in the LDH
structure. However, when cobalt is present in the trivalent state, Al-free LDHs can be designed ,
leading to new types of catalysts for the synthesis of alcohols and hydrocarbons or
decomposition of N2O, one of the green house gasses.134,135 Synthesis in a N2 atmosphere led to
the formation of a brucite-like hydroxide with a sharp OH stretching mode around 3655 cm-1,
intermediate between the bands observed for Mg(OH)2 at 3698 cm-1 and Co(OH)2,3 around
3632 cm-1. Increasing the partial O2 pressure results in the formation of a hydrotalcite-like
phase replacing the hydroxide phase as evidenced by a broad band around 3454-3449 cm-1.136 It
was indicated by the authors that the weak bands around 633 and 569 cm-1 in the spectra of the
samples treated at 60° C could be ascribed to the presence of a small amount of a Mg-modified
Co3O4 phase. This seems however questionable as these bands also show up in the infrared
spectra of non-heat treated samples and no corroboration can be found in other analytical
results such as XRD. It is more probable that these bands represent the Eu(OH) and A2u(T) lattice
vibrations similar to the bands around 653 and 535 cm-1 observed for Mg/Al-hydrotalcite.65,76
Hansen et al.137 and Del Arco et al.138 have described the synthesis of Co2+/Fe3+-LDHs. It
was pointed out that during the synthesis and treatments such as drying or hydrothermal aging,
a part of the Co2+ can oxidise to Co3+, as has been observed before for other Co2+ containing
LDHs.87 Table 5 shows the observed band positions for the vibrational modes related to the
hydroxide sheets in comparison to Co/Al-LDH. In addition to the mid-infrared spectrum,
Hansen et al.137 reported three bands around 194, 206 and 337 cm-1 in the far-infrared region.
The split up of the band around 200 cm-1 into two separate modes around 194 and 206 cm-1 is
not directly clear from the figure reported. Based on factor group analysis one would expect
two bands in this region related to the TOice 1h and LOice 1h observed around 202-214 cm-1 and
340-354 cm-1 for Mg/Al-LDHs.64 The 337 cm-1 band reported by Hansen et al.137 was however
interpreted as being a lattice vibration and the other two bands were not assigned at all. Del
Arco et al.138 reported the UV-VIS spectra of Co/Fe-LDHs. In comparison to other UV-VIS
spectra of Co-containing LDHs, these spectra only show very weak and broad bands due to the
fact that these bands are obscured by the much more intense charge transfer transitions
involving the Fe3+. Still for Co2+ a broad band can be recognised around 387 nm with shoulders
around 540 and 668 nm. A shoulder around 300 nm towards lower wavelength was interpreted
as being due to charge transfer processes involving the Co2+. The spectrum of the material air
dried at 70°C was quite different from the other samples, as it basically showed only a broad
absorption between roughly 300 and 700 nm with a maximum around 400 nm. This is
comparable to the spectrum of Co3O4 and might indicate the presence of some oxidised Co in
the sample.
Table 4 FT-IR band positions in the low frequency region of LDHs containing Ni in combination with other trivalent metals.
Ni/Al [65] Ni/Al [100] Ni/Fe [127] Ni/Fe [128] Ni/Mn [129] Ni/V2 [130] Ni/V3 [130]
/cm-1 /cm-1 /cm-1 /cm-1 /cm-1 /cm-1 /cm-1
385 384
435 480 500
558 560 563 520
525 522
597 620
753 720 731 732 677
760 770 776
846 843 843
913
Table 5 FT-IR band positions related to the hydroxide sheets of Co/Fe-LDH in comparison to Co/Al-LDH
Co/Fe [136] /cm-1 Co/Fe [137] /cm-1 Co/Al [65] /cm-1 Co/Al [86] /cm-1
3573
3400 3445 3474 3440
925
861
764 770 733 785
624 635
588 602
516 540 548 549
489 Not analysed 424
SIMPLE INTERLAYER ANIONS

Most of synthetic, but also naturally occurring LDHs, contain CO32- as the interlayer anion.
Other regularly used anions include NO3-, OH-, SO42- and Cl- in addition to ClO4- and CrO42-. In
exchange experiments an order of preference can be determined:
CO32- > NO3- > OH- ≈ Cl- > SO42-

In many syntheses of LDHs, starting solutions of metal nitrates have been used and even
though it is the intention to synthesise the carbonate interlayered LDH, small amounts of the
nitrate may be incorporated in the interlayer region.65,66,101 Similarly, Rousselot et al.118
observed that during the synthesis of NO3-containing LDHs still small amounts of CO32- were
incorporated. The presence of both anions will be reflected in the infrared and Raman spectra.
The presence of Cl- as the interlayer anion in LDHs will not be discussed in this paragraph, as it
does not result in any vibrational modes in the infrared or Raman spectra. However, chlorine
containing LDHs are of interest for spectroscopic research as it effectively removes all the
interference of interlayer anion vibrational modes with the LDH lattice modes in the lower half
of the infrared and Raman spectrum.
CO32-
The mostly observed interlayer anionic group is CO32-. When the carbonate species is
present as a free ion not involved in any bonds, it will exhibit a space group D3h. As a result,
three bands, the bending non-planar mode ν2(A”2), the antisymmetrical stretching mode ν3(E’)
and the bending angular mode ν4(E’), will be observed in the infrared spectrum around 880,
1415 and 680 cm-1, while the symmetric stretching mode ν1(A’1) is infrared inactive. In the
Raman spectrum one will observe ν1(A’1), ν3(E’) and ν4(E’).139,140 However, changes can be
expected when the carbonate ion is intercalated in the LDH structure as it will be affected by
interactions with interlayer water molecules and/or OH- groups from the LDH layers. In
comparison with free CO32-, a shift towards lower wavenumbers is generally observed.
Interaction between interlayer water molecules and the carbonate ion is reflected by the
presence in the OH- stretching region of the infrared spectrum around 3000-3100
cm-1.65,67,71,75,84,86,101,108,117,118,122,123,128,129,133,138 This band has been attributed to the bridging
mode H2O-CO32- (see also Fig. 1). In contrast to this interpretation, Châtelet et al.69 ascribed a
band at 3050 cm-1 to solvation water molecules highly condensed into the micropores. Most
LDHs with carbonate as the interlayer anion show infrared bands around roughly 1360-1400,
875 and 670 cm-1. Table 6 summarizes the carbonate band positions observed for LDHs
containing different di- and trivalent metals. Hernández-Moreno et al.100 stated that the nature
of the hydroxide sheets has hardly any influence on the band positions, which is confirmed by
the small shift within a range of approximately 30 cm-1 of the ν3 mode independently of the di-
and trivalent cations present.
The shift towards lower wavenumbers indicates a loss of freedom compared to free CO32-
and as a consequence a lowering of the carbonate symmetry from D3h to probably C2v or Cs. In
one paper symmetry lowering to D3 has been suggested79 as a possibility, but this has to be
considered to be incorrect. As a result of this symmetry lowering the infrared inactive ν1 mode
will be activated. Indeed, a weak band has been observed around 1050-1060 cm-1 (Table 6). In
addition the ν3 mode shows a small splitting in the order of 30-60 cm-1. Some papers have only
reported the activated ν1 in combination with a single ν3 band.118,122,123 In these cases the ν3
band seems to be broadened due to an overlap of the two split modes ν3 and ν3a (Fig. 2). Based
on X-ray diffraction, ionic size and charge density, it has been widely accepted that the
orientation of the carbonate anion within the interlayer space is such that its C3 axis is
perpendicular to the hydroxide sheets of the LDH.141
Figure 2 Comparison of the infrared and Raman spectrum of the interlayer carbonate modes in Mg/Al-LDH in
the range between 400 and 1600 cm-1. Indicated are also the bands associated with the presence of some
interlayer nitrate.
An interesting experiment reported by Rey et al.142 may help in the interpretation of this
symmetry lowering. They showed that upon heating a Mg/Al-LDH to 100°C the
water-carbonate bridging mode around 3165 cm-1 disappeared together with the water-bending
mode around 1616 cm-1, as expected upon dehydration. At the same time, the relatively broad
carbonate ν3 mode at 1363 cm-1 becomes clearly split into two bands around 1357 and 1391
cm-1 (∆ν3 34 cm-1) together with a strong sharp band around 1538 cm-1 indicating a change in
the carbonate symmetry upon dehydration of the LDH. The authors interpreted the split of the
initial ν3 as being the 1391 and 1538 band with a ∆ν3 of 147 cm-1, which seems rather
unrealistic. A more realistic alternative explanation might be the formation of a bicarbonate ion
upon dehydration due to proton transfer from the hydroxide sheets to the carbonate ion. A
similar option was discussed by Clause et al.20 and Barriga et al.79 for their observation of a
band around 1500-1550 cm-1. In a relative large number of spectra the bands associated with
the ν2 and ν4 modes have not been observed as separate modes due to strong overlap with other
modes associated with the hydroxide sheets.
Table 6. FT-IR interlayer CO32- vibrational modes as function of di-/trivalent metal composition of the LDH.
Only a very limited number of Raman studies have been reported so far on the interlayer
carbonate anion in LDHs. As already indicated at the beginning of this paragraph, three modes
will be observed in the Raman spectrum: the symmetrical stretching vibration ν1(A’1), the
antisymmetrical stretching vibration ν3(E’) and the bending angular vibration ν4(E’) around
1063, 1415 and 680 cm-1, respectively, for the free CO32- anion.63,139,140 In accordance to the
findings of Moroz and Arkhipenko,63 Kloprogge and Frost65 and Hickey et al.66 observed very
weak ν3 and ν4 modes around 1053 and 1403 cm-1. In addition, the ν4 mode is relatively broad.
The weak band at 1053 cm-1 overlaps with a very strong and sharp band at 1061 cm-1, which
was initially ascribed as being due to the lowering of the carbonate symmetry. However, more
detailed information points to the incorporation of minor amounts of nitrate as a second
interlayer anion caused by the synthesis from metal nitrates, which might explain not only the
strong 1061 cm-1 band, but also the strong broadening of the 1403 cm-1 band. Like in the
infrared spectra, both ν3 and ν4 bands show a minor shift of approximately 10 to 15 cm-1 to
lower wavenumbers. However, for the ν4 mode, Kloprogge and Frost65 reported a minor sharp
band at 694 cm-1, which indicates a similar sized shift, but in the opposite direction. A
reasonable explanation for this band was given by Kagunya et al.,64 who showed the presence
of a band at 698 and 695 cm-1 in the Raman spectra of Mg/Al-LDHs with OH- and CO32- as
interlayer anion, respectively, and assigned this vibration as the Eg(T) mode. This band will then
fully overlap the much weaker carbonate ν4 mode. Detailed examination of the 694 cm-1 band
indicates a rather sudden broadening, supporting an overlap between these two bands. Similarly,
Kagunya et al.64 gave an alternative assignment for the 1061 cm-1 band as the Eg(R) (OH) mode,
which they observed in both the carbonate and the hydroxyl interlayered LDHs.
NO3-
Like free carbonate, free nitrate NO3- will exhibit a space group of D3h with A1’ Raman
actively only, A2” infrared active only and 2E’ both Raman and infrared active.36 This means
that the out-of-plane symmetric deformation mode ν2, antisymmetric stretching mode ν3 and
antisymmetric deformation mode ν4 will be observed in the infrared spectrum around 830,
1350 and 680 cm-1, while the symmetric stretching mode ν1 together with afore mentioned ν3
and ν4 modes will be observed in the Raman spectrum around 1049, 1355 and 690 cm-1,31 Table
7. Fig. 3 shows the infrared and Raman spectra of interlayer nitrate in Mg/Al-LDH. Miyata16
was one of the first to use infrared spectroscopy to study nitrate as the interlayer anion in LDHs,
as it represents a very strong tool to study anion exchange processes in these types of layered
materials. He reported a complex spectrum with a weak ν1 vibration around 1050 cm-1 together
with split ν2 and ν3 modes. Mode ν2 was observed as two bands around 820 and 840 cm-1, while
for ν3 four bands were observed around 1230, 1380, 1490 and 1690 cm-1 for ν3. The presence of
a weak ν1 indicates a lowering of the symmetry, which was not indicated by Miyata,16
activating this Raman active mode. The four ν3 peaks were interpreted as belonging to two
pairs around 1390 and 1490 cm-1, and around 1230 and 1690 cm-1. The splitting of
approximately 100 and 460 cm-1 together with the much lower intensity of the second pair was
explained by attributing the first pair to predominating monodentate nitrate anions in the
interlayer together with a small amount of bidentate nitrate anions. Hernández-Moreno et al.100
also reported a split of the ν2 mode with peaks at 840 and 825 cm-1 and of the ν3 mode at 1425
and 1385 cm-1 for Li/Al-LDH. The split of the ν2 supports the vision of Miyata16 of the
presence of both mono- and bidentate nitrate in the interlayer region. However, the presence of
only two bands for ν3 contradicts this interpretation. An alternative explanation may be that the
840 cm-1 band is actually associated with the Eu(R)(OH) mode normally observed around 857
cm-1,64 thus leaving a single ν2 mode around 825 cm-1 together with a split ν3 mode around
1425 and 1385 cm-1.
Figure 3 Comparison of the infrared and Raman spectrum of the interlayer nitrate modes in Mg/Al-LDH in the
range between 400 and 1600 cm-1. Indicated are also the bands associated with the presence of some interlayer
carbonate.
This type of splitting of the ν2 and ν3 modes was not observed in other studies.18,64,70,136,143
Kagunya et al.64 reported only two bands around 1000 and 1385 cm-1 as the symmetric and
antisymmetric anion modes, while López et al.70 reported bands around 1382, 830 and 668 cm-1.
A broad band around 1059 cm-1 was solely assigned as being an Al-O type vibration. Like with
carbonate, all nitrate modes show a slight shift towards lower wavenumbers due to the
interaction with the surrounding interlayer water molecules causing a loss of freedom and
therefore possibly a lowering of the symmetry. This is corroborated by the occurrence of a
weak ν1 vibration in the infrared spectra. However, a clear split of the ν3 mode has not been
reported so far by others. This may partly be due to the fact that in many cases the exchange
between nitrate and carbonate is only partial, thereby complicating the infrared spectra due to
overlapping bands.18,143 The same problem has been observed when LDHs were synthesised
from metal nitrates, where small amounts of nitrate can be incorporated in the interlayer next to
the carbonate.65,66,101,118
The Raman spectrum of nitrate in Li/Al-LDHs was reported by Dutta and Puri.110 The
symmetric stretching mode ν1, antisymmetric stretching mode ν3 and antisymmetric
deformation mode ν4 for free nitrate will be observed in the Raman spectrum around 1049,
1355 and 690 cm-1.31 Incorporation of the nitrate anion in the interlayer of LDH resulted in four
bands around 720, 1060, 1356 and 1409 cm-1. The splitting of the ν3 mode into two bands is in
agreement with the observed splitting in the infrared spectrum of nitrate-LDH supporting a
lowering of the symmetry. A band at 3623 cm-1 in the OH-stretching region was interpreted as
being due to the hydroxyl groups in the LDH sheets hydrogen-bonded to the nitrate oxygen
atoms in the interlayer. Dutta and Puri110 concluded from these observations that the orientation
of the nitrate anion in the interlayer must be similar to that of the carbonate anion with each
oxygen atom at a site around the OH-groups with N at the centre along the C3 axis, while other
studies based on X-ray diffraction, ionic size and charge density concluded that the nitrate
anion is probably oriented with its C3 axis parallel to the hydroxide layers (i.e. different from
the orientation of CO32- with its C3 axis perpendicular to the hydroxide layers).141
Table 7 FT-IR vibrational modes of free and interlayer NO3-, SO42- and ClO42-
Free NO3- [16] [100] [64] [70] [110]

IR/cm-1 Raman/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 Raman/cm-1
1049 1050 1000 1059 1060
1
830 820/840 825/840 830
2
1350 1355 1230/1380/ 1385/1425 1385 1382 1356/1409
3 1490/1690
680 690 668 720
4
Free SO42- [100] [127] [110]

IR/cm-1 Raman/cm-1 IR/cm-1 IR/cm-1 Raman/cm-1
981 985 980 986
1
451 500 457/467
2
1104 1104 1110/1160 1140 split 1116
3
613 613 620 650 620
4
Free ClO42- [16] [8]

IR/cm-1
Raman/cm-1 IR/cm-1 IR/cm-1
928 943 Very weak
1
460 476 450
2
1128 1128 1150/1126/ 1100/1150
3 1112/1095
645 645 630
4
SO42-
The free sulphate anion SO42- has a site symmetry of Td corresponding to a space group
Oh7 with the ν3(F) and ν4(F) modes both Raman and infrared active, while the ν1(A1) and ν2(E)
modes are only Raman active36 with ν1 around 981, ν2 around 451, ν3 around 1104 and ν4
around 613 cm-1 (Table 7). In Fig. 4 the infrared and Raman spectra are shown, indicating the
active sulphate modes in Mg/Al-LDH. In naturally occurring hydrotalcite-type minerals, in
addition to the normally present carbonate anion, sulphate forms an important second interlayer
anion. Good examples are honessite, hydrohonessite and carrboydite.105,126,127 Bish and
Livingstone127 observed for honessite the sulphate ν1, ν2, ν3 and ν4 modes at 980, 500, 1140 and
650 cm-1, respectively. The ν3 mode is clearly split, but no separate band positions were given.
The infrared spectrum of synthetic hydrohonessite was very similar to that of the naturally
occurring honessite,126 although splitting of the ν3 mode is only visible as a weak shoulder on
the low wavenumber side of the comparatively broad band, in contrast to the (hydro)honessite
reported by Bish and Livingstone,127 where the weaker of the two bands is observed as a
separate band or shoulder at the higher wavenumber side. The fact that these authors found all
four modes to be infrared active indicates that the symmetry of the sulphate anion has been
lowered from Td for the free anion to C318 or C3v, which would result in activation of the two
infrared inactive modes plus splitting of the ν3 mode.36 Dutta and Puri110 observed bands
associated with the sulphate anion in Li/Al-LDH in the Raman spectrum around 457, 467, 620
(all three weak), 986 and 1116 cm-1 (broad). The splitting of ν2 and the broadening of the
antisymmetric stretching mode ν3 indicate a significant symmetry lowering. Dutta and Puri
suggested D2, which is however not compatible with the infrared data where all four bands have
been observed. For similar reasons, C3 site symmetry, as suggested by Bish,18 is not compatible
with the Raman data.110 Therefore, based on combined observations in both the infrared and
Raman spectra, the conclusion has tos be that the site symmetry is most probably C2v with ν1
(A1) infrared and Raman active, ν2 (A1) infrared and Raman active, ν2 (A2) only Raman active,
and ν3 and ν4 (A1 + B1 + B2) all infrared and Raman active.36
Figure 4 Comparison of the infrared and Raman spectrum of the interlayer sulphate modes in Mg/Al-LDH in
the range between 400 and 1800 cm-1.
For the related layered hydroxide mineral known as carrboydite, (Ni,Cu)14Al9(SO4,CO3)6

(OH)43.7H2O, sulphate bands were observed roughly around 1000, 540, 1120+1180, and 600
cm-1 for ν1, ν2, split ν3 and ν4, respectively, as the band positions had to be determined from the
printed spectrum.105 Miyata and Okada14 are the only ones who reported a triple splitting for
both ν3 and ν4 together with weak ν1 and ν2 modes, which they tried to explain by assuming that
the sulphate anion forms a bridge-type bidentate bond. It is unclear what bond is formed and
also no explanation is given for the triple split. Examination of the spectra shown indicates that
it seems more logical to assume that this split has to be ascribed to the low quality of the
infrared spectrum. Several other papers have reported the infrared spectra of sulphate anions in
LDHs. For Li/Al-LDH, Hernández-Moreno et al.110 reported that ν1 was observed around 985
cm-1 together with a split ν3 around 1110 and 1160 cm-1 and ν4 around 620 cm-1. The ν2 mode
was not reported by these authors as a separate band due to strong overlap with other lattice
vibrations. However, a minor band is shown in the spectrum near 465 cm-1, which was not
identified as the possible sulphate mode ν2. Several other authors only show a broad band
around 1100-1150 cm-1 without visible splitting for the ν3 mode, but still with all other three
vibrational modes infrared active.18,70,74 This broadening was explained by López et al.70 to be
due to the presence of an overlap with the band around 1059 cm-1 assigned to M-O vibrations.
But even after heating to 150°C, where a differentiation is observed between the lattice mode at
1023 cm-1 and the sulphate mode ν3 at 1148 cm-1, no splitting was observed, but still a broad
band. Only after heating to 600°C a shoulder becomes visible around 1162 cm-1 in addition to
the strong major band around 1102 cm-1, proving the presence of initially two similarly strong
overlapping bands. Kooli et al.74 reported that the ν3 band did not show an effective split and
that the two modes around 620 and 450 cm-1 cannot be observed. However, in contrast to their
claims, careful examination of the infrared spectrum reproduced in this publication74 for
Mg/Zn/Al LDH with a Zn/Mg ratio of 0.2 clearly shows an absorption around 1200 cm-1 as a
shoulder to the very broad band around 1100 cm-1, in addition to two very broad bands around
600 and just above 400 cm-1. Even though most of these last two broad bands have to be
attributed to the LDH lattice vibrations, the presence of the ν2 and ν4 sulphate bands can not be
excluded based on the presented spectra.
ClO4-
The free perchlorate anion, ClO4- is in terms of structure and symmetry quite similar to the
sulphate anion, and also has a site symmetry Td, which means that ν1 and ν2 are only Raman
active with bands around 928 and 460 cm-1, while ν3 and ν4 are both infrared and Raman active
with bands around 1128 and 645 cm-1,36 Table 7. However, the ClO4-tetrahedron is very easily
distorted, resulting in the activation of the ν1 in the infrared spectrum, while ν3 and ν4 are often
split.37 This is also clearly visible in the infrared and Raman spectra presented in Fig. 5. Miyata
is about the only one whom has given a detailed description of the infrared spectrum of
perchlorate as an interlayer anion in LDH.16 He reported ν1 and ν2 bands around 943 and 476
cm-1, while ν3 was split into four bands at 1150, 1126, 1112 and 1095 cm-1. He was not sure
about the split for ν4 into two or three bands around 640 and 629-633 cm-1. Based on the
observed band positions and splitting in comparison to those of [Cu(biph)SO4] (biph=biphenyl)
he concluded that the perchlorate has to be present as a bridging type bidentate. It has been
shown for several of these types of compounds that the strength of the ν1, the band positions
and the size of the splitting are not necessarily a proof for the presence of mono- or bidentate
ligands as chelate or bridging types. Based on the quality of the spectrum presented, the
splitting is questionable, especially that of the ν4 mode, but one can conclude that the site
symmetry of the perchlorate has been lowered upon intercalation in the interlayer of LDHs due
to distortion of the free perchlorate tetrahedron. This will consequently lead to activation of the
ν1 and ν2 modes and the splitting of the other two modes. Brindley and Kikkawa8 have reported
the exchange of carbonate by perchlorate in LDH by treatment with perchloric acid. At high
crystallinity they observed a larger basal spacing, indicating the presence of water molecules
associated with the perchlorate ions in the interlayer. Drying resulted in a decrease in basal
spacing. Although they did not give a detailed description of the corresponding infrared spectra,
some general observations can be made. In the highest crystalline material a strong band due to
carbonate can be seen around 1355 cm-1, together with a band around 1100 cm-1 due to the
perchlorate ν3 mode, which clearly shows a shoulder around 1150 cm-1 indicating that this
mode is split. The ν1 mode is very weak and hardly visible, while the ν4 gives a clear peak
around 630 cm-1 together with a very strong peak at 450 cm-1, which can be ascribed to the ν2
mode.
INTERLAYER METAL COMPLEXES
CrO42-
As discussed in the previous sections for the sulphate and the perchlorate anions, also free
chromate anions, CrO42-, have a tetrahedral structure with site symmetry Td. This leads to ν1
and ν2 as Raman active modes around 847 and 348 cm-1 plus ν3 and ν4 as infrared and Raman
active modes around 884 and 368 cm-1.36 Miyata and Okada14 have shortly described the
infrared spectrum of chromate as the interlayer anion in LDH. Between 1300 and 400 cm-1 they
observed mainly very broad bands with a strong peak at 885 cm-1 accompanied by a clear
shoulder around 950 and two very minor bands at 865 and 845 cm-1. Due to the restriction of
the spectral region to 1300-400 cm-1, the ν2 and ν4 modes were not observed. The weak band at
865 cm-1 was interpreted as being the ν1 mode, while the other three were attributed to the
splitting of the ν3 mode. This interpretation is highly questionable and it makes more sense to
assign the ν1 mode to the weak band at 845 cm-1, while the strong band can be interpreted as
being the main ν3 mode. No explanation was given by Miyata16 for the strong difference both in
intensity and bandwidth for the splitted ν3 mode. Châtelet et al.69 experimented with the anion
exchange of carbonate by chromate. The diffuse reflectance Fourier-transformed infrared
(DRIFT) spectra shown are not very informative and basically show bands that can be assigned
to carbonate. However, a small band becomes visible around 860 cm-1 after anion exchange,
which might be interpreted as a chromate band. Insufficient detail in the spectrum prevents one
from assigning this band to either ν3 or ν1.
Figure 5 Comparison of the infrared and Raman spectrum of the interlayer perchlorate modes in Mg/Al-LDH in
the range between 400 and 1300 cm-1.
Fe(II)- and Fe(III)- cyano-complexes
A number of cationic cyano-complexes including various metals including metals such Co,
Mo and Ru, have been used to intercalate LDHs.144-146 However, for spectroscopic studies,
including infrared, Raman and Mössbauer spectroscopy, the hexacyanoferrate complexes

[Fe(CN)6]4- and [Fe(CN)6]3- have been widely used.144 The hexacyanoferrate anion forms a
regular octahedron with cyanide ligands in the corners leading to site symmetry Oh. Selection
rules imply that A1g, Eg and F2g modes will be Raman active only, while 2F1u is infrared active
only and F2u is inactive.36 Based on XRD and infrared measurements, Kikkawa and Koizumi147
and Braterman et al.148 have suggested that the C3 axis of the octahedron (i.e., the rotational
axis trough the triangular faces of the octahedron) is oriented perpendicular to the hydroxide
sheets of the LDH. Braterman et al.148 argued that theoretically the C-N vibrations would
correspond to A1g, Eg and T1u, from which the first two are Raman active and the last one is
infrared active. However, the first two modes are also observed in the infrared spectrum as very
weak bands, while the T1u bands splits in two bands assigned to Eu and A2u, indicative of a
decrease in symmetry from Oh to D3d.
Qualitative studies have shown that the iron-hexacyano-complexes can change their
oxidation state upon intercalation in LDHs.149-151 A change in the oxidation state of the iron in
cyanoferrate complexes is reflected in the C≡N stretching frequency, which shifts roughly from
2050-2070 cm-1 for Fe(II) to 2115-2125 cm-1 for Fe(III),152,153 Fig. 6. This shift can be
explained by the decreasing π-bonding between the iron and the CN-groups for
hexacyanoferrate(III) compared to hexacyanoferrate(II).154 Idemura et al.149 prepared a 84%
Fe(CN)63- intercalated LDHs by anion exchange of a nitrate-LDH with potassium and sodium
salt solutions under careful exclusion of carbonate. The infrared spectrum showed two bands
around 2120 and 2040 cm-1 indicating that a part of the Fe(III) was reduced to Fe(II) during
intercalation. Intercalation with pure Fe(CN)64- resulted in only a single band around 2040 cm-1
if the sample was dried in vacuum, but the other band appeared when dried in air. Similar
observations of partial oxidation and reduction of Fe(II) and Fe(III) in intercalated cyanoferrate
complexes have been reported by various scientists, although small shifts have been reported
depending on the starting source of the cyano-complex. 120,155-159
Figure 6 Effect of the pillaring process on the IR spectrum of a (NO3)-Mg/Al-LDH (Mg/Al ratio 2.46) before
(A) and after (B) being pillared with Fe(CN)63- (Reprinted from Microporous and Mesoporous Materials, 30,
Nijs et al., Evaluation of the microporosity of pillared [Fe(CN)6]-MgAl-LDHs, 243-253, 1999, with
permission from Elsevier Science).
Yao et al.159 showed that the intensity of the band at 2030 cm-1 increased upon aging of the
intercalated LDH, indicating an increased oxidation of the Fe(II) with time. Incorrectly they
ascribed this band as being due to a CN- group in which the bond strength was weaker due to
the interaction with the surface of the Mg/Al-LDH. Holgado et al.157 presented additional proof
for the partial reduction-oxidation of the iron in the interlayer cyano-complex by Fe-K XANES
measurements, while Idemura et al.149 observed the reduction of Fe(III) to Fe(II) in Fe(CN)63-
intercalated LDH by Mössbauer spectroscopy. In addition to the shift observed due to oxidation
or reduction of the iron, Crespo et al.158 pointed out that the precise position of the C≡N
stretching frequency in hexacyanoferrate(II) is probably also influenced by the hydrogen
bonding between the interlayer water molecules or the hydroxyl groups of the LDH sheets and
the cyano groups.
Hansen and Koch156 found that partial oxidation occurred when the cyanoferrate
exchanged LDH was dried in an oven at 70-100°C or when it was washed in
oxygen-containing non-aqueous solvents. However, no oxidation was observed when
oxygen-free solvents were used or when the sample was dried at room temperature. Based on
these observations, they concluded that the oxidation takes place because of the oxygen
dissolved in the solvent and when the solid is dried above room temperature the fast removal of
water from the interlayer favours migration of oxygen into the interlayer, causing the oxidation
of the Fe(II) to Fe(III). Oxidation of Fe(II) to Fe(III) in the hexacyano-complex requires some
adjustments in the interlayer in order to maintain the charge balance with the positively charged
hydroxide sheets of the LDH. One possibility is an exchange of a cyanide ligand by water or
hydroxyls according to the reaction:
[Fe(CN)6]4- + H2O → [Fe(CN)5H2O]3- + CN-
These cyanide ions are not expelled from the interlayer when water is the replacing ligand.
Hansen and Koch156 reported a very weak and broad adsorption band around 2039 cm-1 and a
sharp band at 2027 cm-1, which is quite far from the normally observed band for free cyanide
around 2080 cm-1. This may indicate that the cyanide is bound to the cations in the LDH
hydroxide sheets. The above-mentioned aquo-substituted complex oxidises easier than the
initial hexacyanoferrate(II).160
Fernández et al.120 observed, in addition to the two strong bands around 2118 and 2042
cm , two weak shoulders at 2089 and 2060 cm-1. The presence of the band at 2042 cm-1 proofs
-1
partial reduction of Fe(III) to Fe(II). Several studies have shown that reduction can take place
under high pressure, for example during grinding. 150,161,162 In most studies the infrared spectra
were recorded by applying KBr discs prepared under high pressure, which might be an
explanation for the partial reduction. However, infrared spectra recorded by diffuse reflectance
FT-IR (DRIFT), in which no pressure is applied, showed the same effect of partial reduction of
the Fe(III) to Fe(II).157 Fernández et al.120 pointed out that when reduction is assumed to take
place and taking into account that the hexacyanoferrate ions are known to be outer-sphere
electron-transfer reductants or oxidants,163,164 it is easy to explain the origin of the two weak
shoulders around 2089 and 2060 cm-1 due to a lowering of the site symmetry. Free Fe(CN)64-
has a site symmetry Oh with A1g, Eg and T1u modes, the first two are normally inactive in the
infrared, but will become active due to symmetry lowering. Fernández et al.120 concluded that
all this means that the partial reduction took place because of the stress generated in the
hexacyanoferrate(III) anion between the hydroxide sheets of the LDH. Reduction can also be
induced by heating Fe(III)-hexacyano intercalated LDH. Nijs et al.165 showed that upon heating
at 325°C in air the sharp infrared band at 2115 cm-1 from the CN vibration in Fe(CN)63- was
broadened and shifted to 2050 cm-1, indicating the reduction of Fe(III) to Fe(II), further heating
resulting in a decrease in intensity of the 2050 cm-1 band, which disappeared almost completely
around 500°C. This also shows that at 325°C the CN-ligands were not expelled from the
complex, while heating to 500°C resulted in the almost complete removal of the CN-ligands.
Extra information about the symmetry of the hexacyanoferrate anion and its reduction
when intercalated in LDHs can be gained from comparison of the Raman spectra with the
infrared spectra. Dutta and Puri110 reported the Raman spectrum of hexacyanoferrate(II)
intercalated Li/Al-LDH. As already indicated above, free Fe(CN)64- will give three vibrational
modes with A1g at 2098 cm-1 and Eg at 2062 cm-1 in the Raman spectrum, and T1u at 2044 cm-1
in the infrared spectrum. For the intercalated LDH, bands were observed in the Raman
spectrum at 2094, 2074, 2063, 2042 and 2027 cm-1, clearly supporting the fact that a reduction
in the site symmetry has taken place. However, no indication is given about the possibility of
partial oxidation of Fe(II) to Fe(III), commonly observed by other authors in the infrared
spectra, giving rise to extra bands in the Raman spectrum thereby complicating the
interpretation. Lowering of the site symmetry to C3 would predict four bands in the Raman for
both the Fe(II) and Fe(III) hexacyano anions, resulting in theoretically eight modes. In practice,
one can expect that several of these modes will overlap resulting in the observation of only five
bands. However, Braterman et al.148 argued that the activation of A1g and Eg modes and splitting
of the T1u bands in two bands assigned to Eu and A2u indicates a decrease in symmetry from Oh
to only D3d (from which C3 forms a subgroup).
In contrast to the relatively difficult ligand exchange of one of the cyanide groups by water,
exchange with nitrate is relatively easy. Pure sodium nitrosylpentacyanoferrate(III) shows an
IR N≡O stretching mode at 1940 cm-1 together with four bands in the C≡N stretching region
around 2040-2143 cm-1.166 When nitrosylpentacyanoferrate is intercalated in LDHs, the
intensity ratio of the N≡O stretching mode to the C≡N stretching modes is much smaller than
expected. This indicates that during the intercalation the N≡O ligand was eliminated from the
complex.149 The presence of two other bands at 2040 and 2050 cm-1 indicated the formation of
a reduced complex containing Fe(II) instead of the Fe(III) in the initial complex. The presence
of Fe(II) was also confirmed by the observation of the M-C≡N bending mode around 580 cm-1.
As suggested abov,e a mechanism was proposed in which the stress of the hydroxide sheets on
the complex not only induces the reduction of the iron, but also eliminates a neutral N≡O ligand
while taking up a water molecule as a replacement.
Vanadates and molybdates

The intercalation of various vanadate anions in LDHs has received quite a lot of interest
because of its potential in catalytic applications. Various vanadates exist depending on the
polymerisation degree, which is strongly pH-dependent. At low pH between roughly 1 and 3
decavanadates (such as V10O26(OH)24-, V10O27(OH)5- and V10O286-) are formed, while between
pH 4 and 6 metavanadates (such as VO(OH)3, VO2(OH), V3O93-, V4O124-) are the predominant
species. At high pH, between 8 and 11, pyrovanadate anions like VO3(OH)2-, HV2O73- and
V2O74- are observed, transforming to pure vanadate VO43- at even higher pH.144 Therefore, the
intercalation process will also be pH dependent. Griffith and coworkers have reported the
Raman spectra of oxovanadates in solutions as function of pH.167,168 The most prominent bands
assigned to the stretching motion of the V-O bond were observed in the region between 800 and
1000 cm-1. It was shown that, as a general trend, one can observe a shift towards higher
frequencies when the number of terminal oxygen atoms decreases. Increasing polymerisation
of the vanadium atom along with branching to form oxovanadate complexes will lead to an
increase in the V-O stretching frequencies in the Raman spectrum.
A thorough characterisation of the Raman spectra of Li/Al-LDHs intercalated with various
vanadate species depending on the intercalation pH was reported by Twu and Dutta.169 The
Raman spectrum of the LDH exchanged at pH=10 was characterised by bands around 350, 483,
837 and 878 cm-1, which can best be assigned to V2O74- ions (351, 503, 810, 850 and 877 cm-1
for V2O74- in solution). The presence of other species such as VO43-, HV2O73- and (VO3)nx- was
excluded based on the absence of bands around 340, 820, 915 and 945 cm-1. Based on the
equilibrium existing in the solution at pH 10, one would expect V2O74-, HV2O73- and HVO42- to
be present in a molar ratio of 6:3:1, which supports the conclusion that V2O74- must form the
predominant intercalated species with the two sharing VO3 tetrahedra oriented parallel to the
hydroxide sheets. Lowering the exchange pH to 5 results in some changes in the Raman
spectrum indicating the incorporation of another vanadium species. In this case, Raman bands
were observed around 358, 520, 606, 877 and 944 cm-1, together with two weak bands around
330 and 977 cm-1. These last two bands were shown to disappear upon washing, which was
interpreted as being due to the fact that the species was adsorbed on the outer surface of the
LDH. The Raman spectral bands belonging to the V2O74- ion are weaker than in the previous
sample. The more prominent bands around 360, 520 and 944 cm-1 can be assigned to V4O124-,
which has comparable bands in solution at 360 and 945 cm-1. The Raman bands of the adsorbed
species are characteristic for V10O286- species. Therefore, the major species in this case is
V4O126- plus a minor amount of V10O286- on the outside surface. At the lowest pH, Raman bands
were observed around 326, 353, 521, 605, 835, 946 and 982 cm-1. In contrast to the previous
sample, the bands at 326 and 982 cm-1 did not appear upon washing. This means that V4O126-
still forms the major interlayer anion, but a minor amount of V10O286- is now present in a state
that makes removing by washing impossible.
The infrared spectra have been discussed in various papers170-178 (Fig. 7), but in less detail
than the Raman spectra discussed by Twu and Dutta.169 Table 8 gives a summary of the bands
observed in LDHs with various metal substitutions. Ulibarri et al.170 prepared
decavanadate-intercalated Mg/Al-LDH by exchange terephthalate intercalated LDH with a
solution containing NaVO3 at a pH of 4.5. The infrared spectrum showed a strong band at 977
cm-1 together with bands around 830, 751, 682 and 600 cm-1. These values are comparable to
the values reported by López-Salinas and Ono179 for V10O286- intercalated Mg/Al-LDH. In the
case of Ni/Al-LDH the bands show a minor shift to 964, 810, 748, 598 and 520 cm-1.171
Additional information from V-K XANES for the presence of the decavanadate was reported
by Del Arco et al.175 The XANES at the V-K edge for the LDH sample was almost identical to
that of crystalline decavanadate [(n-C6H13NH3)(V10O28).2H2O], indicating that vanadium is
indeed present as V5+ forming decavanadate clusters. They also reported a single band at 320
cm-1 in the Raman spectrum coinciding with a similar band for decavanadate in aqueous
solution prepared by dissolving NaVO3 at pH 4.5. Barriga et al.177 observed a broadening of the
infrared bands when the samples were prepared at a higher pH (around 7 instead of 4). They
indicated that a possible explanation might be the presence of two different coexisting
polyoxovanadate species. The X-ray diffraction suggested the presence of a biphasic material
with different (003) spacings of 9.6 and 7.2 Å.
Bahranowski et al.178 described, in addition to the infrared spectrum of the decavanadate
intercalated LDH, also the infrared spectrum of pyrovanadate, V2O74-, intercalated LDH. The
band at 910 cm-1 is comparable to the antisymmetric ν(VO2) vibration typical for both HV2O73-
and (VO3)nx- anions, while the band at 630 cm-1 may be due to the antisymmetric ν(VOV) mode
in (VO3)nx- chains.167 Based on the infrared data only it is impossible to distinguish which of the
two anions has been intercalated in the LDH. However, the broad maxima in the X-ray
diffraction pattern was interpreted as being caused by the presence of both pyro- and
metavanadate intercalation, which was also supported by the chemical analyses.
While quite a large number of papers have been published on the intercalation of vanadates
in LDHs and their infrared and Raman spectra, so far only one paper has been devoted to the
Raman spectroscopy of molybdate intercalation in LDHs. The chemistry of molybdate
complexes in solution is simpler, resulting in a reduced number of possible species compared to
the previously discussed vanadates.180 In basic solutions with a pH higher than 7, MoO42- forms
the primary species at concentrations of 0.1 M. This species condenses to heptamolybdate
Mo7O246- in the pH range between 4 and 6. Molybdenum plays an important role in
heterogeneous catalysis and molybdates have for example been used to prepared pillared
clays.111 Twu and Dutta181 reported experiments to intercalate both species in Li/Al- and
Mg/Al-LDHs. Intercalation of Li/Al-LDH with the MoO42- species failed due to hydrolysis of
the molybdate anion and incomplete replacement of the Cl- anion. The Raman spectra of the
wet sample and the sample dried in a N2 atmosphere were almost identical to that of MoO42- in
solution prepared by dissolving Na2MoO4 in water. While the free anion gives bands at 328,
850 and 898 cm-1 assigned, respectively, to the bending, antisymmetric and symmetric
stretching modes of the MoO4 unit, the wet and N2 dried samples gave bands around 320, 600,
850 and 898 cm-1. The 600 cm-1 band is a Li/Al-LDH lattice vibration. Drying in air resulted in
new bands around 918, 1047 and 1068 cm-1. The latter two bands are characteristic for
carbonate in the interlayer region of the LDH, while the band at 918 cm-1 can be assigned to
HMoO4-. In the presence of CO2 from the atmosphere the following reactions seem to take
place:
MoO42- + H2O → HMoO4- + OH-

OH- + CO2 → HCO3-
HCO3- → H+ + CO32-
Figure 7 Evolution of the infrared spectra during the exposure to air of the freshly obtained LDH. The infrared
spectrum of LDH(VO3) is also given for comparison. (Reprinted from Solid State Ionics, 98, Han et al.,
Intercalation process of metavanadate chains into a nickel-cobalt layered double hydroxide, 85-92, 1997, with
permission from Elsevier Science).
Table 8 Infrared and Raman vibrational modes of polyoxovanadate anions intercalated in various LDHs.
Li/Al [170] Mg/Al [179] Ni/Co [177] Mg/Al [171] Mg/Al [174] Ni/Al [172] Ni/Cr [173] Zn/Cr [175] Co/Cr [176] Co/Cr [176] Zn/Al [178]
Raman/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 IR/cm-1 Raman/cm-1 IR/cm-1
V2O74- V2O74-/ (VO3)nx- V10O286- V10O286- V10O286- V10O286- V10O286- V10O286- V10O286- V10O286-
(VO3)nx-
280
351 338 322 320
389
503 538 520 524 ? 510 505
600 598 598 590 ? shoulder 598
670 678 682 674
776 751 shoulder 748 740 743 741 745
810 826 830 816 810 805 812 812 815
850
877 874
910 949 977 960 964 960 961 964 960
The overall reaction in the interlayer of the Li/Al-LDH destroys the hydroxide layers due
to an imbalance between the collective size (>50 Å2) of the HCO3- and HMoO4- anions
neutralising the charge (approximately 25 Å2 per unit charge), causing destabilisation of the
hydroxide sheets.
Intercalation of a Mg/Al-LDH with Mo7O246- was performed via an intermediate
containing terephthalate as the interlayer anion. X-ray diffraction showed a basal spacing of
12.2 Å, indicating that the molybdate complex is aligned with its C2 axis parallel to the
hydroxide layers. The Raman spectra of both the wet and dried intercalated LDH compare well
with the spectrum of free Mo7O246- in solution The bands at 898 and 950 cm-1 were assigned to
the antisymmetric Mo-O-Mo and symmetric stretching modes of Mo-O (terminal) bonds. The
band at 360 cm-1 was attributed to a Mo=O bending mode. Upon heating at 400°C only a
broadening was observed, while the 950 cm-1 band shifted to 912 cm-1, which was explained by
a change in the local environment rather than a chemical change. This indicates that no
depolymerisation takes place upon heating in contrast to the vanadates, which show the
formation of oligomeric species at temperatures even below 200°C.
Phosphates and Phosphonates
The interaction of phosphates with LDHs has attracted some interest because of its role in
phosphate mobility in anaerobic soils and sediments in relation to environmental problems
related with the release of heavy metals and the use of fertilisers. Adsorption of HPO42- on
nitrate-LDH resulted in a characteristic infrared band at 1057-1064 cm-1, while at high P
concentrations two shoulders at 1120 and 990 cm-1 were observed in addition to the initial
band.182 Comparison with the infrared spectrum of free phosphate, with bands at 1067-1077
and 988 cm-1,183-185 indicated that the phosphate in the interlayer of the LDH behaves almost
similar and is only electrostatically bonded. Alternatively, the phosphate can be bound to one
metal atom in the hydroxide layer in the form of (MO)PO2(OH). In this case, the PO2
antisymmetric and symmetric stretching modes have been ascribed to the absorption bands at
1120 and 1067-1064 cm-1. The observation of a shoulder at 1120 cm-1 for the phosphate
intercalated LDH indicates that some of the phosphate is possibly present in this form.
Several studies have reported the infrared spectra of HPO42- and H2PO4- intercalated
Zn/Al-LDHs (Fig. 8).186.188 The two papers by Badreddine and coworkers186,187 report very
similar experiments with only minor differences in exchange pH (8 versus 9) and
orthophosphate concentration (0.01 M versus 0.025 M). Although the infrared spectra look
similar, some interesting shifts in the band positions can be observed, which were not discussed
by the authors. At pH 8 and an orthophosphate concentration of 0.01 M, orthophosphate bands
were observed at 1220, 1050, 870 and 550 cm-1 assigned, respectively, δ(P-OH), ν3(P-O),
ν1(P-O) and ν4(P-O).140,183 Increasing the pH to 9.2 and the orthophosphate concentration to
0.025 M shifted these bands to 1240 (∆ +20 cm-1), 1044 (∆ -6 cm-1), 766 (∆ -104 cm-1) and 557
cm-1 (∆ +7 cm-1). The interpretation of these bands and the observed shifts are quite confusing,
as for free PO43- bands are normally observed 938 (ν1), 420 (ν2), 1017 (ν3) and 567 cm-1 (ν4)
while HPO42- display bands around 858 (ν1), 989 (ν2), 535 (ν3), 1080 (ν4) and 535 (ν5).36 These
authors also have not taken into account the presence of certain LDH lattice modes in the same
region as where the phosphate bands are observed. Even more confusing are more recently
published results by the same group,189 where they report the spectra of PO43-, HPO42- and
H2PO4- to be identical after intercalation. However, these molecules have different symmetries
and point groups, and therefore follow different selection rules, resulting in differences in the
infrared vibrational modes that can be observed (Fig. 8b).
Although Costantino et al.188 do not describe the infrared spectra of HPO42- and H2PO4-
intercalated Zn/Al-LDH, their interpretation seems more logical than those presented
above.186,187,189 Intercalation of H2PO4- gave a constant interlayer distance independent upon
drying over P4O10 or heating at 150-200°C. The infrared spectrum also did not change and
showed characteristic band around 1000 cm-1. This indicated the presence of deprotonated
phosphate (free PO43-, ν3 1017 cm-1) in the interlayer, formed by a reaction of the acidic H2PO4-
with the hydroxyls of the LDH hydroxide sheets forming a layered Zn/Al-hydroxyphosphate.
In contrast, HPO42- intercalation was quite different. Dehydration via drying over P4O10 or via
heating, resulted in a decrease of the interlayer distance from 10.8 to 8.2 Å. The infrared
spectrum also changed upon dehydration. The initial 1100 cm-1 band with a shoulder near 1000
cm-1 changes to a single band around 1000 cm-1, indicating partial deprotonation during the
intercalation, with further deprotonation during the dehydration. The difference between
HPO42- and H2PO4- can probably be explained by the lower acidity of HPO42- compared to
H2PO4-.
Figure 8a Comparison of the IR spectra of the exchanged phase (Zn/Al-LDH-HPO4), Zn/Al-LDH-Cl precursor
and Na2HPO4.12H2O. (Reprinted from Materials Research Bulletin, 33, Khaldi et al., Preparation of a
well-ordered layered nanocomposite from zinc-aluminum-chloride layered double hydroxide and
hydrogenphosphate by ion exchange, 1835-1843, 1999, with permission from Elsevier Science).
Figure 8b FT-IR spectra for the precursor [Zn/Al-Cl-LDH] (a) and the material obtained from the exchange of
Cl- by PO3- (b), PO43- (c), HPO42- (d), H2PO4- (e), P2O74- (f) and P3O105- (g). (Reprinted from Materials
Letters, 38, Badreddine et al., Ion exchange of different phosphate ions into the zin-aluminium-chloride layered
double hydroxide, 391-395, 1999, with permission from Elsevier Science).
Badreddine et al.189 reported other phosphate intercalates including PO3-, P2O7- and
P3O10-Zn/Al-LDH and shortly reported some characteristic bands. The PO3-LDH was
characterised by four bands at 480, 560, 1100 and 1260 cm-1, which they ascribed to the
deformation and bending vibration (while deformation and bending are two terms for the same
vibration) and ionic valence vibrations ν(P-O) and ν(P=O), characteristic for metaphosphates.
The infrared spectrum of P2O7-LDH was characterised by bands at 560, 780, 920, 1100 and
1145 cm-1. These bands were assigned as the angular deformation vibration of external PO3
groups δ(O-P-O), the symmetric valence vibration of P-O-P bridges, the antisymmetric valence
vibration, while the band at 1100 and the doublet at 1145 cm-1 were ascribed to symmetric
valence vibration ν(P-O) and antisymmetric valence vibration ν(O-P-O), respectively. Finally,
the P3O10-LDH showed infrared bands around 580, 780, 900, 980, 1120 and 1215 cm-1. These
bands were assigned to the angular deformation vibration of external PO3 groups δ(O-P-O),
harmonic of deformation vibration P-O-P, antisymmetric valence vibration ν(P-O-P), valence
vibration ν(P-O), antisymmetric valence vibration of PO3 groups and the antisymmetric
valence vibration ν(O-P-O), respectively.
Silicates
Incorporation of silicates in LDHs has received some special interest because of its relation
to natural processes. It has been suggested by several scientists that the interaction of LDHs
with silicates may result in a transformation to phyllosilicates (clays).190-193 Schutz and
Biloen191 described the reaction of Mg/Al- and Li/Al-LDHs with a solution of amorphous
silicic acid in NaOH under reflux conditions (100°C/18 h). This reaction resulted in an increase
in basal spacing from 7.97 to 11.9 Å. 27Al and 29Si MAS-NMR revealed that no bonds were
formed between the hydroxide sheets of the LDH and the interlayer silicate anion. Instead, only
a single peak was observed in the 29Si spectrum at -104 ppm, indicating a Q3(0Al) coordination
with a Si-O-Si bond angle higher than 140°, comparable to the signal observed for talc (-98
ppm)or synthetic sodium silicate (-102 ppm). In addition, electron diffraction showed a
superstructure characteristic of a two-dimensional hexagonal unit cell with a = b = 5.2 Å, being
the repeating distance between six-membered Si-O-Si rings. The infrared spectrum shows a
strong Si-O stretching band at 1000 cm-1 with a shoulder around 1080 cm-1 and a peak at 1220
cm-1. A similar peak has been observed for sepiolite, where a band at 1200 cm-1 corresponds to
a 180° Si-O-Si bond angle.
Yun et al.194 applied a different method to intercalate LDH with silica. They firstly reacted
the LDH with tetraethylorthosilicate (TEOS), followed by what they called “intragallery
hydrolysis” of the TEOS. Silica-intercalated LDHs were achieved at room temperature for
Mg3Al- and Mg4Al-LDH, while for Mg2Al the temperature had to be increased to 100°C under
reflux conditions. This might have to do with the stronger H-bonding inhibiting the penetration
of the TEOS molecules into the interlayer regions. The resulting LDHs exhibited gallery
heights around 7.0-7.2 Å. Strong overlapping silicate stretching vibrations were observed in the
infrared region between 950 and 1200 cm-1, similar to the bands reported by Schutz and
Biloen191 although the bands are broader in this study. However, no specific band positions and
their assignments were reported by Yun et al.194
Hansen182 described the exchange of NO3- and CO3-LDH with Na2SiO3.9H2O solution at
pH=9. At this pH only a part of the silicic acid is present as trihydrogen silicate ions. He
observed that the amount adsorbed both in the interlayer and on the outside was only half of the
theoretical amount. The heated LDH interlayer distance of 3.7-4.4 Å is slightly different from
that observed by Schutz and Biloen.191 It indicates that the silica tetrahedra are oriented with the
S4 axis (but not the C3 axis) perpendicular to the hydroxide sheets and with fairly large
tetrahedral angles of 120-150°. In the stretching region, four SiO4 bands were found around 915,
1030, 1110 and 1196-1240 cm-1. The last three bands agree quit well with the bands observed
by Schutz and Biloen191 around 1000, 1080 and 1220 cm-1. With increasing amounts of silica
adsorbed, the 1030 cm-1 became stronger, while the 1110 cm-1 turned into a shoulder. The
intensity of the 1200 cm-1 band increased and shifted towards higher frequencies. Hansen182
pointed out that the relatively high frequencies indicate that polymerisation takes place in the
interlayer. The presence of a band at the high frequency around 1220-1240 cm-1, assigned to the
antisymmetric stretching mode of the Si-O-Si bond, has been explained by a Si-O-Si angle
close to 180°.191,195 The interlayer distance of less than 4.4 Å prohibits the formation of linear
Si-O-Si bonds by polymerisation of free [SiO4] tetrahedra. Therefore, it is more logical to

assume that the silica polymers form bonds with the LDH hydroxide sheets. An alternative
explanation given for the 1220-1240 cm-1 band might be the assignment to the OH bending
vibration of OH coordinated to Si, as observed for acid silicates. This explanation does not
involve the formation of bonds with the LDH hydroxide sheets. For the CO3-LDH, exchange
with silicate is only limited to the external surfaces, resulting in only a broad maximum in the
infrared spectrum around 990-1020 cm-1.
Polyoxometalates
Several polyoxometalates with the Keggin structure (12 metal-containing octahedra

surrounding a tetrahedrally-coordinated cation in the centre) have been used to expand the
LDH layers. Kwon and Pinnavaia196 successfully intercalated Zn/Al-LDH with
α-[SiV3W9O40]7- resulting in a basal spacing of 14.5 Å. Based on a comparison with
α-[SiV3W9O40]7-, it was concluded that the complex had to be oriented with its C2-axis
perpendicular to the hydroxide layers of the LDH. In this orientation the number of hydrogen
bonds between the Keggin complex and the hydroxyl groups of the LDH layers is maximised.
The infrared spectrum of the intercalated compound with ν(M-O) at 959 cm-1, ν(Si-O) at 913
cm-1 and ν(M-O-M) at 780 cm-1 is very similar to the potassium-hydronium salt containing the
[SiV3W9O40]7-, unit with comparable bands at 965, 915 and 780 cm-1.
Wang et al.197 reported the successful intercalation of Mg/Al-LDH with various
Keggin-type polyoxometalates ranging from [PW12O40]3- to [PV4W8O40]7-. This is in strong
contrast with the findings of Kwon and Pinnavaia,196 who were unable to intercalate their
Mg/Al- and Zn/Al-LDHs with [PW12O40]3-. The infrared spectrum shows the complete
disappearance of the initially present interlayer nitrate. Furthermore, there are minor changes in
the infrared bands compared to the polyoxometalate salt. The double band around 1390 cm-1
together with some bands around 500 cm-1 completely disappeared after intercalation, while the
band around 1610 cm-1 with a clear shoulder at lower wavenumbers was replaced by a single
band around 1610 cm-1, indicating a certain interaction of the polyoxometalate with the LDH,
lowering its freedom and symmetry.
Hu et al.198 showed the infrared spectrum of SiW11O398- and SiW11O39Z(H2O)6- (Z = Co2+,
Ni or Cu2+) intercalated Zn/Al-LDH and the effect of heating on the infrared spectrum (Fig. 9).
2+
Intercalation of the polyoxometalates resulted in a minor shift of the ν(Si-O) from around 1000
cm-1 to around 997 cm-1. A similar small shift was observed for the ν(W=Od) around 952 cm-1.
A shift to both higher and lower frequencies depending on Z was observed for the ν(W-Ob-W)
mode around 870-910 cm-1 and the ν(W-Oc-W) modes around 785-795 cm-1 and 715-744 cm-1.
No obvious other changes were observed for these four characteristic groups after intercalation.
Pinnavaia et al.199 reported on the successful use of swelling organic molecules such as
glycerol in order to prepare pillared LDHs with H2W12O406- directly from the carbonate
containing LDH as a precursor. A similar method was followed by Weir and Kydd200 by using
adipic acid as the swelling organic molecule. The final product contained only the H2W12O406-
anionic complex as there were no residual bands that could be attributed to CO32- or adipate
anions. In the highest charged LDHs the chemical analysis indicated the presence of more
Keggin ions than those necessary to balance the positive layer charge, which can be caused by
partial protonation of the Keggin ions in the interlayer, thus decreasing their formal negative
charge. The compensation of the excess charge may be achieved by the incorporation of Na+ or
NH4+, as ammonia and sodium hydroxide are used during the synthesis. However, the infrared
spectrum does not reveal any ammonium bands. Characteristic bands of the Keggin complex
are observed in the low frequency region, where they partly overlap with the bands associated
with the hydroxide layers of the LDH. Unfortunately, no detailed description or band
assignment has been given by Weir and Kydd.200 Based on their published figure of the infrared
spectra of the intercalated LDHs, three or four characteristic bands can be observed in the
region between ca. 500 and 1000 cm-1, probably associated with various W-O vibrational
modes (Fig. 10).
Figure 9 IR spectra of the Zn/Al-LDH samples pillared with SiW11CoO396- calcined at 763 K (a), 613 K (b),
478 K (c), 418 K (d) and 298 K (e). (Reprinted from Catalysis Today, 30, Hu et al., Synthesis, stability and
oxidative activity of polyoxometalates pillared anionic clays ZnAl-SiW11 and ZnAl-SiW11Z, 141-146, 1996,
with permission from Elsevier Science).
SOME SELECTED INTERLAYER AND ADSORBED

ORGANIC COMPLEXES
The interlayer anions and water molecules in LDHs can be exchanged for a range of
organic anions and polar molecules of various sizes.19,201-204 Intercalation can be achieved by
swelling in water followed by anion exchange (in the case the interlayer anion is not CO32-), by
calcination and reconstitution of the structure using the “memory effect” (when the anion is
CO32-) or by preparation of an enlarged interlayer space by exchange with organic acids,
glycerol or comparable molecules. So, Hansen and Taylor205 used glycerol intercalates in the
exchange of CO32- with other anions. Although the other anion was present in the LDH in their
first experiments, it was possible to distinguish some bands belonging to the glycerol around
2875 and 2935 cm-1 ascribed to the C-H stretching modes and possibly the band around 1060
cm-1. Exchange of pyroaurite with pure glycerol gave more recognisable bands around 930, 995,
1050, 1085, 1115, 1405, 2885 and 2940 cm-1. No shift was observed in the OH-stretching band
of the hydroxide layers around 3420 cm-1. Furthermore, since interlayer CO32- was completely
removed, the two sharp, medium intensity bands around 1325 and 1385 cm-1 must also be
associated with the glycerol. Hansen and Taylor indicated that these could be ascribed to CH2
and/or OH-bending vibrations of glycerol or one of its alteration products in the LDH interlayer.
They also observed an increase in the intensity of the 1610-1630 cm-1 band due to the
OH-bending mode of water, indicating that the glycerol intercalated LDH is more hydrophobic
than the untreated LDH.
Figure 10 FT-IR spectra of (a) authentic (NH4)6H2W12 salt, (b) Mg2Al[H2W12]-LDH, (c)
Mg3Al[H2W12]-LDH, (d) Mg4Al[H2W12]-LDH and (e) Mg3Al[CO3]-LDH. Samples were oven dried at
95°C for 4 h. then pressed into a KBr disk. (Reprinted from Microporous and Mesoporous Materials, 20, Weir
and Kydd, Synthesis of metatungstate pillared layered double hydroxides with variable layer composition.
Effect of the Mg:Al ratio on the microporous structure, 339-347, 1998, with permission from Elsevier Science).
Sánchez-Martín et al.206 studied the adsorption of the herbicide glyphosate

(N-(phosphonomethyl)glycine) by LDHs. Glyphosate is an amphoteric molecule which
changes from a univalent positive charge at pH below 2 to a trivalent negative charge at pH

above 10. In order to get a better understanding of the mechanism involved, they compared the
undissociated glyphosate, glyphosate adsorbed on the LDH and on a 500°C-calcined LDH at
pH values of 3.5, 5.6 and 11.0. In the non-dissociated glyphosate, C=O bands are observed in
the infrared spectrum at 1732 and 1434 cm-1, while in the dissociated form these bands shift
towards 1634 and 1406 cm-1, respectively. The vibrations associated with P-OH and P-O- are
always observed at 1171 and 1084 cm-1, except at pH=11, where the molecule is fully
dissociated and only the band at 1984 cm-1 is observed. Table 9 gives an overview of the effects
of pH and adsorption on the infrared vibrations of the glyphosate. X-ray diffraction shows that
there is no significant change in the basal spacing of the LDH, suggesting that the glyphosate is
mainly adsorbed on the outer surface of the crystals, although a minor reflection around 10.27
Å indicated some intercalation of glyphosate., At pH 3.5 and 5.6 the C=O bands did not shift
upon adsorption on the LDH, while the P-OH and P-O- bands shifted by 27 and 69 cm-1 towards
lower frequencies. For the calcined LDH small shifts of 20 and 8 cm-1 (pH 3.5) and 34 and 10
cm-1 (pH 5.6) were observed for the C=O bands upon adsorption of the glyphosate. The P-OH
and P-O- were also shifted to lower frequencies, and a broad band was observed around
1138-1068 cm-1 (pH 3.5) and 1135-1066 cm-1 (pH 5.6). At pH=11.0 neither the C=O or the
P-OH and P-O- bands were affected by adsorption on the LDH, whereas the former was
affected in the glyphosate adsorbed on the calcined LDH. These results indicate that the
adsorption takes place via a ligand exchange mechanism between the metal cations in the LDH
hydroxide layer and the P-OH and C=O groups of the glyphosate. In the calcined LDH there
seems to be a simultaneous interaction of both groups with the metal ions, probably via the
formation of a chelate or bidentate complex.
In a similar type of study, Hermosín et al.207 had looked at the adsorption of trinitrophenol
(TNP) on LDHs and their 500°C-calcined products because phenols, with their height toxicity
and widespread use, form an important group of organic contaminants of natural waters. Under
the acidic conditions applied in this study, the TNP is present in the phenolate form, which can
be expected to replace the interlayer carbonate anion in the LDH, or participate in the
reconstitution of the original LDH structure from the calcined material. Their general
observation was that much more TNP was adsorbed by the calcined LDH causing the
reconstitution of the original LDH structure at relatively low pH values. This reconstitution
resulted in an increase in pH due to the consumption of protons.203 Analysis by X-ray
diffraction indicated that the TNP-LDH and the TNP-reconstituted LDH exhibited the same
crystal structure, with a basal spacing of 13.6 Å -compared to the original LDH with a basal
spacing of 7.3 Å- confirming the presence of the TNP as the interlayer anion. The infrared
spectra of both the TNP-LDH and the TNP-reconstituted LDH showed the characteristic bands
of the aromatic C-H mode around 3080 cm-1, the C=C mode of the ring around 1558, 1499 and
1487 cm-1, the aromatic and symmetric N=O mode around 1636, 1609 and 1338 cm-1
respectively, the C-O mode of the deprotonated phenol groups around 1371 cm-1, and the C-N
mode around 1281 cm-1. These frequencies compare well with those observed for potassium
picrate. In addition, the expanded LDHs, and especially the reconstituted LDHs, showed a
decrease in the intensities of the interlayer water bands around 3500 cm-1, while the initial
OH-stretching band at 3498 cm-1 was split into two bands around 3646 and 3434 cm-1, which
was interpreted as being due to the presence of two different environments for this type of water.
This effect was explained by the different sizes and polarities of the interlayer carbonate and
picrate anions, together with the different interlayer spacing of the corresponding LDHs.
Nanocomposites consist of LDH particles intercalated with organopolymer molecules. A

good example form is the intercalation of LDH with polyanaline, based on interlamellar
oxidative polymerisation of aniline. Challier and Slade208 described the synthesis of this
nanocomposite on Cu/Cr-LDHs pre-pillared with terephthalate and hexacyanoferrate in order
to create enough interlamellar space to introduce the aniline. After the introduction of the
aniline, basal spacings of 13.3 or 13.5 Å were observed in the X-ray diffraction patterns of the
LDHs previously expanded by teraphthalate and hexacyanoferrate, respectively. This increase
in basal spacing indicates that the aniline is oriented within the interlayer with its aromatic ring
perpendicular to the hydroxide layers. Infrared spectroscopy was used by Challier and Slade208
to observe the degree of polymerisation of the aniline in the interlayers of the LDH. Table 10
gives an overview of the bands associated with the interlayer polyaniline. In the final product
no aniline monomers were observed, since the characteristic bands of free and protonated
aniline around 3520-3450 cm-1 (νas[NH2]), 3420-3350 cm-1 (νs[NH3+]) and a combination band
at 2650 cm-1 were absent in the infrared spectrum.209 Strong bands, however, were observed
around 1487 and 1299 cm-1, ascribed to a ring-breathing and a phenyl-nitrogen CN mode,
which can be considered as fingerprint bands of polyaniline.210 The presence of some interlayer
carbonate may prevent a more detailed study of this region due to overlapping vibrations. Other
bands observed were around 1591, 1482 and 1295 cm-1 suggesting an emeraldine base form.
Shacklette et al.210 have shown that the free amine form, leuco-emeraldine, exhibits four
vibrational modes around 1600 (weak), 1500 (strong), 1290 (medium) and 820 cm-1 (weak). In
comparison with bulk polyaniline, the phenyl-ring and ?nitrogen modes were shifted to slightly
lower frequencies due to hindering by the hydroxide layers of the LDH. Furthermore, two more
bands around 696 and 752 cm-1 were interpreted as being due to the presence of a small amount
of short-chain oligomers. Upon the intercalation with aniline and the consequent
polymerisation reaction, the amount of teraphthalate and the hexacyanoferrate strongly
decreased, indicating a diminution in the amount of anionic species and hence in the positive
layer charge of the LDH. This was explained by an electron-transfer reaction between the
aniline monomers and the copper in the hydroxide sheets, leading to partial reduction of the
Cu2+ sites.
Table 9 Infrared band positions (in cm-1) of the C=O, P-OH and P-O- groups of free glyphose and of glyphosate adsorbed on LDH and calcined
LDH at different pH values [206].
Free glyphosate Glyphosate-LDH Glyphosate-calcined LDH

pH ν1C=O ν2C=O νP-OH νP-O- ν1C=O ν2C=O νP-OH νP-O- ν1C=O ν2C=O νP-OH νP-O-
3.5 1634 1406 1171 1084 1634 1402 1144 1015 1614 1398 1138-1068 -
5.6 1634 1406 1171 1084 1634 1403 1114 1015 1600 1396 1135-1066 -
11.0 1634 1406 - 1084 1634 1402 - 1087 1610 1370 - 1087
Table 10 Infrared band positions (in cm-1) of the polyaniline intercalated in Cu/Cr-LDH [208].
Polyaniline intercalated in Polyaniline intercalated in Free leuco-emeraldine Assignment [208-210]

hexacyanoferrate-LDH teraphtalate-LDH [210]
1591 1600 Ring mode of quinoid structures
1482 1487 1500 Ring mode
1295 1299 1290 Phenyl-nitrogen mode ν(CN)
1209 1216 δC-H in plane; 1:4 substitution
1165 δC-H out of plane; 1:4 substitution
873 δC-H out of plane; 2 adjacent H atoms
808 820 δC-H out of plane; 2 adjacent H atoms
752 770-730 δC-H out of plane; 5 adjacent H atoms, short-chain
oligomers
696 696 710-630 δC-H out of plane; 5 adjacent H atoms, short-chain
oligomers
591 Aromatic ring deformation
506 510 Aromatic ring deformation
Tagaya et al.211 described nanocomposites based on the reconstitution of calcined

Zn/Al-LDH in carbonate-free water followed by anion exchange an organic solvent
(acetonitrile) with organic acid chlorides. For most of these acid chlorides they only reported
the basal spacings of the resulting intercalated LDHs. Only for the reaction of benzoyl chloride
with the reconstituted LDH resulting in an expanded phase with a basal spacing of 11.2 Å, an
infrared spectrum was reported. Tagaya et al.211 indicated that the amount of hydroxyl groups
has strongly diminished and interpreted this fact as being due to an esterification reaction.
However, they did not work out the details of the organic acid bands in the infrared spectrum to
support this reaction. No reaction was observed with the normal carbonate-containing LDH or
with the calcined product. In the presence of interlayer water it seems more likely to expect the
incorporation of benzoic acid instead of esterification. Indeed, the infrared spectrum of the
intercalated compound shows the characteristic bands of benzoic acid.212
Compounds containing tetracyanoquinodimethane are of interest for their specific
magnetic and charge conducting properties. Bonnet et al.213 have described the intercalation of
the tetracyanoquinodimethane radical anion in Zn/Al/Cl-LDH via coprecipitation at a constant
pH of 7 and by calcination at 350°C and reconstitution of the LDH, both under a CO2-free
nitrogen atmosphere. After intercalation, the LDHs showed an expanded basal spacing around
16.4 Å. Based on the dimensions of the radical anion, Bonnet et al.213 concluded that the anion
is probably in a perpendicular orientation between the LDH hydroxide layers. In the infrared
spectrum a strong characteristic band due to the -C≡N was observed around 2190 cm-1.
However, they do not make any comments on the minor band visible at slightly lower
frequency around 2135 cm-1 in the spectrum of the intercalated LDH, which is absent in the
spectrum of the pure tetracyanoquinodimethane salt. The broad band containing various
overlapping vibrations between 1352 and 1600 cm-1 were attributed to the vibrational modes of
the benzene ring showing a clear broadening upon intercalation. However, in this region also
the carbonate bands are normally present, and no evidence is given that the LDHs were
completely carbonate free. Therefore, the presence of a small amount of interlayer carbonate
anions cannot be excluded. A small band around 1192 cm-1 was interpreted as being due to the
dimerisation of the tetracyanoquinodimethane radicals, a situation that is thermodynamically
favoured. However, within the interlamellar space it is more likely that the radical molecules
will stack like a pack of cards forming a sort of polymer instead of a dimer. Unfortunately, the
infrared spectrum presented by Bonnet et al.213 is not informative enough to confirm this
polymerisation reaction.
Relatively much interest has been shown in LDHs intercalated with sulfonates and
phosphonates.214-218 These relatively large organic molecules have been of interest for several
reasons such as the preparation of nanocomposites, pillared LDHs, UV-absorbing agents (e.g.,
in plastics like PVC), biomedical applications (drug delivery systems, reinforcing agents in
composites from biomaterials), etc. Franklin et al.214 described the intercalation of Mg/Al and
Zn/Al-LDHs with both the monovalent and divalent anions derived from
5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid (BHMBS). BHMBS is a known dibasic
acid that has a strong sulfonic acid group and a much weaker phenolic group. It was shown that
the divalent anion was easily incorporated in the LDH by exchange with the exchangeable
nitrate anions, resulting in an expanded basal spacing of 13.8 Å. The presence of the divalent
anion in the interlayer was confirmed by infrared spectroscopy, which showed a good
agreement with the spectrum of the disodium salt of BHMBS in the region between 1150 and
1550 cm-1 (Table 11). Characteristic in this region are the symmetric and antisymmetric SO2
stretching vibrations around 1170 and 1350 cm-1, respectively.212 Intercalation of the
monovalent anion, where only the sulfonic group is ionised, was much more difficult and was
achieved by an acid-decomposition reaction of the carbonate form of the LDHs, resulting in a
basal spacing of 20 Å. This difficulty of intercalating the monovalent anion was ascribed to the
interconversion to the divalent anion within the lamellar space of the LDH. Again, the infrared
spectrum of the intercalated compound was comparable to that of the monosodium salt of
BHMBS (Table 11). Although thirteen bands were reported for the BHMBS salts and
intercalated compounds, no detailed assignment was presented. Neither was any information
given on how the LDH hydroxide layers and the orientation of the BHMBS anions influence
the infrared spectrum in comparison to the salts of BHMBS, since especially the antisymmetric
SO2 stretching mode is sensitive to hydrogen bonding.212 Treatment of the 13.8 Å LDH by
washing with NaOH or prolonged washing with water resulted in the formation of a new phase
with a basal spacing of 15.4 Å, which was thought to be due to the intercalation of a mixed
monovalent BHMBS-hydroxide ion. However, UV-VIS analysis showed that the BHMBS had
properties between those observed for the monovalent and divalent BHMBS anions
intercalated in LDHs, although the infrared spectrum was closer to that of the divalent phase.
Table 11 Infrared and UV-VIS band positions and relative intensities of 5-benzoyl-4-hydroxy-
2-methoxybenzenesulfonate (BHMBS) intercalated LDH and the corresponding BHMBS
sodium salts [214].
IR Band positions Divalent Disodium Monovalent Monosodium

(cm-1) BHMBS-LDH BHMS salt BHMBS-LDH BHMS salt
Basal spacing 13.8 Basal spacing 20Å
Å
1180 strong strong medium medium
1210 medium medium
1220 strong strong
1250 strong strong
1270 strong strong
1310 weak weak
1350 medium weak medium medium
1380 weak weak
1420 medium medium
1450 medium medium weak weak
1470 medium medium weak
1490 weak weak
1510 medium medium weak
UV-VIS (nm)
321 medium 318 broad
323 weak
334 medium
342 weak
370 medium 363 broad
Kanezaki216 intercalated Mg/Al-LDH with naphthalene-2,6-disulfonate (N26DS),

resulting in an expanded phase with a basal spacing of 16.8 Å. A similarly expanded phase was
found for the naphthalene-1,5-disulfonate (N15DS) intercalated LDH. N15DS was also used
by Putyera et al.215 for their intercalation and calcination experiments, but they did not report
the X-ray diffraction pattern of the expanded LDH. Kanezaki observed that in the interlayer
region, N26DS or N15DS coexist with carbonate anions, as shown by chemical analyses and
the carbonate bands in the infrared spectrum around 1367, 1361 and 1360 cm-1, overlapping the
1395 and 1336 cm-1 bands observed for free N15DS salt (Table 12). The band at 923 cm-1 for
the free salt has been ascribed to the S-O stretching vibration of the SO3 group, which is known
to shift towards lower frequencies upon coordination through an oxygen atom.139 In the
spectrum of the intercalate this shifted band is probably hidden under a number of intense
bands around 800 cm-1. The two bands at 1047 and 1209 cm-1 corresponding to
non-coordinated S-O bonds in the SO3 group are not influenced by the intercalation process.
Similar bands in the infrared spectrum were observed by Putyera et al.215 for the N15DS
intercalated LDH with clearly recognisable bands around 1210, 1050 and 610 cm-1. Other
bands associated with the N15DS are visible, but with very low intensity, and the band
positions were not as such reported. Putyera et al.215 noted that the intensities and the band
shapes of the antisymmetric and symmetric S-O modes at 1210 and 1050 cm-1 are different
from those in the corresponding salt. Kanezaki216 concluded that one oxygen from the SO3
group is coordinating to the hydroxide layer of the LDH, probably to the Al3+, while the other
two oxygen atoms are not coordinated to the LDH structure. This seems to be in contradiction
with the results of Putyera et al.,215 who interpreted the change in shape and intensity of the two
S-O stretching modes to be due to strong interactions with the LDH hydroxide layers, resulting
in the formation of non-identical sulfonate groups in the LDH interlamellar space.
Table 12. Infrared absorption bands of naphthalene-1,5-disulfonate intercalated LDH in the

region below 1500 cm-1 in comparison to the corresponding sodium salt [215,216].
N15DS-LDH [216] (cm-1) N15DS-LDH [215] (cm-1) N15DS salt (cm-1)

Assignment [139]
1500 Visible* 1501 Skeleton
- - 1395 Combination band
- - 1336 Combination band
1238 Visible 1237 δC-H
1206 1210 1209 νO-S-O
1159 - 1162 δC-H
1043 1050 1047 νS-O
- - 923 νS-O
663 - 662 -
611 610 607 νS-O
*Observed in spectrum but no peak position reported
Wilson et al.217 studied the properties of nanocomposites based on the intercalation of

LDHs with poly(styrenesulfonate), PSS, and poly(vinylsulfonate), PVS. Intercalation of LDHs
with these organic compounds resulted in the formation of expanded phases with d003 values of
12.7 (PVS-LDH) and 21 Å (PSS-LDH), respectively, consistent with a bilayer thickness of the
incorporated compounds The infrared spectra reveal that in both samples still a small amount of
interlayer carbonate and water are present. PSS and PVS are characterised by a strong and
relatively sharp band at 1040 and 1196 cm-1, respectively, due to S-O vibrations (in RSO
species). Although there are significant differences in the spectra between the two intercalated
compounds (Fig. 11), these differences are not discussed. Neither do the authors use the
spectroscopy as a means to gain more information about the way the organic compounds are
oriented in the interlayer, or how they are bonded to the hydroxide layers of the LDH.
Nijs et al.218 studied the intercalation of phenylphosphonic acid (PPA) in Mg/Al-LDHs
with different Mg/Al ratios. They observed that only in the case of a Mg/Al ratio of 2/1 stable
intercalates could be formed with a d-spacing of 15.8 Å. Slightly acidic conditions around pH 6
were necessary to facilitate the exchange, but too acidic conditions resulted in a leaching-out of
Mg. As in the case of the PVS and PSS intercalated LDHs,217 a small amount of carbonate was
found in the interlayer region, as observed by a band in the infrared spectrum around 1365 cm-1.
PPA intercalated in the LDH was characterised by two C-H stretching vibrations of the
aromatic group around 3054 and 3076 cm-1, only slightly visible on top of the much stronger
OH-stretching modes of the LDH, four unassigned bands in the region between 2000 and 1700
cm-1, a sharp band assigned to the P-C stretching mode around 1438 cm-1, four not very clear
vibrations of the O3O-C group around 1140, 1068, 1040 and 990 cm-1, and finally some
characteristic bands of the monosubstituted phenyl ring around 753, 723 and 694 cm-1. No clear
differences between the spectra of PPA in the interlayer of the LDH and pure PPA were reported,
therefore no assumptions can be made about possible bonding mechanisms between the PPA
and the LDH upon intercalation.
Figure 11 FTIR absorbance spectra for LDH samples: (a) LDH-CO3, (b) LDH-PVS and (c) LDH-PPS.
(Reprinted from Applied Clay Science, 15, Wilson et al., Surface and interfacial properties of
polymer-intercalated layered double hydroxide nanocomposites, 265-279, 1999, with permission from Elsevier
Science.
WATER
Water in LDHs can be present in various forms. In general one can recognise (i) water in
the interlayer between the hydroxide layers, which may or may not form bridging-type bonds
with the exchangeable anions, and (ii) water adsorbed on the outer surface, or (iii) free water in
between the particles. Water bending modes can be recognised in the infrared spectra between
ca. 1500-1700 cm-1 accompanied by OH-stretching vibrations in the 3000-4000 cm-1 region. In
the Raman spectra these bands are generally very weak or are even absent, especially the
bending vibrations. Depending on the strength with which the water molecule is
hydrogen-bonded to other molecules, a shift towards higher frequency in the bending region
can be observed in the spectra, in contrast to the stretching region where a shift to lower
frequency is observed. Normally minerals containing physically adsorbed water give strong
infrared bands around 3450 cm-1 and 1630 cm-1. Generally speaking, monomeric,
non-hydrogen bonded water (i.e., in the vapour phase) gives bands around 3755 and 1595 cm-1,
while in the liquid phase these bands shift to 3455 and 1645 cm-1 and in ice to 3255 and 1655
cm-1. When water is bound to the surface of a mineral the strength of the hydrogen bond will
determine where the OH-bending and stretching vibration will be observed. For water adsorbed
on clay minerals the OH-stretching modes of weak hydrogen bonds occur in the region between
3580 and 3500 cm-1, while strong hydrogen bonds are observed below 3420 cm-1. When water
is coordinated to cations in cationic clay minerals the stretching vibration occurs around 3220
cm-1, corresponding to an ice-like structure. In both cationic clay minerals and LDHs a strong
overlap exists in the OH-stretching region between the M-OH bands of the hydroxide layers
and the OH-bands of water. Therefore, for the study of water in and on LDHs, the OH-bending
region of the infrared spectrum is much more informative. Table 13 gives an overview of the
effects of the LDH hydroxide sheets composition and the interlayer anions or complexes on the
infrared OH-bending mode of water. For all LDHs, this band is observed in the range between
ca. 1580 and 1655 cm-1. No clear effect can be seen due to variation in either the divalent or the
trivalent cations present in the hydroxide layers. The interlayer anion, however, does have a
significant effect on the position of the OH-bending mode of the interlayer water. Similar
values are observed for carbonate and sulphate anions, but a significant shift towards lower
wavenumbers by about 20 cm-1 is observed for hydroxyl and nitrate interlayer anions. An
intermediate effect is observed for chromate. Also pillaring with decavanadate results in a
strong shift towards lower wavenumbers compared to the corresponding carbonate-containing
LDHs. In general this indicates that the pillaring results in a weakening of the hydrogen bonds
of the interlayer water molecules to its surrounding anions.
Table 13 Infrared water bending vibrational positions as function of di- and trivalent metal
composition of the LDH and as function of the interlayer anion.
M2+ M3+ Interlayer anion Band position (cm-1)

Reference
[63] Mg Al CO32- 1640
[65] Mg Al CO32- 1655
[65] Mg Al OH- 1628
[65] Mg Al NO3- 1629
[69] Mg Al OH- 1625
[70] Mg Al CO32- 1591
[70] Mg Al Cl- -
[70] Mg Al SO42- 1642
[70] Mg Al CrO42- 1639
[117] Mg Al CO32- 1647
[171] Mg Al V10O286- 1653
[117] Mg Ga CO32- 1644
[124] Mg Mn CO32- 1660
[205] Mg Mn SO42- 1640
[205] Mg Fe SO42- 1630
[125] Mg/Mn2+ Mn3+ CO32- 1643
[173] Mg Cr CO32- 1620-1640
[173] Mg Cr V10O286- 1620
[136] Mg/Co2+ Co3+ NO3- 1622
[75] Mg/Zn Al SO42- 1580-1600
[175] Zn Cr CO32- 1638
[175] Zn Cr V10O286- 1619
[178] Zn Al V10O286- 1623
[205] Zn Fe SO42- 1630
[17] Ni Al CO32- 1625
[65] Ni Al CO32- 1643/1697
[102] Ni Al CO32- 1640
[172] Ni Al CO32- 1635
[172] Ni Al V10O286- 1620
[205] Ni Fe SO42- 1630
[65] Co Al CO32- 1646
[87] Co Al CO32- 1640
[91] Co Al CO32- 1640
[176] Co Cr CO32- 1634
[176] Co Cr V10O286- 1618
[205] Co Fe SO42- 1630
[127] Ni Fe CO32- 1615
[127] Ni Fe SO42- 1615
[130] Ni V CO32- 1635-1367
[173] Ni Cr CO32- 1620-1640
[173] Ni Cr V10O286- 1620
INFRARED EMISSION SPECTROSCOPY DURING THE THERMAL

TREATMENT OF LDHS
The thermal behaviour of LDHs plays an important role in the preparation of
heterogeneous catalysts based on mixed metal oxides or metal on oxide carriers (see Part II of
this book). In these systems a close interaction of two or more metals are required on an atomic
scale. Some papers report Mg/Al-LDH as a catalyst precursor. Suzuki and coworkers described
the aldol condensation reaction between formaldehyde and acetone and halide-exchange
reactions between alkyl halides over a heat-treated Mg-LDH.219,220 Corma et al.221 studied the
condensation of benzaldehyde with ethyl acetoacetate over a calcined Mg-LDH. In most
studies involving the calcination of LDHs the samples were first heated at a given temperature
for a certain period of time, followed by cooling to room temperature in order to record the
infrared spectra. Rey et al.140 described how after heating at 100°C the OH-bending mode of
the interlayer water around 1616 cm-1 has disappeared, while in the OH-stretching region new
bands associated with the hydroxide sheets were observed around 3690 and 3416 cm-1. At the
same time, the carbonate band at 1363 cm-1 showed a split in two bands around 1538 and 1391
cm-1. The OH-stretching band was observed to shift towards higher frequencies while
decreasing in intensity up to 300°C, after which it had completely disappeared. The carbonate
bands remained visible, although strongly decreased in intensity, up to temperatures above
600°C.
Kloprogge and Frost222,223 have reported the IES spectra of LDHs where the trivalent
cation was Al3+ combined with Mg2+ (Fig. 12), Zn2+, Co2+ or Ni2+ as the divalent cations. The
OH-stretching region at 200°C is dominated by a broad band around 3400-3500 cm-1 with a
shoulder around 2950 cm-1. This shoulder corresponds to the CO3-H2O bridging mode
observed in the FTIR spectrum at 2938 cm-1. The band at 3400-3500 cm-1 and the shoulder
around 2950 cm-1, which are both associated with interlayer water, quickly disappeared upon
further heating. The M-OH stretching modes hidden in the broad band around 3400-3500 cm-1
decreased in intensity during heating and disappeared at approximately 500°C, which is
slightly higher than the temperature observed in the DTA/TGA pattern for the end of the
dehydroxylation or as observed by Rey et al.140 in IR spectra of calcined and cooled samples.
This difference in behaviour is probably associated with diffusional problems within the LDH
crystals in the IES.
In the region below 1000 cm-1, Mg/Al-LDH showed a major change around 350-400°C. In
this temperature range the bands at 772, 923 and 1029 cm-1, corresponding to the ‘Al’-OH
out-of-plane deformation and doublet deformation modes, completely disappeared. New bands
were observed at 713, 797 and 1075 cm-1. The first and the last band, accompanied by the band
around 545 cm-1, indicated the formation of spinel (MgAl2O4).37 The band around 713 cm-1,
however, is also very close to the νLO position of MgO at 717 cm-1.36 X-ray diffraction of the
heated LDH confirmed the presence of both spinel and MgO as breakdown products.
The region between 850 and 1250 cm-1 showed four bands around 874 (ν2 interlayer CO32-),
955 (‘Al’-OH deformation), 1033 (‘Al’-OH deformation) and 1112 cm-1 (ν1 interlayer CO32-) in
the absorption spectrum, while the 200°C IES spectrum showed five bands at ca. 958, 1010,
1071, 1130 and 1185 cm-1. All of these bands exhibited a minor shift towards lower
wavenumbers upon heating. In contrast, from the four overlapping bands (based on band
component analysis) around 1341, 1398, 1532 and 1582 cm-1, the last two bands shift towards
lower wavenumbers. The 1341 and 1398 cm-1 bands, associated with the ν3 modes of the
interlayer CO32- anions, however, show first a shift towards higher wavenumbers between 300
and 350°C, followed by either a disappearance or a decrease in wavenumber between 600 and
650°C. Above 300°C the 1341 cm-1 band has disappeared, whereas the other band remains
visible although it strongly diminishes in intensity. A similar effect is observed for the 1341
cm-1 band of the Zn-containing hydrotalcite, but at a slightly lower temperature. This suggests
that there are more than one carbonate species present, which react differently upon heating,
instead of the observed split being due to a decrease in the carbonate site symmetry. One
possible option is that the interlayer carbonate ions are located near different metal ions in the
hydroxide sheets. Another possibility is that the different carbonate ions are located at similar
positions near the hydroxide surface, but one as a real interlayer anion and the other as an
adsorbed anion on the outer surface of the crystal. Based on its position and the fact that both
bands at 1463 and 1539 cm-1 are very sensitive to the change in composition, it seems very
likely that these bands represent combination modes of the bands observed at 558 plus 923 cm-1
and of the bands at 638 plus 923 cm-1. Similar combinations can be found for the Zn-containing
hydrotalcite. The combination bands in both samples show a decrease in intensity as the
dehydroxylation takes place above approximately 250°C, in agreement with the DTA/TGA
data.
Figure 12 Infrared emission spectra of Mg/Al-LDH between 450 and 3800 cm-1 at temperatures from 200° to
800°C at intervals of 50°C.
Similar results were obtained by Herman et al.224 for Cu/Zn/Al-LDH, based on IR spectra
at high temperatures obtained from a specially designed Pyrex reactor with KBr windows
holding the sample. Prior to the recording of the spectra the reactor was evacuated to 10-3 Torr
in order to remove gases formed during the heating process. The broad band due to the
OH-stretching modes of the hydroxide sheets strongly diminished in intensity upon heating and
disappeared around 400-450°C, while the carbonate was still present around these temperatures.
Unfortunately, they did not report the effects of further heating on the final product, as they
used the carbonate containing product as a catalyst for methanol synthesis.
Cobalt plays an important role in heterogeneous catalysis and the incorporation of Co in
LDHs has been described for the preparation of mixed metal oxide catalysts. In the simplest
case, Mg is replaced by Co225-228 for the preparation of Fischer-Tropsch catalysts.227,228 In other
cases Co was added as a second or third metal to hydrotalcites in which Mg and Al were
replaced by Zn, Cu and Cr.229-231
For Co/Al-LDH the OH-stretching region showed that dehydroxylation took place below
350°C.223 As also observed for the Mg/Al-LDH, due to diffusional problems and differences in
heating rate compared to the TGA/DTA, the temperatures observed in the IES are slightly
higher. This is also true for the decarbonation reaction that can be observed by a decreasing
intensity up to about 500°C. In the region below ca. 1000 cm-1 the Co/Al-LDH showed a major
change around 400°C. In this temperature range the bands at 781, 918 and 1029 cm-1,
corresponding to the ‘Al’-OH translation mode and the doublet deformation modes previously
observed in the infrared absorption spectrum at 733 and 1054 cm-1,65 completely disappeared.
Also the carbonate modes ν2 and ν4 at 846 and 652 cm-1 disappeared. New bands were observed
around 519 and 637 cm-1. The formation of these bands indicates the formation of either a
spinel-like material (CoAl2O4) or CoO or Co3O4 or both.37 The band at 584 cm-1, initially
ascribed to the ‘Co’-OH translation mode,65 disappeared during heating at 300°C, and a new
band appeared around 583 cm-1, which probably represents the corresponding Co-O mode.
One of the variations in cations comprises takovite, in which Mg is replaced by Ni. Heat
treatment under reducing conditions converts the takovite in a Ni/Al2O3 catalyst for
methanation of CO, Fischer-Tropsch reactions and steam reforming of methane.91-94,141,232-235
The IES spectra of Ni/Al-LDH (takovite) showed the dehydroxylation and dehydration by the
decrease in intensity of the OH-stretching bands in the 3000-4000 cm-1 region up to ca. 450°C.
The two strong carbonate bands around 1450 cm-1 diminished in intensity up to about 500°C,
after which no more changes were observed, similar to what was observed in the IES spectra of
Mg/Al- and Co/Al-LDHs. The changes in the low wavenumber region were small and difficult
to observe. The bands at 715, 1007 and 1161 cm-1 are all associated with ‘Al’-OH translation
modes, whereas the two bands at 660 and 852 are the ν2 and ν4 modes of the interlayer
carbonate, respectively. The remaining band at 598 cm-1 is associated with the ‘Ni’-OH
translation mode. A change in the low wavenumber region of the takovite IES spectra due to a
change in the crystalline phase was observed from 300° to 350°C. All the bands observed at
200°C disappeared, while new bands were formed around 563, 638, 710 and 787 cm-1. These
bands suggest more the formation of a spinel-like phase than that of corundum (α-Al2O3).37 As
for the Mg-hydrotalcite, the XRD pattern of the calcined takovite showed the presence of a
spinel phase and NiO. So, the infrared emission spectral results support the reaction observed
by Sato et al.236 in which a NiAl2O4 spinel phase + NiO is formed under a nitrogen atmosphere
and not Al2O3 + NiO as indicated by Titulaer et al.237 and by Jitianu et al.,238,239 who observed
that the products formed are strongly dependent on the initial Ni/Al ratio in the LDH. In
samples with low Al content, NiO was the major product, characterized by a band at 460 cm-1,
whereas the remaining Al was thought to fill the tetrahedral and octahedral interstices like in an
incipient transition alumina phase as shown by a band around 800 cm-1. Heating at 900°C
resulted in the formation of an inverted spinel type phase. However, increasing the Al-content
resulted in the observation of possibly γ-alumina (bands around 580 and 780 cm-1) at 450°C,
and at 900°C a nickel spinel-type phase with a band associated with condensed AlO6 octahedra
around 600 cm-1.
Only a limited number of papers have reported on the spectral changes upon thermal
treatment or calcinations of other LDHs. Labajos et al.122 reported on the thermal behaviour of
Mg/V-LDH. They described an unusually high temperature of 500°C at which the interlayer
water disappeared, evidenced by the disappearance of the H2O-CO3 bridging mode at 3020
cm-1 and the OH-bending mode at 1630 cm-1. This is more than 200°C higher than normally
observed for LDHs containing, for example, Mg/Al. At very high temperature (above 1000°C)
they observed bands that can be ascribed to tetrahedral VO4 species (916, 873, 704, 480, 469
and 340 cm-1) together with bands that can be ascribed to MgO. The vanadate bands are also
very close to those observed for magnesium ortho-vanadates. Corresponding X-ray diffraction
measurements showed, in agreement with the IR data, that the V3+ is oxidized to V5+ and
Mg3V2O8 is formed as the stable phase.
In a similar type of study, Labajos and Rives123 reported on the thermal behaviour of
Ni/Cr-LDHs. The carbonate band ν3 band disappeared around 400°C, while at the same time
new bands were formed at 950 (plus a shoulder at lower wavenumbers) and 793 cm-1. After
heat treatment at 500°C these bands are split into four bands around 952, 906, 779 and 675 cm-1.
These bands, although somewhat shifted, suggest the formation of a NiCrO4-type phase, as
pure NiCrO4 has been characterized by bands at 940, 782 and 690 cm-1. Calcination at 700°C,
however, gave a spectrum similar to that of Cr2O72- instead, which was confirmed by X-ray
diffraction exhibiting reflections belonging to NiO and NiCr2O7. Similar results were obtained
for Ni/Mn-LDH,129 where NiO was observed at 450°C together with either NiMnO3
(ilmenite-type) or NiMn2O4 (spinel-type), depending on the initial composition. At this stage,
in the IR spectrum still residual hydroxyls and carbonate groups were observed around 3420,
1400 and 1358 cm-1. After calcinations at 700°C all the hydroxyl and carbonate has
disappeared and in the IR spectrum bands were observed only in the lattice region below 800
cm-1.
CONCLUSIONS
As shown in this chapter, spectroscopic methods, especially infrared and Raman
spectroscopy, are strong techniques to study the structure of inorganic compounds such as
LDHs and their modifications. Until recently the accent has been mainly on infrared
spectroscopy and only limited information is available on Raman spectroscopy. Till now a
major problem with the use of infrared spectroscopy in the existing literature is that it is mainly
used just to report the spectra and band positions without any further study of what these bands
can tell about the structure. This is especially true for molecules present in the interlayer region.
Combination of both infrared and Raman methods in the near future will result in a much more
detailed understanding, as more information comes available by the determination of active and
inactive Raman and infrared modes and the corresponding site symmetries and space groups.
Further information can also be gained from spectral data in combination with X-ray diffraction
about the possible orientation of interlayer molecules in the interlayer region and bonding to the
LDHs hydroxide layers. A relatively new technique for the study of thermal transformations in
minerals, infrared emission spectroscopy or IES, has been shown to be a strong technique to get
more detailed information about the thermal transformations while they are actually are taking
place at certain temperatures. Understanding these processes is of major importance for the
tailor-made preparation of heterogeneous catalysts based on calcined LDHs.
ACKNOWLEDGEMENTS
The financial and infra-structural support of the Queensland University of Technology,
Centre for Instrumental and Developmental Chemistry is gratefully acknowledged. The writing
of this paper would not have been possible without the valuable help of several people within
our centre, especially Leisel Hickey, David Wharton and Llew Rintoul.
REFERENCES
1. L. Hickey, J.T. Kloprogge and R.L. Frost, Klei, Glas en Keramiek 21 (2000) 7-11+27.
2. E. Manasse, Am. Soc. Toscana Sci. Nat., Pisa PV 24 (1915) 92.
3. G. Aminoff and B. Brome, K. Sven Vetenskapsakad. Handl. 9 (1930) 23 (Chem. Abst. 26
(1932) 397).
4. C. Frondel, Am. Miner. 26 (1941) 295.
5. W. Feitknecht and G. Fisher, Helv. Chim. Acta 18 (1935) 555.
6. W. Feitknecht, Helv. Chim. Acta 25 (1942) 131.
8. G. W. Brindley and S. Kikkawa, Am. Miner. 64 (1979) 836.
10. W. T. Reichle, Solid State Ionics 22 (1986) 135.
11. W. T. Reichle, CHEMTECH 16 (1986) 58.
12. W. T. Reichle, J. Catal. 94 (1985) 547.
14. S. Miyata and A. Okada, Clays Clay Miner. 25 (1977) 14
15. S. Miyata, T. Kumura, H. Hattori and K. Tanabe, Nippon Kagaku Zasshi 92 (1971) 514.
17. G. J. Ross and H. Kodama, Am Miner. 52 (1967) 1036.
18. D. L. Bish, Bull Miner. 103 (1980) 170.
19. S. Miyata and T. Kumura, Chem. Lett. (1973) 843.
20. O. Clause, M. Gazzano, F. Trifirò, A. Vaccari, and L. Zatorski, Appl. Catal. 73 (1991)
217.
21. C. Barriga, J. M. Fernández, M. A. Ulibarri, F. M. Labajos, and V. Rives, J. Solid State
Chem. 124 (1996) 205.
22. K. Fuda, K. Suda, and T. Matsunaga, Chem. Lett. (1993) 1479.
23. C. Depege, L. Bigey, C. Forano, A. de Roy, and J. P. Besse, J. Solid State Chem. 126
(1996) 314.
24. A. S. Bookin, V. I. Cherkashin, and S. A. Drits, Clays Clay Miner. 41 (1993) 631.
25. G. Busca, F. Trifiro, and A. Vaccari, Langmuir 6 (1990) 1440.
26. R. S. Mulukulta and C. Detellier, J. Mater. Sci. Lett. 15 (1996) 797.
27. V. A. Drits, T. N. Sokolova, G. V. Sokolova, and V. I. Cherkashin, Clays Clay Miner. 35
(1987) 401.
28. A. R. West, ‘Solid State Chemistry and its Applications’, (Wiley, New York, 1990, 310).
29. A. Vaccari, Catal. Today 41 (1998) 53.
30. M.K. Titulaer, Geologica Ultraectina 99 (1993) Ph. D. Thesis Utrecht University, The
Netherlands.
31. C.N. Banwell, ‘Fundamentals of Molecular Spectroscopy’, (McGraw-Hill Book
Company, London, 1983, 338).
32. N.K. Roberts, In ‘Surface Analysis Methods in Materials Science’, (D.J. O’Connor, B.A.
Sexton, R.St.C. Smart, eds.) Springer Series in Surface Sciences, 32 (1992) 187.
33. P.F. McMillan and A.M. Hofmeister, Rev. Mineralogy 18 (1988) 99.
34. W.D. Perkins, J. Chem. Educ. 64 (1987) A269.
35. F.A. Miller and G.B. Kauffman, J. Chem. Educ. 66 (1989) 795.
36. S.D. Ross, ‘Inorganic Infrared and Raman Spectra’, (McGraw-Hill Book Company,
London, 1972, 414).
37. J.A. Gadsden, ‘Infrared Spectra of Minerals and Related Inorganic Compounds’,
(Butterworth & Co. (Publishers) Ltd., London, 1975, 277).
38. Van der Marel and Beutelspacher, ‘Atlas of Infrared Spectroscopy of Clay Minerals and
their Admixtures’, (Elsevier Amsterdam, 1976).
39. W.P. Griffith, In: ‘Spectroscopy of Inorganic-based Materials’ (R.J.H. Clark and R.E.
Hester, eds.) (John Wiley & Sons Ltd, New York, 1987) 119.
40. W. Kaye, Spectrochim. Acta 6 (1954) 257.
41. W. Kaye, Spectrochim. Acta 7 (1955) 181.
42. G.R. Rossman, Rev. Mineralogy 18 (1988) 193.
43. A.M. Vassalo, P.A. Cole-Clarke, L.S.K. Pang and A. Palmisano, J. Appl. Spectrosc. 46
(1992) 73.
44. R.L. Frost and A.M. Vassallo, Clays Clay Miner. 44 (1996) 635.
45. R.L. Frost, K. Finnie, B. Collins and A.M. Vassallo, In: Proc. 10th Int. Clay Conf., Adelaide,
Australia, July 1995 (Fitzpatrick, R.W., Churchman, G.J. and Eggleton, T., eds.), CSIRO
Publications (1995) 219.
46. D.L. Allara, D. Teicher and J.F. Durana, Chem. Phys. Lett. 84 (1981) 20.
47. D. Kember, D.H. Chenery, N. Sheppard and J. Fell, Spectrochim. Acta 35A (1979) 455.
48. P. Baraldi and G. Fabbri, Appl. Spectrosc. 38 (1984) 668.
49. D.B. Chase, Appl. Spectrosc. 35 (1981) 77.
50. G. Fabbri and P. Baraldi, Appl. Spectrosc. 26 (1972) 593.
51. L.M. Gratton, S. Paglia, F. Scattaglia and M. Cavallini, Appl. Spectrosc. 32 (1978) 310.
52. B. Jonson, B. Rebenstorf, R. Larsson and M. Primet, Appl. Spectrosc. 40 (1986) 798.
53. J. Mink and G. Kersztury, Appl. Spectrosc. 47 (1993) 1446.
54. J.T. Kloprogge and R.L. Frost, Thermochim. Acta 320 (1998) 245.
55. M.J.D. Low, Nature 206 (1965) 1089.
56. J.T. Kloprogge and R.L. Frost, N. Jb. Miner., Mh. (1999) 62.
57. J.T. Kloprogge, S. Komarneni, K. Yanagisawa, R. Fry and R.L. Frost, J. Coll. Interf. Sci. 212
(1999), 562.
58. J.T. Kloprogge, R. Fry and R.L. Frost, J. Catal. 184 (1999) 157.
59. J.T. Kloprogge, R.L. Frost and J. Kristof, Can. J. Anal. Sci. Spec. 44 (1999) 33.
60. R.L. Frost and J.T. Kloprogge, Spectrochim. Acta 55A (1999) 2195.
61. R.L. Frost, Chemistry in Australia, 63 (1996) 446.
62. J.T. Kloprogge and R.L. Frost, Klei, Glas en Keramiek 19 (1998) 22.
63. T.N. Moroz and D.K. Arkhipenko, Sovjet Geology and Geophysics 32 (1991) 52.
64. W. Kagunya, R. Baddour-Hadjean, F. Kooli and W. Jones, Chem. Phys. 236 (1998) 225.
65. J.T. Kloprogge and R.L. Frost, J. Solid State Chem. 146 (1999) 506.
66. L. Hickey, J.T. Kloprogge and R.L. Frost, J. Mater. Sci. 35 (2000) 4347.
67. F.A. Mumpton, H.W. Jaffe and C.S. Thompson, Amer. Miner. 50 (1965) 1893.
68. S. Koritnig and P. Süsse, Tschermaks Min. Petr. Mitt. 22 (1975) 79.
69. L. Châtelet, J.Y. Bottero, J. Yvon and A. Bouchelaghem, Coll. Surf. A 111 (1996) 167.
70. T. López, P. Bosch, M. Asomoza, R. Gómez and E. Ramos, Mater. Lett. 31 (1997) 311.
71. F.M. Labajos, V. Rives and M.A. Ulibarri, J. Mater. Sci. 27 (1992) 1546.
72. M.L. Valcheva-Traykova, N.P. Davidova and A.H. Weiss, J. Mater. Sci. 28 (1993) 2157.
73. H.D. Lutz, ‘Structure and Bonding’, (Springer Series 82, 1992).
74. F. Kooli, K. Kosuge, T. Hibino and A. Tsunashima, J. Mater. Sci. 28 (1993) 2769.
75. F. Kooli, K. Kosuge and A. Tsunashima, J. Mater. Sci. 30 (1995) 4591.
76. J.T. Kloprogge, L. Hickey and R.L. Frost, in preparation (2000).
77. JA. Gadsden, ‘Infrared Spectra of Minerals and Related Compounds’, (Butterworth,
London Brisbane Scarborough Wellington Durban, 1975).
78. L. Hickey, J.T. Kloprogge and R.L. Frost, in preparation (2000).
79. C. Barriga, F. Kooli, V. Rives and M.A. Ulibarri, In ‘Synthesis of Porous Materials.
Zeolites, Clays, and Nanostructures,” M.L. Occelli and H. Kessler (eds.)(Marcel Dekker,
New York, 1996) 661.
80. G. Natta, In ‘Catalysis’, P.H. Emmett (ed.)(Reinhold, New York, 1955, vol. 3, ch. 3).
81. I.M. Campbell, In ‘Catalysis at Surfaces’, (Chapman and Hall, London, 1988).
83. G. Fornasari, S. Gusi, F. Trifiro and A. Vaccari, Ind. Eng. Chem. Res. 26 (1987) 1500.
84. F. Trifiro, A. Vaccari and G. Del Piero, In ‘Studies in Surface Science and Catalysis", Vol.
39 Characterization of Porous Solids, Proceedings of the UIPAC symposium (COPSI),
Bad Soden, Germany, April 26-29, 1987’, K.K. Unger, J. Rouquerol, K.S.W. Sing and H.
Kral (eds.) (Elsevier Science Publishers, Amsterdam, 1988) 571.
85. S. Morpurgo, M. Lo Jacono and P. Porta, J. Mater. Chem. 4 (1994) 197.
86. S. Kannan and C.S. Swamy, J. Mater. Sci. Lett. 11 (1992) 1585.
87. M.A. Ulibarri, J.M. Fernández, F.M. Labajos and V. Rives, Chem. Mater. 3 (1991) 626.
88. L. Bruce, J. Takos and T.W. turney, In ‘Symposium on new catalytic materials and
techniques’. (Div. Petroleum Chemistry, Amer. Chem. Soc, 1989) 502.
89. M. Blanchard, H. Derule and P. Canesson, Catal. Lett. 2 (1989) 319.
90. S. Kannan, S. Velu, V. Ramkumar and C.S. Swamy, J. Mater. Sci. 30 (1995) 1462.
91. E.B.M. Doesburg, H. Hakvoort, H. Schaper and L.L. Van Reijen, Appl. Catal. 7 (1983)
85.
92. E.B.M. Doesburg, P.H.M. De Korte, H. Schaper and L.L. Van Reijen, Appl. Catal. 11
(1984) 155.
93. O. Clause, M. Goncalves Coelho, M. Gazzano, D. Mateuzzi, F. Trifiro and A. Vaccari,
Appl. Clay Sci. 8 (1993) 169.
94. J.R.H. Ross, M.C.F. Steel and A. Zeini-Isfahani, J. Catal. 52 (1978) 280.
95. J.E. Moneyron, A. Deroy and J.P. Besse, Sensors Actuators B4 (1991) 189.
96. P. Olivia, J. Leonardi, J.F. Laurent, C. Delmas, J.J. Braconnier, M. Figlarz and F. Fievet,
J. Power Sources 8 (1982) 229.
97. R. Barnard, G.T. Crickmore, J.A. Lee and F.L. Tye, J. Appl. Electrochem. 10 (1980) 61.
98. J. Bauer, D.H. Buss, H.J. Harms and O. Glemser, J. Electrochem. Soc. 137 (1990) 173.
99. D.L. Bish and G.W. Brindley, Amer. Miner. 62 (1977) 458.
100. M.J. Hernández-Moreno, M.A. Ulibarri, J.L. Rendon and C.J. Serna, Phys. Chem. Miner.
12 (1985) 34.
101. S. Kannan, A. Narayanan and C.S. Swamy, J. Mater. Sci. 31 (1996) 2353.
102. K.T. Ehlsissen, A. Delahaye-Vidal, P. Genin, M. Figlarz and P. Willmann, J. Mater.
Chem. 3 (1993) 883.
103. F.M. Labajos, V. Rives and M.A. Ulibarri, Spectrosc. Lett. 24 (1991) 499.
104. A.B.P. Lever, ‘Inorganic Electronic Spectroscopy’, 2nd ed. (Elsevier Scientific
Publishers, Amsterdam, 1984).
105. E.H. Nickel and R.M. Clarke, Amer. Miner. 61 (1976) 366.
106. C.J. Serna, J.L. Rendón and J.E. Iglesias, Clays Clay Miner. 30 (1982) 180.
107. K.R. Poppelmeier and S.W. Hwu, Inorg.Chem. 26 (1987) 3297.
108. I. Sissoko, E.T. Iyagba, R. Sahai and P. Biloen, J. Solid State Chem. 60 (1985) 283.
109. A.J. Perrotta, S.Y. Tzeng, W.D. Imbrogno, R. Rolles and M.S. Weather, J. Mater. Res. 7
(1992) 3306.
110. P.K. Dutta and M. Puri, J. Phys. Chem. 93 (1989) 376.
111. J.T. Kloprogge, J. Porous Mater. 5 (1998) 5.
112. V.R.Choudary, A.K. Kinage, C. Sivadinarayana, P. Devadas, S.D. Sansare and M.
Guisnet, J. Catal. 158 (1996) 34.
113. K.J. Chao, S.P. Sehn, L.-H. Lin, M.J. Genet and M.H. Feng, Zeolites 18 (1997) 18.
114. E. López-Salinas, M. García-Sánchez, M.E. Llanos-Serrano, and J. Navarrete-Bolanoz,
J. Phys. Chem. B 101 (1997) 5112.
115. M.R. Weir, J. Moore and R.A. Kydd, Chem. Mater. 9 (1997) 1686.
116. K.M. Dooley and G.L. Price, Catal. Today 31 (1996) Special Issue.
117. M.A. Aramendía, Y. Avilés, J.A. Benítez, V. Borau, C. Jiménez, J.M. Marinas, J.R. Ruiz
and F.J. Urbano, Microporous Mesoporous Mater. 29 (1999) 319.
118. I. Rousselot, C. Taviot-Guého and J.P. Besse, Int. J. Inorg. Mater. 1 (1999) 165.
119. F.A. Mumpton, H.W.Jaffe and C.S. Thompson, Amer. Miner. 50 (1965) 1893.
120. J.M. Fernández, M.A. Ulibarri, F.M. Labajos and V. Rives, J. Mater. Chem. 8 (1998)
2507.
121. J.M. Fernández, C. Barriga, M.A. Ulibarri, F.M. Labajos and V. Rives, Chem. Mater. 9
(1997) 312.
122. F.M. Labajos, V. Rives, P. Malet, M.A. Centeno and M.A. Ulibarri, Inorg. Chem. 35
(1996) 1154.
123. F.M. Labajos and V. Rives, Inorg. Chem. 35 (1996) 5313.
124. H.C.B. Hansen and R.M. Taylor, Clay Miner. 26 (1991) 507.
125. J.M. Fernández, C. Barriga, M.A Ulibarri, F.M. Labajos and V. Rives, J. Mater. Chem. 4
(1994) 1117.
126. E.H. Nickel and J.E. Wildman, Miner. Mag. 44 (1981) 333.
127. D.L. Bish and A. Livingstone, Miner. Mag. 44 (1981) 339.
128. M. Del Arco, P. Malet, R. Trujillano and V. Rives, Chem. Mater. 11 (1999) 624.
129. C. Barriga, J.M. Fernández, M.A. Ulibarri, F.M. Labajos and V. Rives, J. Solid State
Chem. 124 (1996) 205.
130. F.M. Labajos, M.D. Sastre, R. Trujillano and V. Rives, J. Mater. Chem. 9 (1999) 1033.
131. J.H. Moses, A.H. Weiss, K. Matusek and L. Guezi, J. Catal. 86 (1984) 417.
132. A.J. Marchi, J.I. Di Cosimo, C.R. Apesteguía, Catal. Today 15 (1992) 383.
133. A. Monzón, E. Romeo, C. Royo, R. Trujillano, F.M. Labajos and V. Rives, Appl. Catal. A:
General 185 (1999) 53.
134. S. Morpurgo, M. Lo Jacono and P. Porta, J. Solid State Chem. 122 (1996) 324.
135. J.N. Armor, T.A. Braymer, Y. Li, E.P. Petrocelli, E.L. Weist, S Kannan and C.S. Swamy,
Appl. Catal. B: Envorinmental 7 (1996) 397.
136. H.C. Zeng, Z.P. Xu and M. Qian, Chem. Mater. 10 (1996) 2277.
137. H.C.B. Hansen, C.B. Koch and R.M. Taylor, J. Solid State Chem. 113 (1994) 46.
138. M. Del Arco, R. Trujillano, S. Kassabov and V. Rives, Spectrosc. Lett. 31 (1998) 859.
139. K. Nakamoto, ‘Infrared and Raman Spectra of Inorganic and Coordination Compounds’,
5th ed. (John Wiley & Sons, USA, 1997).
140. V.C. Farmer, ‘The Infrared Spectra of Minerals’ (Mineralogical Society, London, 1974).
141. L.E. Alzamora, J.R.H. Ross, E.C. Kruissink and L.L. Van Reijden, J. Chem. Soc.
Faraday Trans. I 77 (1981) 665.
142. F. Rey, V. Fornés and J.M. Rojo, J. Chem. Soc. Faraday Trans. 88 (1992) 2233.
143. E. Evana, R. Marchidan and R. Manaila, Bull. Soc. Chim. Belg. 101 (1992) 101.
144. V. Rives and M.A. Ulibarri, Coord. Chem. Rev. 181 (1999) 61.
145. E. Suzuki, S. Idemura and Y. Ono, Clays Clay Miner. 37 (1989) 173.
146. J. Qiu and G. Villemure, J. Electroanal. Chem. 428 (1997) 165.
147. S. Kikkawa and M. Koizumi, Mater. Res. Bull. 17 (1982) 191.
148. P.S. Braterman, C. Tan and J. Zhao, Mater. Res. Bull. 29 (1994) 1217.
150. K.A. Carrado, A. Kostapapas and S.L. Suib, Solid State Ionics 26 (1988) 77.
151. F.A.P. Cavalcanti, A. Schutz and P. Biloen, In ‘Preparation of catalysts IV’, B. Delmon, P.
Grange, P. A. Jacobs and G. Poncelet (eds.)(Elsevier Amsterdam, 1987) 165.
152. G. Emschwiller, Compt. Rend. 238 (1954) 1414.
153. L. Tosi and J. Danon, Inorg. Chem. 3 (1964) 150.
154. V. Caglioti, G. Sartori and M. Scrocco, J. Inorg. Nucl. Chem. 8 (1957) 86.
155. G. Mao, M. Tsuji and Y. Tamaura, Clays Clay Miner. 41 (1993) 731.
156. H.C.B. Hansen and C.B. Koch, Clays Clay Miner. 42 (1994) 170.
157. M.J. Holgado, V. Rives, M.S. Sanromán and P. Malet, Solid State Ionics 92 (1996) 273.
158. I. Crespo, C. Barriga, V. Rives and M.A. Ulibarri, Solid State Ionics 101-103 (1997) 729.
159. K. Yao, M. Taniguchi, M. Nakata, K. Shimazu, M. Takahashi and A. Yamagishi, J.
Electroanal. Chem. 457 (1998) 119.
160. J.A. Olabe and H.O. Zerga, Inorg. Chem. 22 (1983) 4156.
161. A.R. Champion and H.G. Drickamer, J. Chem. Phys. 47 (1967) 2592.
162. H.A. Larsen and H.G. Drickamer, J. Phys. Chem. 61 (1967) 1299.
163. M. Gordon, L.L. Williams and N. Sutin, J. Am. Chem. Soc. 83 (1961) 2061.
164. E. Pelizzetti, E. Mentasti and C. Baiocchi, J. Phys. Chem. 80 (1976) 2979.
165. H. Nijs, M. De Bock, E.F. Vansant, Microporous Mesoporous Mater. 30 (1999) 243.
166. G. Bor, J. Inorg. Nucl. Chem. 17 (1961) 174.
167. W.P. Griffith and T.D Wilkins, J. Chem. Soc. A (1966) 1087.
168. W.P. Griffith and P.J.B. Lesniak, J. Chem. Soc. A (1969) 1066.
169. J. Twu and P.K. Dutta, J. Phys. Chem. 93 (1989) 7863.
170. M.A. Ulibarri, F.M. Labajos, V. Rives, R. Trujillano, W. Kagunya and W. Jones, Inorg.
Chem. 33 (1994) 2592.
171. F. Kooli, V. Rives and M.A. Ulibarri, Inorg. Chem. 34 (1995) 5114.
173. F. Kooli, I. Crespo, C. Barriga, M.A. Ulibarri and V. Rives, J. Mater. Chem. 6 (1996)
1199.
174. M. Del Arco, V. Rives, R. Trujillano and P. Malet, J. Mater. Chem. 6 (1996) 1419.
175. M. Del Arco, M.V.G. Galiano, V. Rives, R. Trujillano and P. Malet, Inorg. Chem. 35
(1996) 6362.
176. K.S. Han, L. Guerlou-Demourgues and C. Delmas, Solid State Ionics 98 (1997) 85.
177. C. Barriga, W. Jones, P. Malet, V. Rives and M.A. Ulibarri, Inorg. Chem. 37 (1998) 1812.
178. K. Bahranowski, G. Bueno, V. Cortés Corberán, F. Kooli, E.M. Serwicka, R.X.
Valenzuela and K. Wcislo, Appl. Catal. A 185 (1999) 65.
179. E. López-Salinas and Y. Ono, Bull. Chem. Soc. Jpn. 65 (1992) 2465.
180. C.F. Baes and R.E. Mesmer, ‘The Hydrolysis of Cations’ (Wiley-Interscience, New York,
1976).
181. J. Twu and P.K. Dutta, Chem. Mater. 4 (1992) 398.
182. H.C.B. Hansen, In ‘Clays controlling the Environment’, 10th Int. Clay Conf. Adelaide,
Australia, G.J. Churchman, R.W. Fitzpatrick and R.A. Eggleton (eds) (CSIRO
Publishing, Melbourne, 1995), 201.
183. A.C. Chapman and L.E. Thirlwell, Spectrochim. Acta 20 (1964) 937.
184. G.E.B.Y. Ahlijah and E.F. Mooney, Spectrochim. Acta 22 (1966) 547.
185. M.I. Tejedor-Tejedor and M.A. Anderson, Langmuir 6 (1990) 602.
186. M. Badreddine, M. Khaldi, A. Legrouri, A. Barroug, M. Chaouch, A. De Roy and J.P.
Besse, Mater. Chem. Phys. 52 (1998) 235.
187. M. Khaldi, M. Badreddine, A. Legrouri, M. Chaouch, A. Barroug, A. De Roy and J.P.
Besse, Mater. Res. Bull. 33 (1998) 1835.
188. U. Costantino, M. Casciola, L. Massinelli, M. Nocchetti and R. Vivani, Solid State Ionics
97 (1997) 203.
189. M. Badreddine, A. Legrouri, A. Barroug, A. De Roy and J.P. Besse, Mater. Lett. 38 (1999)
391.
190. J.L. Crovisier, J.H. Thomassin, T. Juteau, J.P. Eberhart, J.C. Touray and P. Bailiff,
Geochimica Cosmochimica Acta 47 (1983) 377.
191. A. Schutz and P. Biloen, J. Solid State Chem. 68 (1987) 360.
192. Z. Karim, Soil Sci. Soc. Amer. J. 50 (1986) 247.
193. K. Kuma, W. Paplawsky, B. Gedulin, B. and G. Arrhenius, Origin of Life and The
Evolution of The Biosphere 19 (1989) 573.
194. S.K. Yun, V.R.L. Constantino and T.J. Pinnavaia, Clays Clay Miner. 43 (1995) 503.
195. A.N. Lazarev, ‘Vibrational spectra and structure of silicates’ (Plenum, New York,
1972).
196. T. Kwon and T.J. Pinnavaia, Chem. Mater. 1 (1989) 381.
197. J. Wang, Y. Tian, R.-C. Wang, J.L. Colón and A. Clearfield, Mat. Res. Symp. Proc. 233
(1991) 63.
198. C. Hu, Q. He, Y. Zhang, E. Wang, T. Okahura and M. Misono, Catal. Today 30 (1996)
141.
199. S.K Yun, V.R.L. Constantino and T.J. Pinnavaia, Macroporous Mater. 4 (1995) 21.
200. M.K.Weir and R.A. Kydd, Microporous Mesoporous Mater. 20 (1998) 339.
201. H. Kopka, K. Beneke and G. Lagaly, J. Coll. Interface Sci. 123 (1988) 427.
202. T. Sato and A. Okuwaki, Solid State Ionics 45 (1991) 43.
203. M.A. Ulibarri, J.M. Luque and J. Cornejo, Mater. Chem. Phys. 25 (1990) 81.
204. M.A. Ulibarri, M.J. Hernández and J. Cornejo, J. Mater. Sci. 26 (1991) 1512.
205. H.C.B. Hansen and R.M. Taylor, Clay Miner. 26 (1991) 311.
206. M.J.Sánchez-Martín, M.V. Villa and M.Sánchez-Camazano, Clays Clay Miner. 47 (1999)
777.
207. M.C. Hermosín, I. Pavlovic, M.A. Ulibarri and J. Cornejo, Water Res. 30 (1996) 171.
208. T. Challier and R.C.T. Slade, J. Mater. Chem. 4 (1994) 367.
209. G. Socrates, ‘Infrared Characteristic Group Frequencies’, (Wiley, Chichester, 1980).

210. L.W. Shacklette, J.F. Wolf, S. Gould and R.H. Baughman, J. Phys. Chem. 88 (1988)
3955.
211. H. Tagaya, H. Morioka, J. Kadokawa, M. Karasu and K. Chiba, Supramol. Sci. 2 (1995)
33.
212. D. Lin-Vien, N.B. Colthup, W.G. Fateley and J.G. Grasselli, ‘The Handbook of Infrared
and Raman Characteristic Frequencies of Organic Molecules’, (Academic Press, San
Diego, 1991), 503 p.
213. S. Bonnet, C. Forano and J. P. Besse, Mater. Res. Bull. 33 (1998) 783.
214. K.R. Franklin, E. Lee and C.C. Nunn, J. Mater. Chem. 5 (1995) 565.
215. K. Putyera, T.J. Bandosz, J. Jagieo and J.A. Schwartz, Carbon 34 (1996) 1559.
216. E. Kanezaki, Mater. Res. Bull. 34 (1999) 1435.
217. O.C. Wilson Jr, T. Olorunyolemi, A. Jaworski, L. Borum, D. Young, A. Siriwat, E.
Dickens, C. Oriakhi and M. Lerner, Appl. Clay Sci. 15 (1999) 265.
218. H. Nijs, A. Clearfield and E.F. Vansant, Microporous Mesoporous Mater. 23 (1998) 97.
219. E. Suzuki and Y. Ono, Bull. Chem. Soc. Jpn. 61 (1988) 1008.
220. E. Suzuki, M. Okamoto and Y. Ono, J. Molec. Catal. 61 (1990) 283.
221. A. Corma, V. Fornés, R.M. Martín-Aranda and F. Rey, J. Catal. 134 (1992) 58.
222. J.T. Kloprogge and R.L. Frost, Appl. Catal. A 184 (1999) 61.
223. J.T. Kloprogge and R.L. Frost, Phys. Chem. Chem. Phys. 1 (1999) 1641.
224. R.G. Herman, C.E. Bogdan, P.L. Kumler and D.M. Nuszkowski, Mater. Chem. Phys. 35
(1993) 233.
225. S. Kannan and C.S. Swamy, J. Mater. Sci. Lett. 11 (1992) 1585.
226. M.A. Ulibarri, J.M. Fernández, F.M. Labajos and V. Rives, Chem. Mater. 3 (1991) 626.
227. L. Bruce, J. Takos and T.W. Turney, in ‘Symposium on new catalytic materials and
techniques’, Div. Petroleum Chemistry, Amer. Chem. Soc (1989) 502.
228. M. Blanchard, H. Derule and P. Canesson, Catal. Lett. 2 (1989) 319.
229. P. Courty, D. Durand, E. Freund and A. Sugier, J. Mol. Catal. 17 (1982) 241.
230. G. Fornasari, F. Trifirò and A. Vaccari, Ind. Eng. Chem. Res. 26 (1987) 1500.
231. G. Busca, F. Trifiro and A. Vaccari, Langmuir 6 (1990) 1440.
232. E.B.M.Doesburg, S. Orr, J.R.H. Ross and L.L. Van Reijen, J. Chem. Soc., Chem. Comm.
(1977) 734.
233. Kruissink, E.C., L.L. Van Reijen and J.R.H. Ross, J. Chem. Soc., Faraday Trans. 1 77
(1981) 649.
234. S.D. Jackson, S.J. Thomson and G. Webb, J. Catal. 70 (1981) 249.
235. M.R. Gelsthorpe, K.B. Mok, J.R.H. Ross and R.M. Sambrook, J. Mol. Catal. 25 (1984)
253.
236. T. Sato, H. Fujita, T. Endo, M. Shimada and A. Tsunashima, Reactivity of Solids 5 (1988)
219.
237. M.K. Titulaer, J.B.H. Jansen and J.W. Geus, Clays Clay Miner. 42 (1994) 249.
238. M. Jitianu, M. Bãlãsoiu, R. Marchidan, M. Zaharescu, D. Crisan and M. Craiu, Int. J.
Inorg. Mater. 2 (2000) 287.
239. M. Jitianu, A. Jitianu, M. Zaharescu, D. Crisan and R. marchidan, Vibr. Spectrosc. 22
(2000) 75.
Chapter 6
SOLID-STATE NMR AND EPR STUDIES OF

HYDROTALCITIES
João Rocha
Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
e-mail: rocha@dq.ua.pt
INTRODUCTION
Solid-state NMR spectroscopy is now well established as one of the most powerful tools
available to study hydrotalcites and related systems, providing detailed structural information
on the local environment and dynamic behaviour of the nucleus under investigation. Thermal
decomposition, reconstruction, pillaring and intercalation are the main processes which have
been studied by 1H, 11B, 25Mg, 27Al, 29Si, 31P, 51V, 71Ga and 119Sn NMR. The dynamics and
molecular orientation of interlayer species have been investigated by 1H, 2H, 13C, 15N, 35Cl and
77
Se NMR. Although the first comprehensive solid-state NMR studies of layered double
hydroxides (LDH) and related materials date back to the mid eighties, most of the research in
this field has been published in the last decade. A considerable amount of the work has been
concentrated on the use of relatively simple NMR techniques (such as magic-angle spinning,
1
H to 13C cross-polarisation and high-power 1H decoupling) to elucidate details of the materials
structure. However, more sophisticated experiments, such as multiple-quantum MAS NMR, 1H
and 13C NMR relaxation measurements and 2H exchange NMR spectroscopy, are increasingly
being used, providing a wealth of information on structure and dynamics.
The reference mineral hydrotalcite, discovered in Sweden around 1842, is usually
formulated as [Mg0.75Al0.25(OH)2](CO3)0.125⋅0.5H2O. Hence, it is no wonder that the bulk of
NMR studies on hydrotalcite materials revolve around 1H, 13C and 27Al nuclei. While the two
former are spin I=1/2 nuclei, 27Al is a half-integer quadrupolar nucleus with spin I=5/2.
Quadrupolar nuclei are particularly challenging to the spectroscopist and special care is needed
when recording their solid-state NMR spectra. Although magnesium is present in hydrotalcite,
25
Mg NMR has rarely been used to probe the structure of layered double hydroxides. This is
mainly due to the fact that 25Mg is not only a relatively low natural abundance (10.1%) I=5/2
nucleus, but it also possesses a low gyromagnetic ratio, γ. With recent advances in solid-state
NMR instrumentation, it is now possible to study low γ-nuclei and we hope to see more 25Mg
218 João Rocha
NMR studies in the near future. The natural abundance of 17O (I=5/2) is only 0.038% and this
explains why this NMR-active nucleus does not seem to have been used to probe the local
environment of oxygen in hydrotalcites. Although an expensive exercise, 17O enriched LDH
can, in principle, be synthesised thus enabling NMR studies to be more easily carried out.
EPR seems to have been much less used than NMR to study LDH. The work has been
focused mainly on materials intercalated with a range of metal complexes, oxo and
polyoxometalates. Clearly, EPR complements NMR, allowing a comprehensive study of
systems containing paramagnetic centres. Due to space limitations, here we do not present the
basics of the EPR technique.
SOLID-STATE NMR: BASIC IDEAS

Several NMR-active nuclei are available to study layered double hydroxides and related
materials. Some of these are I=1/2 nuclei with a low natural abundance (eg. 13C) or they may be
ca. 100% abundant (eg. 1H). Other nuclei are quadrupolar with integer (eg. 2H, I=1) or
half-integer (eg. 27Al, I=5/2) spins. Table 1 gives the relevant nuclear spin properties of the
nuclei that have been studied in LDH. Each group of nuclei poses particular problems and the
solid-state NMR techniques used to retrieve the information of chemical interest may be
different. On the other hand, normally, the NMR spectra can not be recorded in the same
manner for solids as for liquids.This is because in the solid state one as to consider a number of
anisotropic interactions which can be overlooked for solutions, as the random molecular
tumbling averages the NMR interactions to isotropic values. The effect of these interactions in
the solid state is to broaden the spectral lines considerably. Although wide-line NMR
experiments may in some cases provide information of chemical interest (for example on
molecular orientation of interlayer species) very often broad spectral lines are undesirable. A
number of methods are available for eliminating or reducing the effects of these broadening
interactions, and these allow high-resolution solid-state NMR spectra to be obtained.
NMR Spectra of I=1/2 Nuclei in Solids
The main broadening effects to be considered for I=1/2 nuclei in solids are the so-called
dipole-dipole interaction and chemical shift anisotropy. The dipole-dipole interaction is due to
the influence of magnetic dipoles from neighbouring nuclei with spin on the magnetic field at
the nucleus under observation. This through-space interaction of the nuclear spins is
orientation-dependent and so for a powder sample (in which all orientations are present) results
in a considerable broadening of the NMR spectral lines. The dipolar interaction depends on a
3cos2θ-1 term, where θ is the angle between the internuclear vector and the static external
magnetic field. This term is averaged to zero by fast sample rotation about an angle of 54.7º to
the magnetic field, a technique known as magic-angle spinning (MAS). High-resolution spectra
may be recorded provided that the sample is spun at speeds of the order of the static linewidth.
In most cases this means spinning at 2-10 kHz or so. However, completely averaging out the
dipolar coupling involving 1H and 19F nuclei is often not possible, even with state-of-the-art
commercial MAS probes capable of achieving 35 kHz MAS rates. The (heteronuclear) dipolar
Solid-State NMR and EPR Studies of Hydrotalcities 219
broadening caused by 1H nuclei on, say, 13C or 31P NMR spectra, may be removed by using
high-power 1H decoupling. For the case of high-resolution 1H NMR spectroscopy proton
decoupling is inappropriate and it may be necessary to use certain multiple pulse sequences,
usually combined with sample spinning (CRAMPS), to reduce the homonuclear dipolar
couplings between protons.
Chemical shift anisotropy is the other major interaction for I=1/2 nuclei in solids. The
electronic shielding at a nucleus responsible for the chemical shift depends on orientation and,
again, for a powder a broad spectral line will result. The chemical shift anisotropy is
characterised by the three principal values of the second rank tensor (corresponding to
shielding along the three symmetry axes at the nucleus studied). MAS averages the chemical
shift to the single isotropic value (equivalent to the one observed in solution) and affords
high-resolution NMR spectra. When MAS rates less than the static linewidth are used sharp
lines are still obtained, but these lines are flanked by spinning sidebands. These are peaks
separated from the true isotropic chemical shift by multiples of the spinning frequency.
Table 1. Selected properties of NMR-active nuclei which have been used to study LDH materials.
Nucleus Spin Natural abundance (%) Gyromagnetic ratio γ Quadrupolar moment

(107 T-1 s-1) (Q fm-2)
1
H ½ 99.985 26.752 -
2
H 1 0.015 4.107 0.288
11
B 3/2 80.42 8.584 4.065
13
C ½ 1.10 6.728 -
15
N ½ 0.37 -2.712 -
25
Mg 5/2 10.13 -1.639 22
27
Al 5/2 100 6.976 14.0
29
Si ½ 4.67 -5.319 -
31
P ½ 100 10.839 -
35
Cl 3/2 75.53 2.624 -8.249
51
V 7/2 99.76 7.049 -5.2
71
Ga 3/2 39.6 8.181 10.6
77
Se ½ 7.6 5.125 -
119
Sn ½ 8.58 -10.032 -
Low natural abundance nuclei such as 13C are usually studied with a technique known as
cross-polarisation (CP), which as no bearing upon spectral resolution. This ingenious
experiment involves the transfer of magnetisation usually from nearby protons to the nucleus
under investigation, providing a signal enhancement and allowing shorter recycle times
between successive scans. Cross-polarization is normally combined with MAS and high-power
proton decoupling during acquisition (CP/MAS).
NMR Spectra of I>1/2 (Quadrupolar) Nuclei in Solids
The NMR spectral lines of nuclei with I>1/2 are further broadened by the so-called
quadrupole interaction. These nuclei have a non-spherical distribution of nuclear charge and
possess an electric quadrupole moment which interacts with any electric field gradients
220 João Rocha
(created by the electronic cloud) at the site of the nucleus. The quadrupole interaction is
anisotropic and broad NMR lines are recorded for powder samples. In most cases the effect of
the quadrupolar interaction is much smaller than the Zeeman splitting of energy levels (due to
the external static magnetic field), and we can calculate its influence by perturbation theory.
Although the first-order quadrupole interaction is normally very large (in the MHz range), it
does not affect the transitions between the energy levels m=1/2 and m=-1/2 of a half-integer
quadrupolar nucleus (a I=3/2 nucleus, for example, has 2I+1=4 energy levels, with m=-3/2, -1/2,
3/2 and 3/2). The other transitions present (1/2↔3/2, etc.) are often too broad to be detected.
The 1/2↔-1/2 transition is, however, affected by the smaller (kHz range) second-order
quadrupole interaction. Although MAS (combined with high-power proton decoupling, if
necessary) removes the dipolar and chemical shift anisotropy broadening, it can only sharpen
the second-order quadrupole broadened lines by a factor of less than four. The anisotropic
broadening can not, thus, be completely removed by MAS and this can lead to complicated
lineshapes (powder patterns) in which a single nucleus environment may show more than one
peak maximum in the NMR spectrum. In addition, the observed chemical shift (the centre of
gravity) of the NMR lines is shifted by an amount which depends on the quadrupole coupling
parameters at the nucleus under study (quadrupole coupling constant and asymmetry parameter)
and the magnetic field. This shift and the width of the powder patterns are both inversely
proportional to the external magnetic field.
Some caution is needed in the interpretation of NMR spectra of quadrupolar nuclei. The
true isotropic chemical shift can only be calculated when the quadrupole coupling parameters
are known. In general, it is desirable to work at as high a magnetic field as possible because the
NMR peaks are sharper at high fields and the spectra are simplified. Obtaining reliable relative
intensities for the different resonances usually requires the careful selection of instrumental
parameters. In particular, very short (sometimes < 1µs) and powerful radio-frequency pulses
must be used.
Special techniques are now available for removing dipolar interactions, chemical shift
anisotropy and the anisotropic part of the second-order quadrupole interaction, providing
isotropic spectra of half-integer quadrupole nuclei with unprecedented resolution. In one such
technique, double rotation (DOR), this is achieved by spinning the sample about two axes
simultaneously, one at the magic angle, the other at either 30.6º or 70.1 to the first angle.1 In
dynamic angle spinning (DAS) the sample is spun sequentially about two different angles
(34.7º and 79.2º) to the external magnetic field, with the magnetisation stored by an echo pulse
sequence during the angle switching period.2,3 Much of the NMR signal may be lost during this
period when the samples relaxation is fast (as is often the case for quadrupole nuclei). Both
DOR and DAS require special dedicated NMR probes and their implementation still poses
technical problems. In 1995 a revolutionary new two-dimensional technique known as
multiple-quantum (MQ) MAS NMR spectroscopy has been introduced.4 It only requires a
conventional MAS NMR probe and its practical implementation is relatively straightforward.
The simplest MQ MAS NMR pulse sequence consists of two short and powerful
radio-frequency pulses separated by a delay t1 which is incremented.5 The first pulse generates
single and multiple-quantum coherences. By carefully cycling the phase of this pulse, it is
possible to retain only the triple- (or quintuple-) quantum coherence which, after evolving
during time t1, is transferred selectively into a single-quantum coherence, by the second pulse,
and is observed during the acquisition time t2. Isotropic echoes appear at times t2 = R t1; in a
triple-quantum 27Al (I=5/2) spectrum, for example, the anisotropic ratio R takes the value 19/12.
After a double Fourier transform in t2 and t1, the various NMR peaks appear along the
anisotropic axis A with a direction ν2 = R ν1, where ν2 and ν1 are the frequencies in the single-
and triple-quantum dimensions. The projection of the (sheared) two-dimensional spectrum
onto axis F1 yields an isotropic, highly resolved spectrum, while the F2 projection is essentially
the ‘conventional’ MAS NMR spectrum.
As stated before, the first-order quadrupole interaction is generally very large and so will
dominate over other broadening interactions. Thus, in the case of integer spin nuclei such as 2H
(I=1), very broad peaks are recorded, but useful information may be obtained, as the lineshape
is very sensitive to any molecular reorientation processes occurring. Wide-line 2H NMR
spectroscopy is, hence, a technique particularly well suited to provide information on the
molecular dynamics of, for example, chemical species residing in the interlayer space of LDH.
However, deuterium is only 0.015% abundant, making routine NMR detection only possible in
2
H-enriched molecules. 1H and 13C (among other nuclei) wide-line NMR and careful
measurement of relaxation times as a function of temperature can also provide valuable
information on molecular orientation and dynamics of interlayer species.
NMR STUDIES ON LAYERED DOUBLE HYDROXIDES

In this review the most relevant solid-state NMR work published until mid 2000 has been
organised by nucleus.
1
H
The ordering of interlayer water in hydrotalcite containing carbonate in the interlayer has
been studied by static 1H and 13C NMR of powder and oriented samples.6 The latter have been
obtained by depositing a LDH suspension on circular quartz plates and drying. The plates were
then stacked inside a NMR sample holder. In a well-oriented sample, the crystallites have their
c axis perpendicular to the quartz plates and the resulting 1H NMR spectrum exhibits
characteristics of a single-crystal spectrum. Pairs of 1H (I=1/2) nuclei in a rigid matrix give rise
to a Pake doublet signal due to intramolecular dipolar interaction. The resonance positions of
the doublet peaks depend on the 3cos2θ-1 term, where θ is the angle between the internuclear
vector and the static external magnetic field. Powder and oriented samples spectra can be
calculated by numerically integrating the relevant equation over all orientations. Fig. 1 shows
experimental and simulated 1H NMR powder spectra of hydrotalcite.6 The separation between
the two peaks left and right from the central peak is about 20.6 kHz. This indicates that the
water molecules giving rise to the Pake doublet are rapidly rotating around their C2 axis, which
reduces the splitting by a factor of 1/2. The central peak observed is due to both water
physisorbed on the outer crystallites surface and slow intramolecular proton exchange. Close
inspection of the spectrum suggests that a broad (ca. 20 kHz) featureless signal ascribed to
hydroxide protons is also present. Selected 1H NMR spectra of oriented samples are shown in
Fig. 2.6 The fact that at θ = 0º the largest separation between doublet signals is observed,
indicates that the C2 axis of the oriented water molecules lies parallel to the c axis of
222 João Rocha
hydrotalcite and therefore stands perpendicular to the layers. The 1H chemical shift anisotropy
has been estimated from the spectra as ca. 13 ppm, much larger than the value calculated by ab
initio methods for a rotating water molecule (0.6 - 2 ppm).6 The large discrepancy points to the
presence of hydrogen-bonding. A similar 1H NMR study of the ordering of interlayer water in
hydrotalcite containing nitrate (instead of carbonate) in the interlayer is also available.7
However, the authors have concluded (probably incorrectly) that water has its C2 axis parallel
rather than perpendicular to the layers. In the same work, 1H spin-lattice relaxation times have
been measured as a function of temperature and a motional activation energy for interlayer
water molecules of 4 kJ/mol was estimated from these data. Such a low value is indicative of
rapid translational mobility of water within the layers present, in spite of the strong hydrogen
bonding which orients the water molecules.
The thermal decomposition of hydrotalcites with carbonate in the interlayer has been
studied by 1H wide-line NMR using carefully out-gassed samples.8 The spectra of the calcined
materials display a broad featureless line due to structural OH groups. Since no interlayer water
is present no Pake doublet is observed. The intensity of the NMR line is proportional to the
amount of OH groups, while the second moment of the spectrum (‘width’) of this line gives
information about distances between those groups. It has been concluded that hydrotalcite
dehydroxylation starts at ca. 125°C and up to 225°C it occurs between adjacent OH groups in
the same layer. Above 225°C, dehydroxylation occurs between OH groups of contiguous layers,
thus collapsing the lamellar structure.
Aramendía et al. studied the thermal decomposition of a [Mg-Ga] LDH by 1H (and 71Ga,
see 3.13) MAS NMR. 9
The polymerisation of silicate anions in the interlamellar domains of [Zn-Al] and [Zn-Cr]
layered double hydroxides has been studied by Depège et al.10 The 1H MAS NMR spectrum of
[Zn-Al] chloride precursors show typical broad unresolved peaks given by hydroxide and water
protons. The [Zn-Al-SiO4] intercalated phases display two main, sharp, resonances at 1.4 and
4.2 ppm, attributed to the OH groups of the brucite sheets and to adsorbed water molecules,
respectively. The unusually high resolution of these 1H MAS NMR spectra is due to weak
1
H-1H dipolar interactions, indicating that the protonated species are isolated, thus excluding
the presence of water molecules in the interlamellar domains, in contact with OH groups of
brucite sheets. The authors concluded that these facts can be explained only by the
polycondensation of silicate species between the [Zn3Al(OH)8]+ sheets.
Useful data on NMR relaxation (T1, T1ρ) of protons in [Zn-Al-Cl] layered double
hydroxides as a function of temperature and NMR frequency may be found in ref. 11.
Figure 1. Experimental and simulated 1H NMR powder spectra (7.0 T) of hydrotalcite. (a) Experimental
spectrum; (b) simulated spectrum (sum of the spectra in parts c and d); (c) simulated spectrum due to oriented
water with C2 rotational freedom; (d) simulated spectrum of physisorbed water. Reprinted from A. van der
Pool, B. L. Mojet, E. van de Ven and E. de Boer, Ordering of intercalated water and carbonate anions in
hydrotalcite. An NMR study, J. Phys. Chem., 98: 4050-4054 (1994),  1994, with permission from The
American Chemical Society.
Figure 2. Experimental (top) and simulated 1H NMR powder spectra (7.0 T) of oriented hydrotalcite for two
angles between the ordering axis and the magnetic field: (a) 0º; (b) 80º. Reprinted from A. van der Pool, B. L.
Mojet, E. van de Ven and E. de Boer, Ordering of intercalated water and carbonate anions in hydrotalcite. An
NMR study, J. Phys. Chem., 98: 4050-4054 (1994),  1994, with permission from The American Chemical
Society.
2
H
The dynamics and orientations of interlayer (deuterated) terephtalate (TA) anions in mixed
anion hydrotalcite-type compounds [Mg1-xAlx(OH)2](AyB1-y)x-2⋅xH2O where A =
p-C6D4(COO)22- and B = CO32-] have been studied by 2H wide-line NMR.12 Two dominant 003
d spacings, 7.6 and 14.2 Å, have been observed by powder XRD in these samples, indicating
that there are at least two interlayer environments. The room temperature 2H NMR spectra of
the prepared materials display two superimposed powder patterns (Fig. 3). The main pattern
224 João Rocha
given by sample 1 is typical of a nearly static phenyl deuteron, with a 136 kHz splitting between
singularities (strong sharp peaks in Fig. 3). It is ascribed to TA molecules that rest nearly flat
between the layers and have little room for reorientation. In contrast, sample 3 spectrum is
dominated by a powder pattern with singularities at ±18 kHz, due to TA anions undergoing
some form of motional process. Variable-temperature 2H NMR spectra of sample 1 (Fig. 4)
show that as the temperature is increased, the broad 136 kHz splitting pattern disappears and
simultaneously the resonances at ±18 kHz emerge. Similar results are observed for the other
samples (although the static-deuteron spectrum persists at higher temperatures for sample 1).
The variable-temperature 2H NMR spectra have been carefully simulated, assuming several
motional models, and compared with experimental spectra. It has been concluded that some of
the TA anions in every sample are oriented perpendicular to the layers and undergo rotational
diffusion about the C-COO- axis at temperatures in the range 245 to 355 K (Fig. 5). The
remainder TA ions are essentially immobile. Two-dimensional 2H-exchange NMR was
instrumental in excluding a possible 180º flip motion of the interlayer TA ions (Fig. 5). The
study also suggests that the presence of CO32- anions in the interlayer, rather then layer charge,
is the main factor affecting the dynamics and orientation of interlayer TA anions.
At least another work is available on 2H NMR of LDH materials.13
Figure 3. Static 2H NMR spectra (11.7 T) of hydrotalcite samples recorded at room temperature. Reprinted
from R. S. Maxwell, R. K. Kukkadapu, J. E. Amonette and H. Cho, 2H solid-state NMR investigation of
terephthalate dynamics and orientation in mixed-anion hydrotalcite-like compounds, J. Phys. Chem., 103B:
5197-5203 (1999),  1999, with permission from The American Chemical Society.
11
B
Hydrothermal synthesis of hydrotalcites pillared with the tetraborate anion has been
reported by Li et al.14 The final material had composition
[Mg0.70Al0.30(OH)2][B4O5(OH)4]0.15⋅0.15H2O. Energy minimisation and geometry optimisation
studies indicate that in the interlayer space the tetraborate anions orient with their tetrahedral
BO4 linkage perpendicular to the hydrotalcite sheets. The 11B MAS NMR spectrum of the
pillared material displays a sharp peak at about 2.9 ppm overlapping with a second-order
quadrupole powder pattern with a singularity at 14.0 ppm, assigned to tetrahedral and trigonal
boron, respectively. In a subsequent study on tetraborate pillared hydrotalcites prepared using a

different procedure, Arco et al. reported similar 11B MAS NMR spectra.15
Figure 4. Variable temperature (°C) static 2H NMR spectra (11.7 T) of hydrotalcite sample 1. Reprinted from R.
S. Maxwell, R. K. Kukkadapu, J. E. Amonette and H. Cho, 2H solid-state NMR investigation of terephtalate
dynamics and orientation in mixed-anion hydrotalcite-like compounds, J. Phys. Chem., 103B: 5197-5203
(1999),  1999, with permission from The American Chemical Society.
Figure 5. Two models for terephtalate reorientation in the interlayer of hydrotalcite (14.2 Å phase) assumed in
2H NMR simulations. The C-COO- bond axis is aligned perpendicular to the hydroxide layers. Model A
considers a 180º flip about the C-COO- bond direction; model B considers uniaxial rotational diffusion in
which the terephtalate anion rotates freely and stochastically about its C-COO- bond axis, instead of in discrete
180º jumps. Adapted from ref. [12].
The isotropic chemical shift, δ, the quadrupole coupling constant, CQ, and the asymmetry
parameter, η, have been extracted by simulating the spectra: tetrahedral boron δ = 3.8 ppm, CQ
= 0.98 MHz, η = 0.93; trigonal boron δ = 21.1 ppm, CQ = 2.7 MHz, η = 0.01 (Fig. 6). Since
the relative populations of the two sites are in a ca. 1 : 1 ratio NMR clearly shows the presence
of tetraborate species, thus excluding the presence of triborate species (for which a
trigonal:tetrahedral ratio of 2 : 1 is expected).
226 João Rocha
Figure 6. Experimental and simulated 11B MAS NMR spectra (9.4 T) of LDH-borate. The individual peaks
used in the simulation are also shown. Reprinted from M. del Arco, S. Gutiérrez, C. Martin, V. Rives and J.
Rocha, Effect of the Mg:Al ratio on borate (or silicate)/nitrate exchange in hydrotalcite, J. Solid State Chem.,
151: 272-280 (2000),  2000, with permission from Academic Press.
13
C
The ordering of interlayer water in hydrotalcite containing carbonate in the interlayer has
been studied by static 13C and 1H NMR of powder and oriented samples.6 The powder NMR
spectrum of hydrotalcite (Fig. 7) is clearly due to a system with axial symmetry. Spectral
simulation yields for the principal values of the chemical shift tensor σ = 119 ppm and σ⊥ =
195 ppm, in good agreement with the values obtained for carbonate in calcite (CaCO3), where
σ = 119 ppm and σ⊥ = 194 ppm. For recording the spectrum of oriented hydrotalcite the
ordering axis has been given an angle of 54.7º with the static magnetic field, so that if the
carbonate anions have their C3 axes parallel to the hydrotalcite c axis a resonance shows up at
the isotropic chemical shift position (170 ppm). Indeed, a nearly isotropic peak has been
observed with a maximum at 174 ppm, confirming that the carbonate trigonal axes are
perpendicular to the hydrotalcite layers.
The incorporation of C60 in layered double hydroxide (LDH) has been reported by Tseng et
al.16 The intercalation has been achieved by dissolving (from hexane or toluene) C60 molecules
into the hydrophobic interlayer of a LDH material previously intercalated with dodecyl sulfate
[Mg2Al(OH)6(C12H25OSO3)]. The materials have been characterised by static 13C NMR and by
spin-lattice relaxation measurements at different magnetic fields. Although the 13C MAS NMR
resonance (at ca. 144 ppm) of intercalated C60 is already sharp (0.21 ppm), it can be further
reduced substantially (0.12 ppm) by adding high-power proton decoupling to MAS. This is an
evidence for the presence of dipolar interaction between 13C nuclei in C60 and protons in
dodecyl sulfate, water molecules in the interlayer space, or hydroxy groups on the LDH. The
measured spin-lattice relaxation times indicate that the dominant interaction contributing to the
NMR relaxation of 13C in pure C60 is chemical shift anisotropy. In contrast, the mechanisms of
non-chemical shift anisotropy become the major contribution to spin-lattice relaxation for C60
intercalated in LDH. The main relaxation paths are likely through dipole-dipole interaction and
spin-rotation. This provides direct evidence that C60 is intercalated between LDH layers so that
the molecule is closely associated with the LDH lattice and experiences increasing dipolar
interaction with interlayer proton-containing species and the layer lattice atoms.
Figure 7. Experimental (top) and simulated 13C NMR powder spectrum (7.0 T) of hydrotalcite. Reprinted from
A. van der Pool, B. L. Mojet, E. van de Ven and E. de Boer, Ordering of intercalated water and carbonate anions
in hydrotalcite. An NMR study, J. Phys. Chem., 98: 4050-4054 (1994),  1994, with permission from The
American Chemical Society.
13
C MAS NMR has been much used to obtain evidence for the intercalation of many other
species in the interlayer of LDH. For example, the presence of the dianion of sebacic acid
(CH2)8(CO2)22-,17 the monoanion of capric acid, CH3(CH2)8COO-,18 monoanion and dianion of
5-bezoyl-4-hydroxy-2methoxybenzenesulfonic acid 19 and the anion of phenylphosphonic acid
20
has been confirmed in the interlayer of LDH. Surprisingly, despite the presence of large
amounts of paramagnetic Fe(III), pyroaurite materials intercalated with a series of
dicarboxylate anions, [Mg6Fe2(OH)16CO3][O2C-(CH2)p-CO2H]2⋅xH2O with p = 1-14, have
been studied by 13C CP/MAS NMR. The data show the high rigidity of the intercalated
aliphatic chain.21
228 João Rocha
15
N
The first 15N NMR study of the dynamical and structural behaviour of nitrate on the
surface-adsorbed and in the interlayer of hydrotalcite-like materials has been recently
published.22 The interlayer nitrate shows a well defined, temperature independent, uniaxial
chemical shift anisotropy powder pattern. Between -100 and +80°C and at relative humidity
(RH) 0 to 100% this species is either rigidly held or in rotation about its threefold axis. In
contrast, the dynamical behaviour for surface nitrate depends considerably on temperature and
RH. For samples at RH = 33%, for example, the surface nitrate is isotropically mobile at
frequencies greater than 100 kHz at room temperature, but it becomes rigid (or rotates about its
threefold axis) at –100°C. For dry samples the surface nitrate is not isotropically averaged at
room temperature. The mobility of interlayer nitrate is intermediate between the mobility of
carbonate and chloride.
25
Mg
The usefulness of 25Mg MAS NMR is clearly illustrated by the work of MacKenzie et al.
on the thermal decomposition of synthetic hydrotalcite with interlayer carbonate ions.23 The
spectrum of parent hydrotalcite displays a characteristic second-order quadrupole powder
pattern and resembles the spectrum of brucite [Mg(OH)2] . The isotropic chemical shifts and
quadrupole parameters for the single magnesium site in these materials are: brucite δ = 14.1
ppm, CQ = 3.15 MHz, η = 0; hydrotyalcite δ = 10 ppm, CQ = 4.4 MHz, η = 0. The relatively
large hydrotalcite quadrupole coupling constant is probably due to the presence of Al
substituents in the octahedral layer. On heating the samples the spectra of hydrotalcite and
brucite behave differently, even at 200°C. The changes observed in the spectrum of hydrotalcite
(δ = 38 ppm, CQ = 3.2 MHz, η = 0) at such a low temperature reflect the changes in the
coordination of some neighbouring Al rather than the onset of Mg(OH)2 dehydroxylation.
Further loss of hydroxyl groups as water at 300°C shifts the NMR peak (δ in the range 38 to 52
ppm) and reduces the quadrupole coupling constant (CQ in the range 1.9 to 2.4 MHz). At the
onset of the final endothermic reaction at 400°C, the NMR line shifts upfield, probably
consisting of a multicomponent spectrum containing a broad peak from MgO which is fully
developed at 600°C. Heating the sample to 1200°C, when MgAl2O4 spinel is detected by
powder XRD along with MgO, sharpens the MgO peak centred at 27 ppm.
Recently Sham and Wu reported the first triple-quantum 25Mg MAS NMR spectrum (of
magnesium formate dehydrate).24 Clearly, similar work may now be extended to hydrotalcite
materials.
27
Al
27
Al is the NMR-active nucleus which has been most used to study LDH materials. The
main reasons for this are: (i) hydrotalcite contains aluminium, (ii) because 27Al is 100%
abundant and its relaxation is relatively fast, good signal-to-noise NMR spectra may be
recorded in a matter of minutes; (iii) 27Al MAS NMR provides useful information on the
aluminium coordination. However, this is a I=5/2 quadrupolar nucleus and, as we have stressed
recording and interpreting the MAS NMR spectra requires some caution and poses certain
problems. Since the lines are broadened by the second-order quadrupole interaction, the
resonances are broad (often several ppm) and features (such as shoulders) in the spectra can not
be immediately attributed to distinct Al sites. Moreover, there is a second-order
quadrupole-induced shift and, as a result, the peak summit does not correspond to the isotropic
chemical shift. This fact makes it sometimes difficult to distinguish between, different Al
coordinations. For example, the isotropic chemical shift of penta-coordinated Al in
aluminosilicates is in the range ca. 30 - 40 ppm while four-coordinated Al resonates at δ > ca.
45 ppm.25,26 Now, the second-order quadrupole shift of a hypothetical Al site with CQ = 3 - 4
MHz and η = 0 in a static magnetic field of 9.4 T (400 MHz) is about 5 - 9 ppm. Hence, unless
an estimate of the quadrupole parameters of the different sites is available, it may be difficult to
clearly distinguish between four- and five-coordinated Al. At least two papers report the
occurrence of five-coordinated Al in calcined [Zn-Al-CO3] LDH on the basis of a 27Al NMR
peak centred at 48 - 49 ppm.27,28 Considering that the isotropic chemical shift for this resonance
must be well in excess of 50 ppm, the correct assignment is probably four-coordinated Al.
An important problem is the quantification of the relative Al populations in a LDH material.
Only for short radio-frequency pulses (flip angles smaller than, at least, π/12) is the 27Al NMR
line intensity almost independent of the quadrupole coupling parameter.26 Only under this
condition can quantitatively correct results be obtained if intensities of distinct resonances
characterised by different quadrupole interactions are compared. Many papers fail to quote in
detail the instrumental conditions used (or quote conditions that do not fulfil the <π/12
flip-angle criterion) and it is, thus, difficult to assess whether the spectra are quantitative or not.
This problem is compounded by the use of modest spinning rates. Indeed, many spectra
available in the literature have been recorded at MAS rates of 5 - 7 kHz or less and the spinning
sidebands overlap with resonances.
Almost all the papers available on 27Al MAS NMR of LDH deal with calcined materials,
although this may not be the main focus of the study. Some of the 27Al MAS NMR papers that
concentrate more on the issue of thermal decomposition are ref. 8, 23, 29-33. Some other useful
references on this subject are ref. 18, 34-40. As an example of the type of 27Al MAS NMR
spectra obtained on a LDH with composition [Mg0.64Al0.36(OH)2](CO3)0.18⋅0.78 H2O), consider
Fig. 8.33 The spectrum of the parent material contains a sharp (full-width at half-maximum
FWHM, ca. 370 Hz) peak at 9.1 ppm with a relatively broad low-frequency shoulder, assigned
to six-coordinated Al. The sheared triple-quantum MAS NMR spectrum (Fig. 9) clearly shows
that the sample contains two types of Al sites (overlapping resonances S1 and S2). The peak S1
displays an important distribution of isotropic chemical shifts. This may be due to the presence
of a range of slightly different Al environments generated by the random insertion of Al in the
layers. Site S2 has an average quadrupole coupling constant much larger than S1. When the
sample is calcined at 250°C the six-coordinated Al peak shifts to 8.8 ppm and broadens
(FWHM 860 Hz), indicating that the structure becomes increasingly disordered. About 25% of
Al(III) ions migrate from octahedral to tetrahedral coordination (peak at 76 ppm), giving raise
to cation vacancies in the layer. At 350°C the structure undergoes major changes. The
four-coordinated Al peak at 76 ppm accounts for ca. 47% of the total area. The six-coordinated
Al resonance is quite broad (FWHM 1400 Hz) and shifts slightly to 9.9 ppm. At 450°C both the
four- and the six-coordinated Al peaks broaden further and shift slightly to 72 and 12 ppm. The
230 João Rocha
unsheared triple-quantum MAS NMR spectrum contains a single four-coordinated Al peak and
two overlapping six-coordinated Al peaks. At 750°C the spectrum changes only slightly, but at
1000°C a totally different spectrum is observed. Triple-quantum MAS NMR shows that two
six-coordinated and three four-coordinated Al resonances are present.
Several papers study the rehydration of calcined LDH materials by 27Al MAS NMR, for
example ref. 8, 30, 33, 35, 37, 39.
The intercalation and pillaring of different anions in LDH has also been the subject of 27Al
MAS NMR studies, for example: pillaring of [Zn-Al] with PW11VO404-,41 and of [Zn-Al] and
[Mg-Al] with PW11O397-;28 intercalation of [Mg-Al] with the anions of phenylphosphonic
acid,20 and [Cd-Al] with the anions of phenylphosphonic acid and 2-carboxyethylphosphonic
acid;42 pillaring and polymerisation of silicates in [Mg-Al],15,43,44 and [Zn-Al];10 pillaring of
[Mg-Al] with borate anions.14,15
29
Si
This is a useful nucleus to study the polymerisation and pillaring of siliceous species in the
LDH interlayer. 29Si MAS NMR is very sensitive to the condensation degree x of
Si(OSi)x(OH)4-x species and to the substitution degree y of the second Si neighbours by another
element, Si(OSi)x-y(OM)y(OH)4-x (M = Al, Ga, …).10 Anionic exchange from LDH-Cl has been
successfully used by Schutz and Biloen to prepare LDH-silicate materials.43 Powder XRD, 27Al
and 29Si MAS NMR suggested the presence of interlayer [Hsi2O5]nn- polymers. Fyfe et al.
reported a partial Cl-/Si8O208- exchange in LDH-Cl, but only when the molar Mg : Al ratio is
equal or lower than 3.44 Carbonate contamination prevents a complete exchange. Yun et al.
used tetraethylorthosilicate to intercalate silicate in LDH materials starting from synthetic
meixnerite, the [Mg-Al] LDH with interlayer hydroxyl groups. They report that silicate anions
are formed by hydrolysis and condensation of silanol groups. The polymerisation of silicate
anions in the interlayer of [Zn-Al] and [Zn-Cr] LDH has also been studied.10 Recently, the
incorporation of silicate in [Mg-Al] LDH by anion exchange from a LDH-nitrate precursor has
been reported.15 The 29Si MAS NMR spectrum of this material displays resonances at -92, -99
and -110 ppm which have been assigned to Si(OSi)x(OH)4-x environments with x = 2 - 4,
respectively. This assignment is supported by the 29Si CP/MAS NMR spectrum which exhibits
only the peaks given by the sites with x = 2, 3. This is because the CP technique leads to a
strong and selective enhancement of these signals, with a characteristic dependence of the
relative intensities on the chosen cross-polarisation contact time, τ. At short τ (such as the 2 ms
the authors have used to record the spectra) those silicons having the shortest Si-H distance,
that is, the x = 2, 3 silicons bearing OH groups, are most effectively cross-polarised and show
the highest intensity. With increasing τ, silicons with larger Si-H distances (x = 4) give rise to
increasing intensity of the signal at -110 ppm and dominate the spectrum at long τ (25 - 30 ms).
The -92 and -99 ppm peaks may also have a contribution from Si local environments where
silanols are replaced by OAl groups.
Figure 8. 27Al MAS NMR spectra (9.4 T) of hydrotalcite and materials calcined at the temperatures indicated.
Reprinted from J. Rocha, M. del Arco, V. Rives and M. A. Ulibarri, Reconstruction of layered double
hydroxides from calcined precursors: a powder XRD and 27Al MAS NMR study, J. Mater. Chem., 9:
2499-2503 (1999),  1999, with permission from The Royal Society of Chemistry.
Figure 9. Triple-quantum 27Al MAS NMR spectrum (9.4 T) of hydrotalcite. Reprinted from J. Rocha, M. del
Arco, V. Rives and M. A. Ulibarri, Reconstruction of layered double hydroxides from calcined precursors: a
powder XRD and 27Al MAS NMR study, J. Mater. Chem., 9: 2499-2503 (1999),  1999, with permission
from The Royal Society of Chemistry.
232 João Rocha
31
P
This nucleus has not been much used to characterise LDH materials. In an interesting study,
Hu et al. intercalated PW11VO404- in [Zn-Al] and studied the orientation of the polyanion in the
interlayer by 31P MAS NMR.41 Pure α-PW11VO404- displays a single resonance at -12.2 ppm
while the intercalated anion gives two peaks at -11.9 and -14.0 ppm on a 2 : 1 intensity ratio.
Now, for substituted Keggin-type PW11VO404- species, the 12 octahedra around the central P
are not identical. If in the intercalated polyanion the C2 axis is perpendicular to the sheet there
are two different sites which the VO6 octahedra can adopt leading to different 31P NMR
chemical shifts whose relative areas should correspond to the ratio of the probability of the two
types of V (2 : 1) in accord with the NMR evidence. If, on the other hand, the α-PW11VO404-
adopts a C3 axis orientation, the probability ratio of the two different V sites is 1 : 1, and can
thus be discounted. The orientational preference of other pillared hetero-polyoxometallates can,
in principle, be studied by this method. The intercalation of phenylphosphonic acid in [Mg-Al]
has also been studied by 31P MAS NMR.20
35
Cl
In an interesting study, Kirkpatrick et al. reported on 35Cl wide-line NMR of chloride

intercalated hydrotalcite and the layered calcium-aluminate hydrate hydrocalumite (Friedel’s
salt).45 In hydrocalumite the Ca,Al distribution is ordered, the interlayer water is directly
coordinated to Ca in the hydroxide layer (creating seven-fold Ca), and the interlayer chloride
and water sites are well ordered. In contrast, in hydrotalcite the Mg and Al of the main
hydroxide layer are disordered over one site but retain the sixfold coordination of Mg in brucite.
The distribution of anions and water molecules in the interlayer space is, thus, disordered.
The 35Cl NMR data for hydrocalumite show that the interlayer Cl- site has uniaxial (or
nearly so) symmetry above 0°C and reduced (triaxial) symmetry at lower temperatures. Indeed,
from 10 to 130°C the second-order powder pattern attributed to interlayer Cl- can always be
simulated with η = 0 (axial or nearly axial symmetry), while below ca. 10°C the patterns are
simulated with η = 0.9 (non-axially symmetric interlayer Cl- site). Differential scanning
calorimetry (DSC) data show this change to be due to a structural phase transition below 6°C.
NMR and powder XRD suggest that this phase transformation is due to dynamical
order-disorder involving the rigid interlayer atomic arrangement at low temperatures and
dynamically averaged interlayer species at high temperatures. The 35Cl NMR data for
hydrotalcite show poorly resolved signal indicating a distribution of Cl- local environments and
a change from triaxial to uniaxial (or nearly so) symmetry at Cl- occurring over a broad
temperature interval below -40°C. DSC data show a broad and poorly defined endothermic
peak in the -100 to -75°C range. This suggests the presence of a phase transition that occurs
over a larger temperature range due to disordered interlayer structure of hydrotalcite.
51
V
This is a I=7/2, almost 100% abundant nucleus which has not been much used to study
LDH. The relatively small quadrupole interaction of 51V results in spectra which are usually
dominated by chemical shift anisotropy. However, this assumption can not always be made,
and the simulation of the static and MAS spectra must consider both the chemical shift and the
quadrupole coupling tensors. This type of simulation is not trivial and in most cases coincident
quadrupole and chemical shift tensors are assumed for simplicity. It has been shown that the
isotropic chemical shift can not be used to determine the coordination of the vanadium
species.46,47 Indeed, the spectroscopic parameter that differentiates between the various
tetrahedral and octahedral vanadium(V) oxide coordination environments is the static NMR
lineshape which is dominated by chemical shift anisotropy. For example, vanadium in an
isolated tetrahedral site (Q1 type) is in a very regular environment, giving rise to isotropic
spectra with chemical shift tensor principal components δ1 ≈ δ2 ≈ δ3 and a chemical shift
anisotropy |δ3 - δ1| ≤ 100 ppm. Q1 environments (VO4 tetrahedra which share one oxygen atom
with one neighbouring VO4 tetrahedron) display asymmetric chemical shift tensors (principal
components δ1 ≠ δ2 ≠ δ3) with a chemical shift anisotropy of 80 - 300 ppm. Distorted Q2
environments exhibit even larger chemical shift anisotropy, in the range 400 - 600 ppm. V
atoms in distorted octahedral environments give signals with almost axial symmetry (δ1 ≈ δ2 ≠
δ3) with a chemical shift anisotropy in the range 500 - 700 ppm. In summary, although
recording 51V MAS spectra with the fastest spinning rates available is very useful, static spectra
should always be recorded.
The first study of pillaring of a LDH material with polyoxometalates has been reported by
Pinnavaia and co-workers. 48 In this work, [Zn-Al] and [Ni-Al] LDHs have been pillared with
V10O286-. 51V MAS NMR shows that the intercalated anion retains its structural integrity.
Consider now the following example of the use of 51V NMR in the study of LDH
materials.49 [Mg-Al] hydrotalcite was impregnated using aqueous solutions of ammonium
metavanadate and subsequently calcined in air at 600°C. The supported metal species have
been studied by 51V static and MAS NMR and by other techniques. The wideline and MAS
NMR spectra of a sample with high vanadium loading (labelled 48V/CH) displays a peak
centred at about -555 ppm. The MAS spectrum consists of a resonance at -555 ppm and a very
weak peat at -609 ppm. Comparison with model compounds indicates the presence of
pyrovanadate α-Mg2V2O7. However, the relative intensity of both peaks suggests the
contribution of another species to the peak at –555 ppm, indicating that Mg3V2O8 may also
form. A similar study is available from the same group.50
A particularly interesting work has been reported by Ménétrier et al.51 The reduction of
mixed nickel-cobalt γ-oxide-hydroxides in a NH4VO3/H2O2 medium leads to LDH materials in
which vanadate species are inserted in order to compensate for the excess positive charges
brought by Co(III) ions. Static 51V NMR spectra recorded after various sample treatments show
that the hyperfine magnetic interaction exerted by unpaired Ni(II) electrons on the inserted
vanadium nuclei allows to determine whether the latter are grafted to the layer or not. Indeed,
the spectra of the pristine materials are dominated by a narrow signal at -600 ppm. Upon
vacuum or thermal treatment, another peak at 850 ppm grows gradually at the expense of the
former. This new signal is less defined and broader than the former one; since a grafting process
is assumed in those conditions, it is attributed to V atoms which are grafted via oxygen to the
234 João Rocha
nickel atoms of the Ni1-yCoy(OH)2 slabs. This assignment is supported by the position of the
NMR peak: while vanadate species are usually found in the -400 to -800 ppm range, the new
signal (at 850 ppm) is shifted by nearly 1500 ppm to high frequency. This implies that a new
type of interaction occurs. Indeed, the existence of V-O-Ni bonds allows the transfer of
unpaired electrons from the Ni(II) to the vanadium via the orbitals overlap. This hyperfine
interaction causes a broadening and a (Fermi contact) shift of the NMR signal vs. that due to V
atoms with no V-O-Ni bond (peak at -600 ppm). The grafting is thus seen by NMR through the
unpaired Ni(II) electrons.
71
Ga
71
Ga and 27Al NMR provide similar information on the structure of LDH materials.
Although 69Ga is also a NMR-active nucleus, so far, it has not been used to study hydrotalcites
and related materials. Even though the nuclear quadrupole moments and the gyromagnetic
ratios are similar for all the three isotopes, the smaller nuclear spin quantum number of 69Ga
and 71Ga (I=3/2) results in much broader widths for these nuclei relative to 27Al (I=5/2), when
the second-order quadrupole interaction is dominant. At the same magnetic field strength, the
relative ratio of the line widths for 27Al, 69Ga and 71Ga is ca. 1 : 6.5 : 2.0.52 This indicates that
solid-state gallium NMR is expected to be much more difficult than aluminium NMR because
it requires much higher MAS rates and shorter 90º pulses to excite the broader spectral widths
observed. Of the two gallium isotopes, 71Ga is more attractive because of its smaller quadrupole
moment and larger gyromagnetic ratio, which compensate for its lower natural abundance.
Bradley et al. have shown that a linear relationship exists between the 27Al and 71Ga chemical
shifts (δ71Ga = 2.83 δ27Al – 4.50).53 Thus, for example, in gallium silicates four-coordinated Ga
resonates at 120 to 224 ppm while six-coordinated Ga resonates at -5 to 55 ppm.
Aramendia et al. studied by 27Al and 71Ga MAS NMR as-prepared and calcined [Mg-Al],
[Mg-Ga] and [Mg-Al-Ga] LDH materials.31,32 As-prepared samples contain octahedral Al (27Al
NMR peak at ca. 9 ppm) and Ga (71Ga NMR peak at ca. -18 ppm) showing that Ga(III) is, like
Al(III), an effective isomorphic substitute for Mg(II). Samples calcined at 500°C contain
octahedral and tetrahedral Al (9.6 ppm, 74 ppm) and Ga (ca. –20 and ca. 60 ppm). The
difficulty in obtaining good quality 71Ga MAS NMR spectra of LDH materials is particularly
evident in certain reports where low spinning rates (5 kHz) have been used.9 At least another
work is available on 71Ga MAS NMR of LDH materials.28 Here, a resonance at 56 ppm is
attributed to tetrahedral gallium, while in principle this shift falls in the range of octahedral
gallium.
77
Se
The first 77Se static and MAS NMR study of the dynamical and structural behaviour of
selenate and selenite in hydrotalcite-like materials has been recently reported.54 The swelling
properties and dynamical behaviour of the anions in the intercalated materials are very different
and the results provide significant new insight into the structure and dynamical behaviour of the
LDH interlayer and surface anions. For example, it has been found that selenate-LDH expands
from a one water layer to two water layer structure in response to increasing relative humidity.
This structural transition can be followed by monitoring changes in the 77Se chemical shift
anisotropy. In contrast, selenite-LDH does not expand with increasing relative humidity and
spectroscopically resolvable surface-adsorbed and interlayer selenite have very different
dynamical characteristics.
119
Sn
It seems that only one paper has been published, so far, on 119Sn NMR of LDH materials.
The spectra of a series of [Mg-Al-Sn] hydrotalcites display broad peaks centred at -580 to -600
ppm, attributed to Sn(IV) in a distorted octahedral environment.40
EPR STUDIES ON LAYERED DOUBLE HYDROXIDES

Much of the EPR work carried out so far on LDH is concentrated on materials intercalated
with species such as halocomplexes, cyanocomplexes, complexes with macrocyclic ligands,
oxo and polyoxometalates. A few studies are available on the redox sites present in the LDH
layers.
The structure of [NiCl4]2- intercalated in [Al-Li] LDH was studied by powder XRD,
EXAFS and EPR.55 The small interlayer distance (2.9 Å), calculated on the basis of a 7.7 Å
basal spacing, indicated that the [NiCl4]2- anion was not in a tetrahedral coordination geometry.
EXAFS yielded for the complex in LDH first-neighbour Ni-Cl distances of 2.1 Å, compatible
with four-fold coordination. Since the EPR spectrum of the intercalated LDH showed no
absorption, the [NiCl4]2- was considered to be square planar (no unpaired electrons) rather then
tetrahedral (two unpaired electrons).
Carrado et al. observed that on grinding crystals of a [Mg-Al]-[Fe(CN)64-] LDH the color
of the sample changed from green to gray.56 EPR spectra displayed a signal near g = 4.1
attributed to Fe(III) in tetrahedral or octahedral environment. Mössbauer spectroscopy also
indicated the reduction of Fe(III) to Fe(II) through pressure during grinding.
Iliev et al. studied the oxidation of 2-mercaptoethanol catalised by Co(II) pthalocyanine
tetracarboxylate or Co(II) pthalocyanine tetrasulfonate intercalated in [Mg-Al] hydrotalcite.57
The EPR spectra of Co(II) and Cu(II) pthalocyanine tetracarboxylate intercalated in
hydrotalcite showed, for a low concentration of the metal phtalocyanine complexes (5 µm g-1 of
LDH support), a hyperfine splitting from 57Co (I=7/2) and 63,65Cu (I=3/2). For the Cu(II)
complex a superhyperfine splitting from 14N (I=1) was also observed. These results are
consistent with magnetically diluted molecules of the complexes in the (low-concentration)
samples. When the complexes concentration was raised to 60 µm g-1 of LDH support, EPR
spectra characteristic of aggregated and microcrystalline complexes were also recorded.
Specifically, a narrow singlet at g = 2.004, characteristic of the Co(II) pthalocyanine
tetracarboxylate sodium salt having defects in the crystal lattice, was observed. This signal did
not disappear after repeated heating-evacuation-purging cycles, meaning that it is not due to
superoxo complexes formed by monomeric cobalt pthalocyanine molecules.
236 João Rocha
The orientation, hydration state and electronic properties of Co(II) tetrakis(N-methyl-4-

pyridiniumyl)porphyrin (CoTMPyP) cation and Co(II) tetrasulphophtalocyanine anion
(CoPcTs), intercalated in negatively charged layered aluminosilicates (hectorite and
fluorhectorite) and positively charged LDH, respectively, were studied in the presence or
absence of water by EPR and powder XRD.58 The intercalated species exhibit very different
orientation in the galleries of layered supports, depending on the charge density of the support
and the hydration state of the galleries. When intercalated on (low charge density) hectorite,
CoTMPyP orients with the plane of the porphyrin parallel to the clay layers. The g tensors for
wet and dry samples (g|| = 1.88, g⊥ = 3.10) indicate that CoTMPyP interacts with the
charge-deficient siloxane oxygens on the clay surface. There is no water coordinated to Co(II)
and the metal d-orbitals are contracted. Hence, in CoTMPyP-hectorite the metal centres can not
be good catalyst sites because they are inaccessible and chemically unreactive. Intercalation of
CoTMPyP in (high charge density) fluorohectorite causes the porphyrin ring to orient at a 27º
angle to the clay layers with water molecules coordinated to Co(II) (g|| = 2.03, g⊥ = 2.42). Upon
vacuum dehydration, the basal spacing decreases from 19.6 to 17.6 Å and the intercalated
complex rearranges into a staggered bilayer with no axial water bound to Co(II). In
CoPcTs-LDH the phtalocyanine orients edge on. ESR (g|| = 2.05, g⊥ = 2.45) indicates that Co(II)
has water in axial coordination sites when wet or air-dried. In hydrated fluorohectorite and
LDH the Co(II) dz2 orbital is high in energy, making the metal center chemically reactive in
catalytic electron-transfer reactions.
Zikmund et al. prepared, under argon, [Mg-Al] hydrotalcite intercalated with square planar
complexes of Co(II) and Schiff bases salen and salophen.59 The basal spacings were 13.1 and
11.6 Å for the salen and salophen derivatives, respectively, suggesting that the anions have their
molecular plane parallel to the LDH layers. After contact with air, the ESR spectra of the
materials displayed a narrow signal (I) with δH = 120 mT showing hyperfine structure, and a
signal (II) with g = 2.02 and δH = 950 mT. The latter signal is removed upon heating at 300°C,
but is restored when the temperature decreases. Since no 59Co hyperfine splitting was observed,
signal I was attributed to superoxide species interacting with Al(III) ions. Signal II resembles
the signal observed for other immobilized Co(salen)-dioxygen complexes.
Salinas and Ono studied the thermal transformation (air and vacuum) of [Mg-Al] LDH
materials pillared with decavanadate isopolyanions (V10O286-).60 At 200°C the intercalated
isopolyanion breaks up into smaller species with V in tetragonal or square-pyramidal
coordination. At 300-350°C these species rearrange to form polymeric vanadate species of the
type [-VO3-]nn- and, simultaneously, part of the V(V) is reduced to V(IV), even when the
sample is calcined in air. The layered structure is still maintained, though the brucite layers are
completely dehydroxylated. The number of V(IV) species increases steadily from 0.1% of the
total V atoms in the interlayers, at 120°C, to 6% at 200°C (calcinations in air). At higher
temperatures the number of V(IV) species decreases. These results suggest that in the 51V NMR
studies reported in references 49 and 50, not all vanadium species are observable. It is, thus,
advisable to use both EPR and NMR data in order to study the thermal decomposition of
vanadium-containing LDH materials. At least another paper is available on the thermal
transformation of LDH materials intercalated with decavanadate anions studied by EPR.61
The one-electron reducing sites and their strength distribution on [Mg-Al] hydrotalcite,
MgO and Al2O3 surfaces have been measured using a series of electron-acceptor molecules
(nitrobenzene, m-dinitrobenzene, sym-trinitrobenzene, 2,4-dinitrotuluene and tetracyanoethene)
with different electron affinity (Eea).62 The resulting surface adsorbed radical anions and their
concentrations have been studied by EPR. For all samples studied, the EPR spectrum consists
of a three lines anisotropic signal attributed to the adsorbed radical anions, the unpaired
electron interacting with only one of the 14N nuclei of the nitro groups, irrespective of the fact
that the acceptor molecule contains one to three nitro groups. The concentration of the reducing
sites on the hydrotalcite and Al2O3 surfaces, but not on the MgO surface, correlates with the Eea
values of the corresponding acceptor compounds. The lack of correlation found for MgO is due
to the fact that on the very strong reducing sites of this surface the acceptor compounds with
very high Eea yield non-paramagnetic di-anion species.
Velu et al. prepared a series of [Mg-Mn-Al] LDH materials which have been studied by
powder XRD, EPR and UV-visible diffuse reflectance spectroscopy.63 Nearly 20% of the metal
ions in LDH can be isomorphously substituted by Mn2+/Mn3+ ions to obtain a single phase
corresponding to a [Mg-Mn-Al] ternary LDH. Partial oxidation of Mn2+ to Mn3+ took place
during the synthesis. The as-prepared samples give a EPR sextet with g = 2.0147 and hyperfine
coupling constant A = 95 G, attributed to Mn2+ ions in distorted octahedral coordination in the
brucite-like layer. Mn3+ is EPR silent owing to its large zero-field splitting. Calcination of the
Mn-containing LDH materials at 450°C in air results in the formation of spinel phases such as
Mn3O4 and MnAl2O4, along with a MgO-like phase. In addition, nearly 50% of the Mn2+ is
oxidized to Mn3+. The as-prepared samples catalyze the liquid-phase oxidation of toluene
producing selectively benzaldehyde/benzoic acid and the catalytic activity increases with
increasing Mn content in the LDH.
[Mg-Al-NO3] LDH materials were partially exchanged with MoO42- and WO42- and used
as heterogeneous catalysts for the decomposition of H2O2 into singlet molecular oxygen
(1O2).64 The intercalated anions were present as monomeric tetrahedral species. With
LDH-MoO42- and H2O2, 1O2 is the prevailing reactive oxygen species, while EPR trapping
detected a minor amount of free OH. radicals which do not contribute to product formation in
olefin oxygenation. LDH-WO42- transforms H2O2 into 1O2 about four times slower than the Mo
catalyst and effects mono-oxygen transfer to electron-rich substrates such as amines and olefins.
In conclusion, LDH-MoO42- is a good heterogeneous catalyst for 1O2 generation, with minimal
interference by undesirable reactive oxygen species.
CONCLUSION
NMR is clearly one of the best tools available to study the structure and dynamics of LDH
materials. Although most of the NMR work has been concentrated on a few NMR-active nuclei
(such as 1H, 13C, 29Si and 27Al), informative reports are available on other nuclei and the future
work can build upon this knowledge. It is fair to say that LDH scientists who are not NMR
specialists may now use this technique to help solving their specific problems. At the same time
many challenges remain to the NMR spectroscopist. Sophisticated experiments, capable of
yielding much more information than simple magic-angle spinning NMR, are now available,
particularly for the study of quadrupolar nuclei, and they can be used to investigate LDH
materials. Useful nuclei, present in hydrotalcites and related materials, which have not been
used or have been largely ignored, such as 17O and 25Mg, deserve more attention. EPR
spectroscopy complements NMR allowing the study of paramagnetic species both within the
238 João Rocha
LDH layers and in the interlayer space. However, EPR seems to have been much less used than
NMR to study these materials and, clearly, more work is necessary. In the near future we hope
to see more innovative work coming out on NMR and EPR studies of LDH and related
materials.
REFERENCES
- Y. Wu, B. Q. Sun, A. Pines, A. Samoson and E. Lippmaa, J. Mag. Reson. 89 (1990) 297.
1) A. Llor and J. Virlet, Chem. Phys. Lett. 152 (1988) 248.
2) K. T. Mueller, B. Q. Sun, G. C. Chingas, J. W. Zwanziger, T. Terao and A. Pines, J. Mag.
Reson. 86 (1990) 470.
3) L. Frydman and J. S. Harwood, J. Am. Chem. Soc. 117 (1995) 5367.
4) C. Fernandez and J. P. Amoureux, Solid State NMR 5 (1996) 315.
5) A. van der Pol, B. L. Mojet, E. van de Ven and E. de Boer, J. Phys. Chem. 98 (1994)
4050.
6) G. Marcelin, N. J. Stockhausen, J. F. M. Post and A. Schutz, J. Phys. Chem. 93 (1989)
4646.
7) F. Rey, V. Fornés and J. M. Rojo, J. Chem. Soc. Faraday Trans. 88 (1992) 2233.
8) M. A. Aramendía, V. Borau, C. Jiménez, J. M. Marinas, F. J. Romero and J. R. Ruiz, J.
Solid State Chem. 131 (1997) 78.
9) C. Depège, F.-Z. El Metoui, C. Forano, A. de Roy, J. Depuis and J.-P. Besse, Chem.
Mater. 8 (1996) 952.
10) J. Dupuis, J. P. Battut, Z. Fawal, H. Hajjimohamad, A. de Roy and J. P. Besse, Solid State
Ionics 42 (1990) 251.
11) R. S. Maxwell, R. K. Kukkadapu, J. E. Amonette and H. Cho, J. Phys. Chem. 103B
(1999) 5197.
12) R. K. Kukkadapu, R. S. Maxwell, M: S. Witkowski, J. E. Amonette and H. M. Cho. In
Program (with abstracts) of the 11th International Clay Conference; June 15-21, 1997,
Ottawa, Ontario, Canada, 1997, pp. A45.
13) L. Li, S. Ma, X. Liu, Y. Yue, J. Hui, R. Xu, Y. Nao and J. Rocha, Chem. Mater. 8 (1996)
204.
14) M. Del Arco, S. Gutiérrez, C. Martin, V. Rives and J. Rocha, J. Solid State Chem. 151
(2000) 272.
15) W.-Y. Tseng, J.-T. Lin, C.-Y. Mou, S. Cheng, S.-B. Liu, P. P. Chu and H.-W. Liu, J. Am.
Chem. Soc. 118 (1996) 4411.
16) S. Carlino and M. J. Hudson, J. Mater. Chem. 4 (1994) 99.
17) S. Carlino and M. J. Hudson, J. Mater. Chem. 5 (1995) 1433.
18) K. R. Frankli, E. Lee and C. C. Nunn, J. Mater. Chem. 5 (1995) 565.
19) S. Carlino, M. J. Hudson, S. W. Husain and J. A. Knowles, Solid State Ionics 84 (1996)
117.
20) L. Raki, D. G. Rancourt and C. Detellier, Chem. Mater. 7 (1995) 221.
21) X. Hou, R. J. Kirkpatrick, P. Yu, D. Moore and Y. Kim, Am. Mineral. 85 (2000) 173.
22) K. J. D. Mackenzie, R. H. Meinhold, B. L. Sherriff and Z. Xu, J. Mater. Chem. 3 (1993)
1263.
23) S. Sham and G. Wu, Inorg. Chem. 39 (2000) 4.

24) S. M. Bradley, R. F. Howe and R. A. Kydd, Magn. Reson. Chem. 31 (1993) 883.
25) G. Engelhardt and D. Michel, High-Resolution Solid-State NMR of Silicates and Zeolites,
John Wiley & Sons, New York, 1987.
26) S. Velu, V. Ramkumar and C. S. Swamy, J. Mater. Sci. 32 (1997) 957.
27) M. R. Weir and R. A. Kydd, Inorg. Chem. 37 (1998) 5619.
28) M. J. Hudson, S. Carlino and D. C. Apperley, J. Mater. Chem. 5 (1995) 323.
29) D. Tichit, M. N. Bennani, F. Figueras and J. R. Ruiz, Langmuir 14 (1998) 2086.
30) M. A. Aramendia, Y. Avilés, V. Borau, J. M. Luque, J. M. Marinas, J. R. Ruiz and F. J.
31) M. A. Aramendia, Y. Avilés, J. A. Benítez, V. Borau, J. Jiménez, J. M. Marinas, J. R.
Ruiz and F. J. Urbano, Microporous Mesoporous Mater. 29 (1999) 319.
32) J. Rocha, M. Del Arco, V. Rives and M. A. Ulibarri, J. Mater. Chem. 9 (1999) 2499.
33) J. Shen, J. M. Kobe and J. A. Dumesic, Langmuir 10 (1994) 3902.
34) L. M. Parker, N. B. Milestone and R. H. Newman, Ind. Eng. Chem. Res. 34 (1995) 1196.
35) M. Belloto, B. Rebours, O. Cause, J. Lynch, D. Bazin and E. Elkaïm, J. Phys. Chem. 100
(1996) 8535.
36) A. Béres, I. Pálinkó, J.-C. Bertrand, J. B. Nagy and I. Kiricsi, J. Mol. Struct. 410-411
(1997) 13.
37) J. Shen, M. Tu and C. Hu, J. Solid Sate Chem. 137 (1998) 295.
38) A. Béres, I. Pálinkó, I. Kiricsi, J. B. Nagy, Y. Kiyozumi and F. Mizukami, Appl. Catal. A:
General 182 (1999) 237.
39) S. Velu, K. Suzuki, M. Okazaki, T. Osaki, S. Tomura and F. Ohashi, Chem. Mater. 11
(1999) 2163.
40) C.-w. Hu, Q.-l. He, Y.-h. Zhang, Y.-y. Liu, Y.-f. Zhang, T.-d. Tang, J.-y. Zhang and E.-b.
Wang, Chem. Comm. (1996) 121.
41) F. M. Vichi and O. L. Alves, J. Mater. Chem. 7 (1997) 1631.
42) A. Schutz and P. Biloen, J. Solid State Chem. 68 (1987) 360.
43) C. A. Fyfe, G. Fu and H. Grondey, Mat. Res. Soc. Symp. Proc. 364 (1994) 907.
44) R. J. Kirkpatrick, P. Yu, X. Hou and Y. Kim, Am. Mineral. 84 (1999) 1186.
45) H. Eckert and I. Wachs, J. Phys. Chem. 93 (1989) 6796.
46) R. H. H. Smiths, K. Seshan, J. R. H. Rossa and A. P. M. Kentgens, J. Phys. Chem. 99
(1995) 9169.
47) T. Kwon, G. A. Tsigdinos and T. J. Pinnavaia, J. Am. Chem. Soc. 110 (1988) 3653.
48) T. Blasco and J. M. L. Nieto, Colloids and Surfaces A: Phys. Engin. Aspects 115 (1996)
187.
49) T. Blasco, J. M. L. Nieto, A. Dejoz and M. I. Vazquez, J. Catal. 157 (1995) 271.
50) M. Ménétrier, K. S. Han, L. Guerlou-Demourgues and C. Delmas, Inorg. Chem. 36
(1997) 2441.
51) H. Kyung, C. Timken and E. Oldfield, J. Am. Chem. Soc. 109 (1987) 7669.
52) S. M. Bradley, R. F. Howe and R. A. Kydd, Magn. Reson. Chem. 31 (1993) 883.
53) X. Hou and R. J. Kirkpatrick, Chem. Mater. 12 (2000) 1890.
54) K. Okada, F. Matshushita and S. Hayashi, Clay Miner. 32 (1997) 299.
55) K. A. Carrado, A. Kostapapas and S. Suib, Solid State Ionics 26 (1988) 77.
56) V. I. Iliev, A. I. Ileva, L. D. Dimitrov, Appl. Catal. A: General 126 (1995) 333.
240 João Rocha
57) L. Ukrainczyk, M. Chibwe, T. J. Pinnavaia and S. A. Boyd, J. Phys. Chem. 98 (1994)

2668.
58) M. Zikmund, K. Putyera and K. K. Hrnciarova, Chem. Papers 50 (1996) 262.
59) E. L. Salinas and Y. Ono, Bull. Chem. Soc. Jpn. 65 (1992) 2465.
60) K. Bahranowski, R. Dula , F. Kooli and E. M. Serwicka, Colloids and Surfaces A 158
(1999) 129.
61) H. Caldararu, A. Caragheorgheopol, A. Corma, F. Rey and V. Fornés, J. Chem. Soc.
Faraday Trans. 90 (1994) 213.
62) S. Velu, N. Shah, T. M. Jyothi and S. Sivasanker, Micropor. Mesopor. Mater. 33 (1999)
61.
63) B. F. Sels, D. E. De Vos, P. J. Grobet, F. Pierard, F. K.-De Mesmaeker and P. A. Jacobs, J.
Phys. Chem. 103B (1999) 11114.
Chapter 7
INVESTIGATING LAYERED DOUBLE HYDROXIDES

BY MÖSSBAUER SPECTROSCOPY
Chr. Bender Koch

Chemistry Department, The Royal Veterinary and Agricultural University
Thorvaldsensvej 40, DK-1871 Frederiksberg C., Denmark.
INTRODUCTION
Mössbauer spectroscopy monitors transitions between nuclear ground and excited states.
The Mössbauer effect is recoil-free emission and resonant absorption of γ-ray in the nucleus.
The usefullness of Mössbauer spectroscopy in the context of LDH relies on the occurence of an
element exhibiting the Mössbauer effect in the cation layer and/or the interlayer, and the
coupling between the hyperfine parameters of the nucleus and the electronic properties of the
element. Regarding the elements investigated, almost all work on LDHs have been done using
the 57Fe isotope which occurs with a natural abundance of 2.1 %. Although the energy shifts of
the nucleus in different electronic environments is fairly small, this is compensated by the
extremely high energy resolution of Mössbauer spectroscopy. In a classical source experiment
the resonant conditions are probed by varying the energy of the γ-quanta using the Doppler
effect. This implies moving a source with an, e.g., constant acceleration, and therefore the
energy unit chosen in Mössbauer spectroscopy is the velocity of the radioactive source. Most
experiments are conducted in transmission geometry and thus the measured quantity is related
to the (relative) absorption of the γ-quanta as a function of the velocity of the source.
The Mössbauer spectral parameters are conviniently divided into the hyperfine parameters
and the lattice associated parameters. The hyperfine parameters are a consequence of electric
and magnetic interactions between the nucleus and the surrounding electrons. The isomer shift
depends on the difference in size of the nucleus in the excited and ground state and on the
difference between the chemical environments in the source and the absorber (sample). The
quadrupole interaction depends on the quadrupole moment and the electric field gradient.
These two interactions are causing the isomer shift (δ) and the quadrupole splitting (∆EQ) that
are derived from the spectra, and assignments of oxidation and spin states are frequently based
on these two parameters and their temperature dependence. Thirdly, the magnetic hyperfine
interaction measures the magnetic induction (Bhf) on the nucleus. This depends on the details in
242 Chr. Bender Koch
the structure and coupling, allowing to differentiate among different structures. Selection rules
determine the allowed transitions, and typically the spectra consist of singlets, doublets, and
sextets or combinations thereof.
Both the quadrupole and the magnetic hyperfine splitting exhibit directional dependent
properties and for materials like LDHs, that may exhibit preferred texture, this may be
important. In general, a texture effect will cause the two lines of a doublet to have unequal
intensity.
The lattice contribution allows to gain insight into the dynamics of the bonding in the
lattice. For layered structures it has to be considered that the likelihood of a non resonant
emission or absorption to occur depends on the stiffness of the lattice, which may vary along
different directions. For highly anisotropic materials like LDHs this may potentially influence
the Mössbauer spectrum, but a convincing case of this effect in LDHs has not been presented.
A well defined position of the cation in the lattice is one that might be considered to possess
a unique local structure that is repeated indefinitely in the crystal. However, changes in, e.g.,
the nearest cations and anions (size and charge) will cause a change in the electric field gradient
of that site and a general smearing out of the electric field gradient for that position in the
crystal. Such changes may cause new components to appear, but effects like broadening and
asymmetries of the lines are also to be expected. It is often assumed that the structure and
chemistry of the anions are invarient, thus emphasising the next nearest cation neighbours
(NNN), but for structures containing hydroxy groups differences in acidities may change the
charge and thus the local electric field gradient. For 2-dimensional structures like LDHs, that
only have cation neighbours within the layer, it may also have to be considered that the nearest
components in the interlayer (water and anions) may influence the electronic environment of
the structural Fe.
The analysis of the spectra is a very important issue to consider. Frequently a Lorentzian
lineshape is used, but other lineshapes may be also be employed. The fitting of broadened and
asymmetric spectra are difficult without the introduction of some purely mathematical
constraints, e.g., assuming linear correlations between hyperfine parameters. Care must be
taken not to introduce substantial artifacts via the constraints.
For more details on the basics of Mössbauer spectroscopy the reader is referred to the
papers by Hawthorne1 and Rancourt.2
The structure of LDHs are based on a metal hydroxide layer with a positive charge, and an
interlayer containing water and the anions.3 They exhibit quite a large variation in the chemical
composition of the metal hydroxide layer and are able of incorporating a wide range of cations
in this layer, most frequently in the di- and trivalent state. In this chapter selected properties of
the LDHs as seen from the perspective of Fe will be presented. Examples have been chosen to
illustrate the structure of the cations in the octahedral layer, their redox properties, the
properties of anions within the interlayer, and decomposition of the structure into mixed oxides.
Cation Ordering in Green Rust and Pyroaurite
The green rusts (GRs) are the Fe(II)Fe(III)-containing LDHs and are known with a number
of different interlayer anions.4 The presence of Fe(II) in GRs makes this mineral a strongly
reducing mineral. A fairly wide range of cation ratios (Fe(II)/Fe(III)) has been reported in the
literature (3 - 0.12),5 but ratios around 2-3 are the most frequent. Many of the published cations
Investigating Layered Double Hydroxides by Mössbauer Spectroscopy 243
ratios are based on chemical analysis and probably affected by oxidation. The application of
Mössbauer spectroscopy to studies of these compounds has been centered on determination of
oxidation states (which for GRs is identical to cation ratios) and coordination. In general the
parameters of the oxidation products are different from the Fe in the GR structure facilitating
studies of formation and reactions using Mössbauer spectroscopy.6,7
The spectrum of GRSO4 produced by oxidation of an Fe(II) solution at a controlled pH of 7
is shown in Fig. 1a. This spectrum exhibits two doublets due to Fe(II) and Fe(III). No
intermediate oxidation states can be detected. The parameters of the Fe(II) are δ = 1.28 mms-1,
∆EQ = 2.92 mms-1 , and Γ (width at half height) = 0.26 mms-1 and for the Fe(III) they are δ =
0.47 mms-1, ∆EQ = 0.46 mms-1 , and Γ = 0.26 mms-1 , all at 80 K. The relative intensities of the
two lines of the doublets are identical and the lines are comparatively narrow. These features
are characteristic for well-defined cation positions and thus indicates that an ordered
arrangement of cation neighbours in the octahedral layer and species in the interlayer exists.
Assuming that Fe(II) and Fe(III) have identical f-factors the relative contents of these cations
can be evaluated directly from the relative areas. For the spectrum in Fig.1a a Fe(II)/Fe(III)
ratio of 2.1 (±0.2) is determined.
Figure 1. Mössbauer spectra of green rusts measured at 80 K. Sulphate(a) and chloride (b) form. (*) fitted
Fe(III) subspectrum; and (+)Fe(II) subspectrum. The sum of the two subspectra are shown as a solid line.
In Fig 1b the spectrum of a GRCl is shown. It may be immediately noted that this
compound contains a smaller amount of Fe(III) and therefore the resolution of the two
components is not as good as in the spectrum above. The parameters of the Fe(II) are δ = 1.26
mms-1, ∆EQ = 2.73 mms-1, and Γ = 0.29 mms-1 and for the Fe(III) δ = 0.44 mms-1, ∆EQ = 0.38
mms-1 , and Γ = 0.28 mms-1 , all at 80 K. From the ratio of the two components a Fe(II)/Fe(III)
ratio of 2.7± 0.2 is determined, i.e. close to 3.
The hyperfine parameters for the sulfate and carbonate forms are very similar, implying
identical structures. However, a comparison of the Fe(II) parameter for the chloride and sulfate
forms reveals significant differences. Hansen et al.8 compared the spectra of a GRCl with the
same sample after exchange of the Cl- with SO42- and found no significant changes in the
parameter of the Fe(II). This indicates that the effect of the interlayer anion on the quadrupole
splitting is small compared to the effect of the cation ratio. Thus the two GR types are
discernable from the parameters of the Fe(II). A similar effect is expected for the parameters of
the Fe(III), but due to the strong overlap of the signals in GRCl the parameters of this
component are less precisely determined.
Some previous studies have used more components for the fitting and this makes
comparison of the actual parameters difficult, but the above results on the cation ratio are in
good agreement with previous studies, clearly demonstrating the two forms of GR with
different cation ordering (sulphate forms,9-13 carbonate forms,14-16 chloride forms,8,17-19 oxalate
form,7 and sulphite form20).
Murad and Taylor,14,21 suggested a random oxidation of Fe(II) in the ordered structure.
Such an oxidation in the solid state would cause a change in NNN of Fe(II) and Fe(III), that
could be expected to induce a change in the quadrupole splitting of the components of the
ordered cation arrangement and possibly also cause new lines to appear. However, in the
spectra measured on samples of GR deliberately oxidised, a line at the position of these
non-ideal components was never clearly resolved. This indicates that the Fe(II) in the ordered
layer does not oxidise by a random process within the layer, but rather uniformly from the edge
eventually producing new Fe(III) oxides. Simple cation ratios (e.g., 2 or 3) are expected for
ordered distributions. However, significant deviations from these ratios are frequently reported,
without being paralleled by broadening of lines or other indications of only local order (see
below for cation order in pyroaurite). It remains to be explained what determines these
variations in cation ratios.
Pyroaurite (MgFe(III)-LDH) can be synthesized by various methods leading to a wide
variation in the cation ratio, Hansen and Bender Koch.22 Mössbauer spectra of pyroaurite
exhibit a characteristic asymmetry examplified in Fig 2. Such spectra cannot be fitted
accurately using one simple doublet. Rather, the shape of the asymmetry suggests that a
linearly correlated quadrupole and isomer shift distribution could be used and indeed the
quality of the fits increase, cf. the two types of fits in Fig. 2.
Among a series of samples, of which some principally might have been expected to possess
an ordered cation distribution based on the analytical determined cation ratio of the samples,
no evidence for cation order was found. However, a general trend was found between the
average quadrupole splitting (using a one doublet model) and the cation ratio.23 This indicates
that, like in GR, the cation ratio (NNN) has a strong influence on the splitting.
Figure 2. Mössbauer spectra of synthetic pyroaurite measured at 298 K. The spectra have been fitted using one
Lorentzian doublet (upper) and a correlated distribution of isomer shift and quadrupole splitting (lower). In the
latter the determined quadrupole distribution is inserted. The cation ratios (Mg/Fe) are 1.61 (a) and 2.48 (b).
Reprinted from C. Bender Koch, Structures and properties of anionic clay minerals, Hyperfine Interactions,
117 (1998) 131-157, with permission from Kluwer Academic Publishers.
It has not been possible to relate the derived quadrupole distributions in a simple way to the
local ordering of the cations. For the two examples shown in Fig. 2 the quadrupole distributions
imply that in general an Fe(III) surrounded by Mg will have a smaller splitting than an Fe(III)
with neighboring Fe(III), but the bimodal distributions are not readily interpreted.
Other effects may also influence the distribution. It has been found that following heating
at low temperature (approximately 70 to 100 °C) the distribution changes significantly.
Because the change has been found to be reversible within a period of a few months, it seems
reasonable to assign the change to differences in the amount and structure of the interlayer
water. Careful chemical analysis of pyroaurite samples have documented variations in the
acidity of the OH groups, which will lead to changes in the charge distribution. Most likely
similar effects influence some of the samples investigated so far. Thus, although the
distribution model gives excellent fit to the data, it is not likely that it will be possible to derive
the details of the cation distribution directly from the quadrupole distribution. Molecular
modelling of local charge contributions from the neighboring cat- and anions offer a possibility
to resolve the different contributions.
A number of other Fe-containing LDHs occur in nature or can be synthesized: e.g.
CoFe(III), NiFe(III)-(reevesite), ZnFe(III). These compounds have been found to exhibit
similar quadrupole distributions.23 Given the increased acidity of these cation it is likely that a
relative stronger influence from the charge of the local anion may be found in these
compounds.
Finally, it has been suggested that also the components in GR may be influenced by some
local variation akin to the one discussed for pyroaurite.10 Some of the uses of different sites for
particular the Fe(II) components may be explained by this, but in particular more details on the
anion stoichiometry in the samples are needed to resolve these issues.
Redox-manipulated Cation Layers
The structural Fe(III) in pyroaurite (MgFe(III)-LDH) is completely reduced and dissolved

under strongly reducing conditions. However, with liquid glycerol at elevated temperatures a
non-destructive, fairly slowly progressing, and incomplete reduction of the Fe(III) is found.
The procedure has been used as an intermediate step in ion-exchange reactions of pyroaurite,
because the accompanying change in layer charge upon reduction facilitates exchange of
interlayer anions.24 The extent of the reduction varies with the temperature and time of the
treatment, but up to 60 % has been accomplished. A series of spectra is shown in Fig. 3
demonstrating the progressive reduction as a function of reaction time indicating that the
reduction under these conditions reaches an extent of 40 % (reached at approximately 30 min
treatment). The large difference in hyperfine parameters between Fe(II) and Fe(III) in the high
spin configuration facilitates distinction between the species. The hyperfine parameters of the
Fe(II) and Fe(III) change slightly as the extent of reduction increases, indicating a minor (next
nearest) neighbourgh effect on the coordination. The reduction is reversible in the sense that a
fully reoxidised pyroaurite (by dioxygen) can be obtained. After very long treatments the cation
ratio changes towards relatively more iron in the octahedral layer, suggesting a selective
dissolution action of the glycerol.
Irreversible electrochemical oxidation of Co(II)Fe(III)-LDH has been reported by Hansen
and Bender Koch.25 At the maximum extent of oxidation this compound has a chemically
determined average oxidation state of the cations, that is increased by approximately +1. In the
Mössbauer spectrum obtained at 298 K, a singlet dominates over a doublet component, Fig. 4a.
The isomer shift of the singlet (-0.14 mms-1 at 298 K) indicates Fe(IV), whereas the doublet has
an isomer shift (0.40 mms-1 at 298 K) indicative of Fe(III). Compared to the untreated
Co(II)Fe(III)-LDH (see Fig 5a) the increase in the quadrupole splitting of the Fe(III)
component (from 0.50 to 0.70 mms-1) indicates an increasingly distorted environment of the
remaining Fe(III) following oxidation, possibly due to removal of hydroxyl groups. At low
temperatures the spectra reveals complex magnetic ordering. The low temperature behaviour
may qualitatively be explained by a simultaneous charge disproportionation of Fe(IV) into
Fe(V) and Fe(III) and magnetic ordering.
Figure 3. Mössbauer spectra measured at 80 K of a pyroaurite heated in glycerol at 170 °C for the indicated
periods of time. (*) fitted Fe(III) subspectrum and (+) Fe(II) subspectrum. The sum of the two subspectra are
shown as a solid line.
Figure 4. A:Mössbauer spectrum of maximum electrochemically oxidised Co(II)Fe(III)-LDH measured at 298

K and fitted to one singlet and one doublet. The sum of the two subspectra are shown as a solid line. B:
Mössbauer spectra of partially electrochemically oxidised Co(II)Fe(III)-LDH measured at 298, 80, and 12 K.
Fits to the two former spectra are shown as a solid line.
Studies of the material oxidised for shorter periods do not indicate formation of Fe(IV).
The spectrum of a partially oxidised sample is shown in Fig. 4b. The parameters of the doublets
at 298 and 80 K show that only Fe(III) is present, but at low temperature the onset of magnetic
ordering is observed (cf. with Fig 5a). This demonstrates the preferential oxidation of Co(II)
causing a broadening of the paramagnetic doublet, and an increase of the magnetic ordering
temperature. The spectrum measured at 12 K cannot be fitted using simple expressions.
Qualitatively it consists of an overlapping of two components: a doublet resembling the
untreated sample (cf. Fig 5) and a complex magnetically ordered component. This is in
agreement with the observation of two series of basal planes in XRD. The oxidation thus appear
to occur particle by particle and element by element.
Figure 5. Mössbauer spectra of Co(II)Fe(III)-LDH (cation ratio 2.2:1) before and after heating at 115 and 300
°C. The spectra were measured at the indicated temperatures.
The Interlayer Space: Bonding and Chemistry of Fe-CN Complexes and

Mechanical Properties
The interlayer in LDHs may host both simple and complex anions and the properties of the
anions may be significantly different from the anion in the liquid (dissolved) state. To
understand the modification of the properties of the anions, studies on their bonding and
chemistry within the LDHs may be helpfull. Mössbauer spectroscopy can potentially
contribute in two ways, as it can explore the electronical properties of both the complex and the
octahedral layer, and the bonding properties of the association between the host and the anion
though the mechanical characteristics.
Fe-containing complexes in the interlayer space of LDHs (e.g. hydrotalcite which is silent
with respect to Fe) have been the subject of a few Mössbauer studies. Fe can be introduced in
the form of fairly robust and rather large anionic cyanide complexes using coprecipitation,26-34
ion-exchange27,32,34-36 or rehydration.32 Hansen and Bender Koch36 compared the [FeII(CN)6]4-
complex in the glassy state (Fig. 6a) with the complex within the interlayer of hydrotalcite (Fig.
6b). The similar isomer shifts of these complexes (Fe(II) and Fe(III) in CN complexes usually
have a low spin configuration) (-0.006 vs. 0.012 mms-1 at 80 K), show that [FeII(CN)6]4- can be
exchanged into the interlayer with only little changes in the structure of the complex. However,
the study also revealed that the reactivity of the complex increased within the interlayer as
minor side-reactions, presumably involving ligand exchange of CN with water and oxidation of
the Fe(II) in the complex, which was detected following rather mild treatments that otherwise
does not affect the complex in the solid state (e.g. drying at 70 °C, Fig. 6c, or washing with
oxygen-containing non-aqueous solvents). The precise origin of the additional doublet
component detected in Fig.6c remains unknown, in part due to its small, yet detectable, amount.
The spectrum shown in Fig. 6b does show some additional broadening in comparison to the
sample measured in the glassy state (linewidth of 0.33 vs. 0.26 mms-1), indicating a slightly
more variable environment. Studies of crystalline Fe(II) cyanide salts have revealed a similar
variation of isomer shifts, that is explained by the difference in the polarising power of the
cation on the π-back donation in the complex.37 Local variation of the polarising power within
the interlayer may also cause small, unresolved shifts in the isomer shift that contribute to the
observed broadening of the singlet. An essentially unpertubed state of the adsorbed anion has
also been reported in other systems.38 Idemura et al.35 reported similar results, but with a
noticeable higher linewidth (Fig. 7b), probably because of sample sensitivity towards
experimental details like drying procedures (see below).
Spectroscopically dramatic effects have been reported following intercalation of
[Fe (CN)6]3-in hydrotalcite.35 Both in the glassy state at 80 K (Fig. 8) and in the solid state of
III
the K-salt, this complex exhibit a doublet (δ = –0.058 mms-1 and ∆EQ = 0.93 mms-1 at 80 K).
Following intercalation in LDH, the spectrum measured at 298 K (Fig. 8b) is dominated by a
singlet with δ = –0.067 mms-1, ie. within the uncertainty identical to the parameters of the
[FeII(CN)6]4- complex in hydrotalcite, Fig 6a. Cooling of the sample to 80 K causes quadrupole
splitted component(s) to appear in the spectrum, Fig 8c. Using, as a first approximation, a fit
having one singlet and one doublet component, it is found that the singlet, also in its
temperature dependence of the isomer shift, behaves like [FeII(CN)6]4-. The doublet has an δ =
–0.050 mms-1 and a ∆EQ = 1.22 mms-1, partly resembling that for the Fe(III) complex. It has
been found that the spectral changes on cooling from 298 to 80 K are fully reversible. These
findings indicate that the complex in the interlayer essentially can be fully reduced to Fe(II) via
an internal redox reaction with the ligand and that the equilibrium of this reaction is shifted
towards Fe(III) when the LDH-complex is frozen in the interlayer. It may also be noted that
using only one doublet component in Figs 8a and 8b does not produce perfect fits, presumably
due to local variations in the surroundings within the glass and the interlayer.
Spectra of the [FeIII(CN)5(H2O)]2- complex in LDH also indicate an apparent reduction of a
large part of the Fe, Fig 9 (singlet with δ = 0.007 mms-1 at 80K). The remaining part of the
spectra are only poorly resolved, making detailed assignments difficult, but nevertheless
highlighting significant changes induced by intercalating.
The reduction of the Fe(III)-CN complexes in the interlayer has been proposed to be
related to the reversible pressure-induced reduction described from high-pressure studies of the
salts.35 It is in this context interesting to compare the spectrum in Fig 8c with that of Idemura et
al.35 measured at 298 K, see Fig 7a : a qualitative strong resemblance is found between the
spectra measured at 80 K and the spectrum measured at 298 K by Idemura et al., indicating the
presence of both Fe(II) and Fe(III) complexes. It is likely that the actual pressure experienced
by the complex within the interlayer depends on the pretreatment of the sample, e.g. drying and
rate of freezing. Idemura et al. dried the samples in vacuum or at 110 °C, effectively removing
a major part of the water of hydration. A high pressure in the interlayer is consequently
achieved at 298 K causing a comparable distortion to the one induced by freezing. It may be
noted that the changes in the spectrum of [FeII(CN)6]4- in the interlayer can be partially
explained by the formation of Fe(II) in the high spin state, as also have been observed in pure
cyanide salts at high pressures.
Figure 6. Mössbauer spectra of [FeII(CN)6]4- in a glass (a), interlayered in hydrotalcite (b), and b after heating
to 70 °C. All spectra were measured at 80 K. The fitted components are shown as solid lines.
Figure 7. Mössbauer spectra of [FeIII(CN)6]3- (a) and [FeII(CN)6]4- intercalated in hydrotalcite and measured
at 298 K. Reprinted from S. Idemura, E. Suzuki and Y. Ono, Electronic state of iron complexes in the interlayer
of hydrotalcite-like materials, Clays Clay Miner., 37 (1989) 553-557, © 1989, with permission from the Clay
Minerals Society.
Figure 8. Mössbauer spectra of [FeIII(CN)6]3- in a glass(a) and interlayered in hydrotalcite (b) and (c). The
spectra were measured at the temperatures indicated. The fitted components are shown as solid lines.
These findings indicate that a specifically designed mixture of states may be achieved by
varying the preparation conditions. It may be usefull to distinguish between electronic effects
on the complex due to the charge of layer and mechanical effects from varying the interlayer
distance.
The Mössbauer fraction depends on the mean square displacement of the nuclei. Thus the
strength of the bonding of the complex anion may indirectly be probed by measurering the
spectral area as a function of the temperature of the absorber. The spectral area of the
[FeII(CN)6]4- complex in the interlayer of hydrotalcite are shown in Fig. 10. At one extreme the
hydrated complex may be assumed to move relatively unrestricted in the interlayer solution,
and for that case a freezing of the interlayer water is expected to decrease movement of the
complex in the interlayer. Accordingly, the f-factor and the resonant absorption area will
increase abruptly. However, due to the high charge of the Fe cyanide complexes, it can be
expected that the complexes are held rather rigidly in the interlayer with electrostatic bonds to
both the surrounding structural layers. In that case the change in spectral area may be expected
to be less abrupt. At the humidity of the laboratory it is expected that the interlayer complex is
hydrated. This water of hydration is expected to freeze at a significant lower temperature in
comparison to liquid water in casu down to around 220 K. Because vibrations in a solid depend
on the temperature, it is convenient to compare the absorption area with an ideal model. The
basis for Fig. 10 is an analytical expression of the dependence of the area on temperature
derived from the Debye crystal model.39 According to this model, a linear relation between the
logarithm of the spectral area and the characteristic temperature of the crystal (ΘD) describe the
relationship for temperatures higher than ΘD/2. For data in Fig. 10, the approximate linear
range can be estimated to temperatures between room temperature (RT) and 150 K, and from
the slope a value for ΘD close to 140 K can be estimated. The absence of a significant change in
the slope in the range between 150 K and RT (where melting of the interlayer water occur)
demonstrates that electrostatic bonding is strong for these complexes. As expected for
compounds with small ΘD, there is a considerable advantage in measurering at low
temperatures.
Figure 9. Mössbauer spectra of [FeIII(CN)5(H2O)]2- interlayered in hydrotalcite. The spectra were measured
at the indicated temperatures. The fitted components are shown as solid lines.
Figure 10. Temperature dependence of the absorption area in the Mössbauer spectrum of [FeII(CN)6]4- in
hydrotalcite between 80 and 298 K. The line is a guide to the eye. Reprinted from H. C. B Hansen and C.
Bender Koch, Synthesis and properties of hexacyanoferrate interlayered in hydrotalcite. I. Hexacyanoferrate
(II), Clays Clay Miner., 42 (1994) 170-179, © 1996, with permission from the Clay Minerals Society.
From the discussion above it is evident that it is far too simple to regard the LDH as just a
simple counter ion for the adsorbed anions.
In addition to the electronical properties the physical orientation of the complex in the
interlayer has been discussed based on XRD data.28,40 Mössbauer spectroscopy can, due to its
directional dependence, be used to study orientation effects in the interlayer. Such studies
require chosing suitable complexes (i.e. one having a sizeable quadrupole splitting), preparing
highly oriented absorbers, and investigating the angle dependence of the ratio of the two lines
of the doublet. No data on LDH-complexes appear to have reached the literature.
STRUCTURAL CHANGES UPON THERMAL TREATMENT OF LDHS

LDHs transform readily into mixed oxide systems on heating, and due to the highly
variable composition they may be used as simple precursors for achieving various structures
and compositions.41 Typically, the mixed oxide produced by static heating at fairly low
temperature possess extensive porosity and reveals no long range structural order as indicated
by XRD.42,43 Mössbauer spectroscopy has been extensively used in investigations of mixed
oxide systems in general,44 and it might also have been expected that the thermal conversion
products of some LDHs would have been investigated. However, no example of such studies
appear in the literature. As an example of the information that can be obtained from Mössbauer
spectroscopy studies on these transformation products, the case of a Co(II)Fe(III)-LDH (cation
ratio 2.2:1) heated statically at 115 °C and 300 °C in air (at the latter temperature Co(II)
oxidises to Co(III)) will briefly be considered. In Fig 5 the spectra of three samples measured at
295 K, 80 K, and 12 K are shown: 1) the unheated Co(II)Fe(III)-LDH, 2) the XRD-amorphous
mixed oxide produced by heating at 115 °C, and 3) the XRD-crystalline mixed oxide produced
by heating at 300 °C. The unheated sample remains paramagnetic down to a temperature below
12 K reflecting the dilute state of Fe(III), and the weak magnetic interactions with the only
potential interactions being within the octahedral layer. From the parameters of the doublets (δ
= 0.35 mms-1 and ∆EQ = 0.49 mms-1 at 298 K) it can be concluded that all the Fe in the LDH is
Fe(III) in the high spin state . Like the LDH samples discussed above, the asymmetry of the
doublets indicate some local variation in the Fe(III) octahedra (see reference 23 for more details
on the Co(II)Fe(III) system).
Supplemental investigations of the three samples using analytical transmission electron
microscopy do not indicate compositional inhomogenieties in the cation ratios among the
samples at these treatment temperatures. Heating of the sample to 115 °C revealed formation of
extensive porosity in the crystallites, partially explaining the absence of long range order in the
sample as evidenced by XRD. However, microdiffraction showed a local well developed
structure indicating a tetragonal ordering (a= 0.833 nm, c= 2.499 nm). Further heating to 300
°C caused the pores to disappear, Co(II) to oxidize, and a lowering of the symmetry to cubic.
Two major changes in the properties of the samples are detected following heating. The
spectra of both heated samples consist of paramagnetic doublets at 298 K having parameters
consistent with high spin Fe(III), as expected in coordination with oxygen. However, the
asymmetry of the doublet is replaced by a distinct broadening of the lines and a significant
increase in the quadrupole splitting (∆EQ average = 0.74 mms-1). The presence of magnetic
order in the 12 K spectrum measured of the heated samples, demonstrates a significant increase
in the interactions that qualitatively may be related to changes in chemical and physical
properties upon heating. Heating at 115 °C removes the interlayer anions and water, thus
facilitating magnetic interaction among the cation layers. The in-layer interaction may on the
other hand expected to be weaken due to the formation of pores. A further strengthening of the
interaction is achieved by annealing of the pores and oxidation of Co(II) after heating to 300 °C,
where a bulk three dimensional structure develops.
It is a characteristic feature of all the magnetically ordered spectra that the lines are not
pairwise identical. Such an asymmetry with a relative sharp line one (lines are numbered from
negative towards positive velocities) and a relative broader line six, can arise by partial
overlapping of two slightly different sextets. Using, as a simplification, a one-sextet fit for the
spectra measured at 12 K, a magnetic hyperfine field of 48.2 and 49.0 T is found for the sample
heated at 115 °C and 300 °C, respectively. The isomer and quadrupole shifts of the two sextets
are very similar: 0.45 mms-1 and ≅ 0 mms-1. Such an asymmetry is well known from
maghemite (γ-Fe2O3) that also yields similar hyperfine parameters. In pure maghemite it is
caused by the presence of two slightly different coordination environments for the Fe in
octahedral and tetrahedral sites.45 The broadening of the doublets of the heated samples
observed at 298 K is consistent with the presence of more than one coordination site, but again
the resolution does not allow significant distinctions.
Although the maximum hyperfine field of the two heated samples are quite similar, it is
noted that the magnetic ordering temperature varies significantly between both samples.
The ferrimagnetic spin structure of maghemite is frequently employed to estimate the
relative occupancy of the two sites by measuring the spectra in applied magnetic field and using
the field–induced splitting of the lines. However, the tetragonal phase produced by heating at
115 °C does not exhibit long range ferrimagnetic order, and therefore this approach does not
provide more details.
It is noteworthy, how relatively easy the Co(II)Fe(III)-LDH converts into a spinel structure
in comparison to other LDHs.42,46
CONCLUSIONS
Mössbauer spectroscopy can provide unique information on the electronic and binding
properties of Fe in LDH structures.
Two types of local cation order can be distinguished examplified by green rusts (often
showing 2:1 or 3:1 ordering) and pyroaurites (distributions). The redox chemistry of Fe(III)
within the metal hydroxide layer is illustrated with examples of electrochemical oxidation of a
Co(II)Fe(III)-LDH and reversible reduction of MgFe(III) by treatment in boiling glycerol. The
chemistry of Fe-CN complexes in the interlayer of hydrotalcite is presented, emphasising the
interdependence of redox changes, bonding strength, and the mechanical properties of the
octahedral cation layer. Changes in the structure following heating is examplified by
Co(II)Fe(III)-LDH readily forming a maghemite-like mixed oxide.
ACKNOWLEDGEMENTS
I wish to acknowledge discussions on various aspects of LDHs with Drs. S. Mørup, H.C.B.
Hansen, R.M. Taylor, and M.D.Bentzon. The manuscript benefitted from comments by the
editor.
REFERENCES
1. F. C. Hawthorne, in Spectroscopic Methods in Mineralogy and Geology, Reviews in
Mineralogy, Vol 18. Mineralogical Society of America (1988) pp. 255-339.
2. D. G. Rancourt, Hyperfine Interactions 117 (1998) 3.
3. V. A. Drits and S. Bookin, in Layered Double Hydroxides: Present and Future, V. Rives
(Ed.), NOVA Sci. Pub., New York (2001), p. 39
4. B. C. H. Hansen, in Layered Double Hydroxides: Present and Future, V. Rives (Ed.),
NOVA Sci. Pub., New York (2001), p. 93
5. D. Lewis, Advances in Geoecology 30 (1997) 345.
6. C. Bender Koch and H. C. B. Hansen, Adv. in Geoecology 30 (1997) 373.
7. P. Refait, A. Charton and J.-M. R. Génin, Eur. J. Solid State Inorg. Chem. 35 (1998) 655.
8. H. C. B. Hansen, S. Guldberg, M. Erbs and C. Bender Koch, Appl. Clay Sci. 18 (2001) 81.
9. A. A. Olowe, J.-M. R. Génin and P. Bauer, Hyperfine Interactions 46 (1989) 437.
10. A. H. Cuttler, V. Man, T. E. Cranshaw and G. Longworth, Clay Miner. 25 (1990) 289.
11. J.-M. R. Génin, A. A. Olowe, N. D. Benbouzid-Rollet, D. Prieur, M. Confente and B.
Resiak, Hyperfine Interactions 69 (1991) 875.
12. H. Drissi, P. Refait and J.-M. Génin, Hyperfine Interactions 90 (1994) 395.
13. J.-M. R. Génin, A. A. Olowe, P. Refait and L. Simon, Corrosion Sci. 38 (1996) 1751.
14. E. Murad and R. M. Taylor, Clay Miner. 19 (1994) 77.
15. H. Drissi, P. Refait, M. Abdelmoulla and J.-M.Génin, Corrosion Sci. 37 (1995) 2025.
16. H. C. B. Hansen and C. Bender Koch, In H. Kodama; A.R. Mermut; J.K. Torrance (eds.)
Clay for our Future (1999). Proc. 11th Int Clay Conf., Ottawa, Canada, 1997, 295.
17. J.-M. R. Génin, D. Rezel, P. Bauer, A. A. Olowe and A. Beral, Materials Science Forum 8
(1986) 477.
18. P. Refait and J.-M. R. Génin, Corrosion Sci. 34 (1993) 797.
19. P. Refait and J.-M. R. Génin, Clay Miner. 32 (1997) 597.
20. L. Simon, J.-M. R. Génin and P. Refait, Corrosion Sci. 39 (1997) 1673.
21. E. Murad and R. M. Taylor, in Long, G.J. and Stevens, J.G. (eds.) Industrial Application of
the Mössbauer Effect, (1987) 585.
22. H. C. B. Hansen and C. Bender Koch, Appl. Clay Sci. 10 (1995) 5.
23. C. Bender Koch, Hyperfine Interactions 117 (1998) 131.
24. H. C. B. Hansen and R. M. Taylor, Clay Miner. 26 (1991) 311.
25. H. C. B. Hansen and C. Bender Koch, Inorg. Chem. 33 (1994) 5363.
27. S. Miyata and T. Hirose, Clays Clay Miner. 26 (1978) 441.
28. S. Kikkawa and M. Koizumi, Mater. Res. Bull. 17 (1982) 191.
29. K. Itaya, H.-C. Chang and I. Uchida, Inorg. Chem. 26 (1986) 624.
30. K. A, Carrado, A. Kostapapas and S. L. Suib, Solid State Ionics 26 (1988) 77.
31. B. R. Shaw, Y. Deng, F.E. Strillacci, K.A Carrado and M.G. Fessehaie, J. Electrochem Soc.
137 (1990) 3136.
32. I. Crespo, C. Barriga, V. Rives and M. A. Ulibarri, Solid State Ionics 101-103 (1997) 729.
33. A. Béres, I. Pálinko, I. Kiriscsi, J. B. Nagy, Y. Kiyozumi and F. Mizukami, Appl. Catal. A,
182 (1999) 237.
34. H. Nijs, M. de Bock and E. F. Vansant, Microporous Mesoporous Mater. 30 (1999) 243.
36. H. C. B. Hansen and C. Bender Koch, Clays Clay Miner. 42 (1994) 170.
37. N. N. Greenwood and T. C. Gibb, Mössbauer Spectroscopy. Chapman and Hall, London
(1971) 659 pp.
38. E. P. Giannelis, D. G. Nocera and T. J. Pinnavaia, Inorg. Chem. 26 (1987) 203.
39. G. K. Wertheim, Mössbauer Effect: Principles and Applications. Academic Press, New
York, 1971, 116 pp.
40. F. A. P. Cavalcanti, A. Schutz and P. Biloen, In Delmon, B. et al. (eds.) Preparation of
Catalysts IV, (1987) pp. 165-174.
41. V. Rives, in Layered Double Hydroxides: Present and Future, V. Rives (Ed.), NOVA Sci.
Pub., New York (2001), p. 115
42. W. T. Reichle, S. Y. Kang and D. S. Everhardt, J. Catal. 101 (1986) 352.
43. P. G. Rouxhet and H. F. Taylor, Chemia, 23 (1969) 480.
44. R. E. Vanderberghe and E. de Grave, in G.J. Long and F. Grandjean (eds.), Mössbauer
spectroscopy applied to inorganic chemistry, (1984) Vol. 3, p. 59.
45. G. M. da Costa, E. de Grave and R. E. Vandenberghe, Hyperfine Interactions 117 (1998)
207.
Chapter 8
SURFACE TEXTURE AND ELECTRON

MINCROSCOPY STUDIES OF LAYERED DOUBLE
HYDROXIDES
Vicente Rives
Departamento de Química Inorgánica, Universidad de Salamanca,
37008-Salamanca (Spain)
fax: +34 923 29 45 74; e-mail: vrives@usal.es
INTRODUCTION
The well known layered double hydroxides (LDHs) are actually layered double
hydroxysalts, as, in addition to the hydroxide anion forming brucite-like layers with partial
M2+/M3+ substitution (compounds with mono- and even tetravalent cations are also known),
they contain another anion(s) between these brucite-like layers, together with water molecules;
strictly speaking, only meixnerite, where the interlayer anion is also hydroxyl, can be
considered as a true LDH.1,2 Nevertheless, the term is applied also to other layered materials
with this structure, and containing different interlayer anions, such as organic anions,
oxoanions (nitrate, chloride, sulphate, etc., carbonate being the commonest), or even
oxometalates and anionic coordination compounds3 or polymers.4 They are also known as
hydrotalcite-like materials, as the structure is related to that of hydrotalcite, a natural (and
easily synthetized) mineral, first discovered in Sweden; its formula is [Mg6Al2(OH)16](CO3) · 4
H2O although it is usually written as [Mg0.75Al0.25(OH)2](CO3)0.125 · 0.5 H2O to evidence its
relationship to brucite, Mg(OH)2.
These materials have found a wide range of commercial and industrial applications,1,5 such
as ion exchangers, molecular sieves, flame retardants, protonic conductors, adsorbents,
catalysts and catalyst precursors, as antacids, etc., in addition to the academic challenge they
represent, being the counterpart of the well known cationic clays (actually, LDHs are also
known as “anionic clays”), and, as these, showing exchange (but anionic) ability; as cationic
clays, they can be pillared with appropriated anions. When calcined, homogeneously dispersed
mixed oxides are formed, which nature and particle size strongly depend on the decomposition
conditions (time, atmosphere, etc.) The calcined material can easily recover the original layered
258 Vicente Rives
structure upon equilibration with moisted air or when it is immersed in aqueous solutions
containing anions.6-9
For these reasons, a knowledge of the morphology of the particles, and, specially, their
specific surface area and pore network, is of paramount importance to understand their behaviour, in
order to modulate and to improve their properties. In this chapter we will review the textural
properties of LDHs and of their decomposition products, analyzing the effect of several synthesis
parameters and of decomposition to modify the texture properties. The morphology of the particles,
and their change along thermal treatments, will be also reviewed.
In order to systematize the study, we will review first the data published on hydrotalcite
itself (or synthetic materials with other Mg/Al molar ratios), and then on LDHs with other
cations in the layers and/or other anions in the interlayer. Secondly, LDHs with intercalated
metal-containing oxoanions and hexacyanoferrate complexes will be studied. Finally, the
evolution in specific surface area upon calcination will be also studied. Unless otherwise stated,
results correspond to adsorption-desorption of N2 at -196 °C, following the well known
analyses of surface area and porosity.10-12
HYDROTALCITE AND HYDROTALCITE-LIKE LDHS

The specific surface area (SSA) of a solid strongly depends on the synthesis method used
to prepare it. LDHs are not beyond this, and so, different values have been reported in the
literature, ranging from a few square meters per gram to more than one hundred. The SSA
values for several synthetic hydrotalcites, prepared following different routes, are summarized
in Table 1. As LDHs are usually prepared by coprecipitation of the corresponding hydroxides,
special attention should be payed to the treatment given to the solid formed, e. g., ageing or
hydrothermal treatment, and the temperature at which this treatment is given (column 2). Also,
as the structure is known to collapse upon heating at rather moderate temperatures,7 the
outgassing treatment given to the sample prior to recording the N2 adsorption-desorption
isotherm is also important (in brackets in column 5). The external surface area of the
crystallites can be evaluated using the equation
Sext = 6 / (D δ)
where D is the average particle diameter (assuming spherical particles) and δ the density of
the crystal. In this case, as the crystallites are esentially hexagonal in shape (see below), the
average particle size can be determined by using the Scherrer equation,35 from line broadening
of the X-ray diffraction maxima corresponding to planes (003) recorded close to d=7.6-7.8 Å
for a Mg,Al-CO3 LDH, and which corresponds to 1/3 of lattice dimension c of the crystal, and
planes (110), recorded close to 1.5 Å, corresponding to 1/2 of dimension a. The average
crystallite size calculated36 for a hydrotalcite-like LDH submitted to hydrothermal treatment at
125 °C for 8 days was 150 nm; taking into account that the density of hydrotalcite is close to 2
g/cm3,37 a value of ca. 20 m2/g can be calculated. This value coincides, within experimental
error, with that determined by nitrogen adsorption,27 Table 1, and so it is concluded that the
sample should not have micropores. Otherwise, the external surface area can be calculated from
the size of the crystallites observed by TEM; Reichle et al.26 have reported a calculated SSA of
12 m2/g for a Mg,Al-CO3 hydrotalcite crystallized at 200 °C for 18 h, acceptably coincident
Surface Texture and Electron Mincroscopy Studies… 259
with the experimental value of 14 m2/g, again demonstrating the lack of internal surface in this
sample.
The SSA value is, however, very much larger for samples which have not been submitted to
hydrothermal treatment, with values ranging between 40 20 and 120 26 m2/g (Table 1). However,
the isotherms recorded for these samples usually belong to type II or type IV in the IUPAC
classification,11 and do not indicate the presence of micropores in most of the cases, despite the
interlayer space can be seen as a pore, but the N2 molecules (kinetic diameter ca. 3.65 Å) do not
access to the interlayer space, and so the measured surface area corresponds only to the external
surface area and adsorption on meso/macropores existing in the samples. It should be
remembered that the heigth of the interlayer is close to 3 Å, from d(003) (ca. 7.8 Å) and the
width of the brucite-like layer, 4.8 Å. 38 This interlayer space is partially filled with carbonate
anions (to compensate the positive electric charge of the layers originated by the Mg2+/Al3+
substitution) and by water molecules; all these interlayer entities are not close-packed, as it can
be concluded from IR spectroscopy, which shows they are oriented, with hydrogen bondings
between the interlayer carbonate and the OH-/H2O groups,27,39 and so, no much room should be
available to accomodate nitrogen molecules, in addition to the problems arising from its access
to the interlayer space.
From results summarized in Table 1, it can be concluded that the chemical composition, i.
e., the Mg2+/M3+ ratio, controlling the occupancy of the interlayer region by carbonate anions,
seems to have no effect on the SSA of the samples, so confirming that N2 molecules do not
reach the interlayer space; values of 103±3 m2/g were obtained,13 for hydrotalcites aged for 2 h
at 60 °C with Mg2+/Al3+ ratios ranging from 1.0 to 4.9. However, the main effect on the surface
area development seems to be the treatments to the slurry obtained during synthesis, before
drying. So, according to Labajos et al.27 the SSA sharply decreases from 115 m2/g for a LDH
aged for 2 h at room temperature, to 35-20 m2/g after hydrothermal treatment at 125 °C at
autogenous pressure for 4 or 8 days, no further decrease in SSA being observed when the
hydrothermal treatment was extended for 13 days. An extremely low value (less than 3 m2/g)
has been reported by Hibino et al.33 for a hydrotalcite hydrothermally treated at 150 °C at 500
kN/m2 for 12 h. The temperature of such a treatment is also important, with SSAs of 120 m2/g
for a LDH crystallized at 65-75 °C for 18 h, but only 12 m2/g if crystallization is conducted at
200 °C.40 The value reported by Costantino et al.32 for a hydrotalcite prepared by homogeneous
precipitation via urea hydrolysis is also rather low (24 m2/g), despite the treatment given to the
slurry was not too severe.
The t-plots (i. e., a plot of the amount of gas adsorbed vs. the thickness of the N2 adsorption
layer) give also some clue about the pores existing in the solid.12 The plots should be a straight
line passing through the origin upon extrapolation in the absence of micropores, as reported by
Labajos et al.27 for their hydrothermally treated samples. However, upwards deviation in the
t-plot of the sample aged at room temperature (displaying the largest SSA for this series of
samples) has been attributed to an increased uptake due to condensation in larger pores,
probably interparticle pores.
Besse et al.23 have reported a detailed study of changes in SSA and in the shape of the N2
adsorption isotherms when the synthesis is carried out in the presence of organic solvents
(methanol, ethanol, propanol, ethylene glycol, glycerol, and acetone, 1:1 mixtures with water).
Although the lattice parameters are roughly coincident in all cases, the crystallinity changes
appreciably: the width at half height of the main diffraction peak close to 7.8 Å, the first one
reflecting the d(003) spacing, changes from 0.623 for the sample crystallized in acetone, to
260 Vicente Rives
1.778 for the sample prepared in glycerol. Changes are also seen in the nitrogen adsorption
isotherms, Fig. 1, and thereof in the surface texture of the samples. All isotherms belong to type
IV, corresponding to adsorption on mesoporous solids,11 i.e., at high pressures, beyond a given
point, there is no more uptake of gas despite the pressure is increased, and on desorption a
hysteresis loop is observed up to a relative pressure close to 0.45, which is associated to
capillary condensation in the mesopores. The isotherms for the samples prepared in water (i. e.,
in the absence of organic co-solvents) and ethylene glycol do not show a limiting adsorption
capacity at high relative pressures, and the H3 type hysteresis shown is characteristic11 of
aggregates of plate-like particles leading to slit-shaped pores, which is in agreement with the
microtexture of the hydrotalcite. Except for ethylene glycol (136 m2/g SSA, and 1.064 cm3/g
for the specific pore volume) and glycerol (54 m2/g and 0.092 cm3/g, respectively) preparations,
the SSAs were in the range 62-94 m2/g for all other samples. It is worthnoting the development
of microporosity in the sample synthetized in glycerol, which may result from the formation of
rather compact aggregates, micropores appearing in the grain boundary region, rather than in
the interlamellar region (as observed for pillared materials, see below). These authors claim
that the process is purely physical in origin, and not chemical, the glycerol molecules probably
aggregating the solid particles during crystallization, and being eliminated during washing,
leaving unaltered the newly created porosity.
Table 1.-Specific surface areas of different Mg,Al-carbonate LDHs
M2+/M3+ ratio Synthesis treatment temp. d(003) (Å) isotherm/ SBET(m2 g-1)/ comments Ref.
type (°C) hysteresis outgassing
4.9 60°C/2 h n.r. n.r. 101 (120) 13
4.29 65°C/ 30 min 7.85 IV 88 (30) drying overnight 70°C & 10 h outgassing 14
4.12 70°C/40 h n.r. n.r. 73 (130) 15
3.33 65°C/ 30 min 7.85 IV 92 (30) drying overnight 70°C & 10 h outgassing 14
3.11 70°C/ 40 h n.r. n.r. 104 (130) 16
3 HT 7.78 n.r. 24 17
3 HT/210°C/18 h 8.5 n.r. 14 (150) 18
3 60°C/ 24 h n.r. II 43 (110) degassing 24 h 19
3 65°C/ 30 min 7.65 IV 40 (100) 20
3 80°C/ 24 h 7.72 n.r. 56 21, 22
3 60°C/2 h n.r. n.r. 106 (120) 13
3 r.t./ 30 h n.r. IV/H3 75 (80) heating 16 h 100 °C in air 23
3 r.t./ 30 h n.r. IV 87 (80) synthetized in H2O/CH3OH 23
3 r.t./ 30 h n.r. IV 88 (80) synthetized in H2O/C2H5OH 23
3 r.t./ 30 h n.r. IV 62 (80) synthetized in H2O/C3H7OH 23
3 r.t./ 30 h n.r. IV 136 (80) heating 16 h 100 °C in air synthetized in H2O/ethylene glycol 23
3 r.t./ 30 h n.r. IV/H3 54 (80) heating 16 h 100 °C in air synthetized in H2O/glycerol 23
3 r.t./ 30 h n.r. IV 94 (80) heating 16 h 100 °C in air synthetized in H2O/acetone 23
2.7 reflux/70°C/18 h 7.9 II/H3 81 (300) 24, 25
2.63 65°C/18 h n.r. n.r. 120 26
2.63 200°C/18 h n.r. n.r. 14 26
2.57 HT 125°C/ 13 days n.r. II 22 (125) 27
2.52 HT/120°C/24 h 7.6 n.r. 23 (120) 28
2.48 HT 7.69 n.r. 19 17
2.45 60°C/ 40 min 7.72 n.r. 94 (90) 29
2.33 HT 125°C/ 8 days n.r. II 21 (125) 27
2.23 HT 125°C/ 4 days n.r. II 35 (125) 27
2.23 stirring 85°C/4 h n.r. n.r. 58 (130) 30
2.0 65°C/ 18 h 7.59 n.r. 80 ±6 m2 g-1 after outgassing at 70, 105 or 180°C or calcination at 31
240 °C
2.0 100°C/ 36 h 7.6 n.r. 24 homogeneous precipitation by urea hydrolyisis 32
2.0 70°C 7.65 n.r. 53 33, 34
2.0 HT 150°C/12 h 7.64 n.r. <3 33, 34
1.97 HT 7.57 n.r. 15 17
1.86 30°C/ 2 h n.r. II 115 (125) 27
1.0 60°C/2 h n.r. n.r. 99 (120) 13
n.r.=not reported
HT=hydrothermal treatment
r.t.= room temperature
262 Vicente Rives
The results reported for LDHs containing other cations in the layers and carbonate, nitrate,
chloride, or sulphate in the interlayer, Table 2, do not differ significantly from those above
commented for Mg,Al-CO3 LDHs, Table 1. In some cases, it is observed that an increase in the
molar fraction of Mg2+ in the layers gives rise to an increase in the SSA, as in the
Mg,Al,Sn-CO3 samples studied by Velu et al.,14 or in Mg,Ni-CO3,NO3 samples reported by
Tichit et al.24,25 In the LDHs containing noble metals studied by Vaccari et al.29 no systematic
change is observed in the SSA with the composition, probably because the low loading of noble
metal in these samples. With respect to the relative molar fraction of trivalent cation, no
systematic behaviour is observed either: so, for samples submitted to hydrothermal treatment,
SSA increases with the Fe/Al ratio,46 but in samples aged at room temperature the opposite
trend is observed.47 However, for Mg,Al,V-CO3 LDHs a decrease in the SSA is observed as the
V/Al ratio is increased.28 In some cases, this increase could be attributed to the co-precipitation
of amorphous alumina or an aluminium hydroxide, with an extremely large specific surface
area development; however, the X-ray diffraction patterns do not show the typical background
expected for the co-existence of crystalline and amorphous solids. For given layer cations and
an interlayer anion, the M2+/M3+ ratio seems to have either no systematic effect on the SSA, as
reported for Zn,Al-Cl samples.58 Finally, the nature of the interlayer anion (other variables,
such as M2+/M3+ ratio, nature of the cations or ageing treatment being the same) may give rise to
changes in the specific surface area, but no systematic variation able to be related to the nature
of the anion can be concluded.57
So, the chemical composition of LDHs containing “small” inorganic anions in the
interlayer, such as carbonate, nitrate, chloride, sulphate, etc., seems to have no effect on their
specific surface areas. The main factor affecting the surface area development seems to be the
treatment given to the sample during synthesis (ageing, hydrothermal treatment, etc.), and the
drying process. In some cases, the use of mixed water-organic solvents seems to modify the
surface texture, by affecting the aggregation of the microcrystallites.
LAYERED DOUBLE HYDROXIDES WITH

INTERCALATED POLYOXOMETALATES
According to the results reported above, the interlayer space is not available to the nitrogen
molecules during the adsorption process if the layers are too close, because of the presence of
“small” inorganic anions in the interlayer space. An attempt to make available this space,
thereof increasing the surface available for adsorption, has been made by intercalation of rather
“large” anions, such as polyoxometalates. In this section we will discuss the surface texture
properties of LDHs containing oxometalates (e. g., chromates, vanadates and molybdates) and
higher polyoxometalates possessing the Keggin-like and related structures. Some data
collected from the literature have been summarized in Table 3. It is interesting to notice that, in
some cases, development of microporosity has been observed.
Besse et al.52 have found that intercalation of chromate or dichromate species in a
Ni,Al-LDH does not change significantly the SSA with respect to the value measured for the
parent chloride form; actually, even a ca. 50% decrease (cf. data in Tables 2 and 3) is observed.
These author attribute this decrease as a consequence of the gentle calcination to which the
samples are submitted before recording the nitrogen adsorption isotherm, which results in
grafting of the anions to the brucite-like layers, and conclude that the measured surface
represents mainly the interparticle voids, rather than the interlamellar space, i. e., a behaviour
similar to that found for compounds which texture properties are summarized in Tables 1 and 2.
The α-plots for both samples are very similar, suggesting the microtextural properties of the
chromate and dichromate forms being almost coincident.
Figure 1.-Nitrogen adsorption isotherms (-196 °C) of N2 on Mg,Al-CO3 LDHs prepared in water-organic
co-solvent mixtures. Wa = water; MOH = methanol; EtOH = ethanol; PrOH = propanol; EtGl = ethyleneglycol;
Gly = glycerol; Ac = acetone. Reprinted from F. Malherbe, C. Forano and J. P. Besse, Use of organic media to
modify the surface and porosity properties of hydrotalcite-like compounds, Microporous Mater., 10 (1997)
67-84, © 1997, with permission from Elsevier Science.
The specific surface area measured for decavanadate-containing LDHs differs greatly,
depending on the preparation conditions. So, Ulibarri et al. have reported66 values ranging from
48 to 89 m2/g for Mg,Al-decavanadate LDHS prepared by anionic exchange (at pH=4.5) of a
carbonate precursor, reconstruction of the calcined precursor, exchange of a terephthalate
precursor, and, in some cases, in the presence of glycerol used as a swelling agent; however, no
systematic change in the SSA with the synthesis method nor the presence of microporosity is
reported. On the other hand, for samples obtained by terephthalate/decavanadate exchange,
Drezdzon has reported a value of 30 m2/g for a Mg,Al-decavanadate,63 and has concluded that
264 Vicente Rives
the decavanadate “pillars” ar very close spaced, with just enough room for gallery water
molecules. For samples with partial terephthalate/decavanadate exchange (SSA in the range
33-40 m2/g for unexchanged and up to 91% exchanged samples) it is possible to increase the
SSA (and thus the porosity) by calcination, which removes the organic anions only.
Table 2.-Specific surface areas of non Mg,Al-CO3 LDHs
LDH M2+/M3+ ratio Synthesis treatment d(003) (Å) isotherm/ SBET(m2 g-1)/ outgassing temp. comments Ref.
hysteresis type (°C)
Co,Al-CO3 2.0 stirred 65°C/30 7.38 n.r. 64 prepared by low 41
min supersaturation
min supersaturation
min supersaturation
Co,Al-CO3 2.0 non-stirred 7.59 n.r. 65 prepared by sequential 41
65°C/24 h precipitation
Co,Cr-CO3 1.86 r.t./24 h n.r. II 86 (125) 42
Co,Fe-CO3 2.72 60°C/30 h 7.57 II 178 dried in air at 70°C 43
Co,Fe-CO3 2.34 HT/100°C/5 days 7.60 II 42 43
Co,Fe-CO3 2.40 60°C/30 h 7.57 II 77 dried in air at r.t. 43
Cu,Ni,Al-CO3 4.44 65°C/24 h 7.6 II 50 Ni:Cu=0.84 44
Mg,Al-Cl 2.11 stirring/80°C/8 h 7.8 IV 50 (120) 45
Mg,Al,Fe-CO3 2.88 HT/120°C/24 h 7.84 II 59 (125) Al:Fe=1.40 46
Mg,Al,Fe-CO3 3.00 r.t./15 h n.r. n.r. 150 (90) Fe:Al=18:7 47
Mg,Al,Ga-CO3 3.35 80°C/24 h 7.76 n.r. 54 Al:Ga = 1.3 21, 22
Mg,Al,Ir-CO3 2.45 60°C/40 min 7.72 n.r. 68 (90) Ir/Mg/Al=0.5/71/28.5 29
Mg,Al,Ir-CO3 2.45 60°C/40 min 7.81 n.r. 51 (90) Ir/Mg/Al=5/71/24 29
Mg,Al,Rh-CO3 2.45 60°C/40 min 7.70 n.r. 84 (90) Rh/Mg/Al=0.04/71/29 29
Mg,Al,Rh-CO3 2.45 60°C/40 min 7.70 n.r. 78 (90) Rh/Mg/Al=1/71/28 29
Mg,Al,Rh-CO3 2.45 60°C/40 min 7.78 n.r. 95 (90) Rh/Mg/Al=5/71/24 29
Mg,Al,Sn-CO3 3.37 65°C/30 min 7.80 IV 86 Mg:Sn=3:0.09 14
Mg,Al,V-CO3 2.17 HT/120°C/48 h 7.6 n.r. 141 (120) V:Al=0.53 28
Table 2.-Specific surface areas of non Mg,Al-CO3 LDHs (cont.)
Mg,Al,Y-CO3 2.8 r.t./8 h 8.09 n.r. 47 (150) Al:Y = 1.3 48
Mg,Cr-CO3 2.12 HT/100°C/11 days 7.64 n.r. 87 (125) 49
Mg,Fe-CO3 2.45 r.t./15 h n.r. n.r. 94 (90) Fe as Fe2+ 47
Mg,Fe-CO3 2.45 r.t./15 h n.r. n.r. 354 (90) 47
Mg,Fe-CO3 2.93 HT/120°C/24 h 7.89 II 48 (125) 46
Mg,Fe,Al,Fe-CO3 2.45 r.t./15 h n.r. n.r. 161 (90) Mg:Fe2+:Fe3+:Al=62:9:2 47
0:9
Mg,Fe,Al,Fe-CO3 2.45 r.t./15 h n.r. n.r. (117 (90) Mg:Fe2+:Fe3+:Al=52:19: 47
20:9
Mg,Ga-CO3 3.55 80°C/24 h 7.80 n.r. 52 21, 22
Mg,Mn,Al-CO3 3.0 65°C/ 30 min 7.65 IV 53 (100) Mg:Mn =59 20
Mg,Mn-CO3 3.0 r.t. 8.06 n.r. 41 (125) Mn2+:Mn3+=4:21 50
Mg,V-CO3 1.60 HT/120°C/48 h 7.6 n.r. 69 (120) 28
Mg,V-CO3 2.45 HT/125°C/7 days 7.68 n.r. 22 (125) 51
Mg,V-CO3 2.48 HT/125°C/18 days 7.81 n.r. 20 (125) 51
Ni,Mg,Al-CO3 3.08 reflux/70°C/18 h 7.46 II/H3 31 Ni:Mg=0.97 25
Ni,Mg,Al-CO3,NO3 1.86 reflux/70°C/18 h 8.7 II/H3 25 (300) Ni:Mg=3.4 24, 25
Ni,Mg,Al-CO3,NO3 2.63 reflux/70°C/18 h 8.2 II/H3 15 (300) Ni:Mg=10.4 24
Mg,Pd,Al-CO3 2.45 60°C/40 min 7.88 n.r. 74 (90) Pd/Mg/Al=5/66/29 29
Mg,Pt,Al-CO3 2.45 60°C/40 min 7.74 n.r. 150 (90) Pt/Mg/Al=4/67/29 29
Mg,Ru,Al-CO3 2.45 60°C/40 min 7.74 n.r. 88 (90) Ru/Mg/Al=0.5/71/28.5 29
Mg,Ru,Al-CO3 2.45 60°C/40 min 7.69 n.r. 87 (90) Ru/Mg/Al=1/71/28 29
Mg,Ru,Al-CO3 2.45 60°C/40 min 7.74 n.r. 84 (90) Ru/Mg/Al=5/71/24 29
Ni,Al-Cl 2.91 8.01 n.r. 98 (100) 52
Ni,Al-CO3 2.23 100°C/36 h 8.0 n.r. 47 homogeneous 32
precipitation
by urea hydrolysis
Ni,Al-CO3 3.44 HT/120°C/48 h 7.58 II 86 (150) 53
Ni,Al-CO3,NO3 2.82 reflux/70°C/18 h 8.3 II/H3 15 (300) 24, 25
Ni,Al-CO3,NO3 1.99 reflux/70°C/18 h 7.9 II/H3 25 (300) 24
Ni,Cr-CO3 4.0 r.t./14 h 7.61 n.r. 210 54
Ni,Cr-CO3 1.82 HT/100°C/20 days 7.50 n.r. 100 (125) 49
Table 2.-Specific surface areas of non Mg,Al-CO3 LDHs (cont.)
Ni,Fe-CO3 2.38 50°C/2 days 7.67 n.r. 94 55
Ni,V-CO3 2.54 HT/125°C/7 days 7.67 II/H4 72 (150) 56
Ni,V-CO3 2.63 HT/125°C/14 7.65 II/H4 92 (150) 56
days
Ni,V-CO3 4.35 HT/125°C/7 days 7.89 II/H3 97 (150) 56
Ni,V-CO3 2.53 HT/125°C/14 7.86 II/H3 99 (150) 56
days
Zn,Al-Cl 1.8 65°C/30 min 7.64 n.r. 48* (120) 57
Zn,Al-Cl 1.0 r.t./2 h 7.67 IV 45 (200) 58
Zn,Al-Cl 2.1 r.t./2 h 7.75 IV 21 (200) 58
Zn,Al-Cl 3.2 r.t./2 h 7.79 IV 38 (200) 58
Zn,Al-Cl 4.1 r.t./2 h 7.82 IV 45 (200) 58
Zn,Al-CO3 1.86 100°C/36 h 7.6 n.r. 25 homogeneous 32
precipitation by urea
hydrolysis
Zn,Al-CO3 3.0 HT/185°C/18 h 8.9 n.r. 83 (120) 59, 60,
61
Zn,Al-CO3 2.1 60°C/3 h 7.64 IV 21 58
Zn,Al-CO3 3.1 60°C/3 h 7.66 IV 25 58
Zn,Al-CO3 1.8 65°C/30 min 7.38 n.r. 45* (120) 57
Zn,Al-NO3 1.7 65°C/30 min 8.53 n.r. 32* (120) 57
Zn,Al-NO3 2 n.r. n.r. n.r. 26 8
Zn,Al-SO4 1.9 65°C/30 min 8.58 n.r. 25* (120) 57
Zn,Cr-CO3 2.00 60°C/3 days 7.61 II/H4 106 (125) 62
*read from a plot in the original reference
n.r.=not reported
268 Vincente Rives
Zn,Cr- and Ni,Cr-decavanadate LDH displayed SSAs ca. 50% of the value for the
carbonate precursor,54,62 while for Co,Cr- and Ni,Al-decavanadates both values were rather
similar,42,53 again suggesting the lack of accessibility of the interlayer galleries to the nitrogen
molecules. However, some differences in the t-plots73 obtained for these samples suggest the
presence of narrow pores, probably associated to voids between different stacks of materials.
For Zn,Al-decavanadate, a wider average pore diameter is found than for the carbonate or
chloride precursors.58 As the synthesis of these decavanadate-containing LDHS is usually
carried out at rather low pH values (to attain polymerization of the vanadate), some partial
dissolution of the precursor LDH cannot be avoided, and may give rise to the increase in
specific surface area sometimes found, specially when the M2+/M3+ ratio is not maintained from
the precursor to the decavanadate-containing material.28 Such a dissolution effect could be
diminished if intercalation is carried out in the presence of terephthalate or any other organic
molecule;66,67 consequently, narrower pore size distribution curves are observed.
Vansant et al.67 have demonstrated the importance of using a preswelling agent on the
development of microporosity in polyoxometalate (POM)-containing LDHs, as no “clean”
exchange was attained when performed without terephthalate preswelling. According to these
authors, the layer charge density arising from the amount of isomorphically substituted Al3+ in
the LDH layers is the crucial parameter with regards to microporosity development, a question
already pointed out by Cavalcanti et al.18 for hexacyanoferrate-intercalated LDHs (see below).
An improving in surface area and microporosity was observed by lowering the charge density (i.
e., decreasing the Al3+ content) on the LDH layers with [Mo7O24]6-, [V10O28]6-, [PV2W10O40]5-, or
[H2W12O40]6- in the interlayers. The high charge density of LDHs may result in “stuffing” of the
interlayer upon incorporation of large POMs; so, an increase in the M2+/M3+ ratio gives rise to a
lower POM population in the interlayer, accounting for large free micropore volume between
the layers. However, the average pore size did not change appreciably for the vanadate and
molybdate samples, as it did for the Keggin-type intercalates. This is a consequence of the
relative sizes of these POMs. As the M2+/M3+ is increased, the POM concentration decreases,
and so the POM-POM average distance increases. The micropores formed in the interlayer can
be considered to have a “rectangular” shape, one side corresponding to the layer-layer distance
(depending on the size of the POM), and the other corresponding to the POM-POM distance
(which depends on the POM concentration). The average pore size will depend on the smallest
of these two distances. So, for relatively “small” POMs (e. g., heptamolybdate or decavanadate)
the average pore size will be determined by the size of the POM, and will not increase further
even in the POM concentration is decreased (i. e., the POM-POM distance is increased); on the
contrary, for “large” POMs (Keggin-type structures) an increase in the average pore size will be
observed as the POM density decreases, reaching larger pore diameters than when using
decavanadate or heptamolybdate.
LAYERED DOUBLE HYDROXIDES WITH INTERCALATED

HEXACYANOFERRATE COMPLEXES
Values reported in the literature for several LDHs containing hexacyanoferrate anions in
the interlayer are given in Table 4. These systems have been widely studied in the literature, as
a way to incorporate a third metal in mixed oxides obtained after high temperature calcination,
and also because these anions are readily incorporated; as their formal charge are -3 or -4, the
electrostatic interactions with the layers are strong, and so competition with carbonate is not
important; moreover, their detection is easy by infrared spectroscopy and Mössbauer
spectroscopy can be applied as well. Adequately treated, they have proved their usefulness as
chromatographic columns, separating H2, O2, and N2.78
Table 3.-Specific surface areas of LDHs with intercalated oxometalates and polyoxometalates
M2+/M3+ synthesis d(003) isotherm/ SBET(m2 g-1)/

LDH ratio treatment (Å) hysteresis type outgassing temp. (°C) comments Ref.
oxometalates and polyoxometalates
Co,Cr-V10O28 1.60 r.t./48 h 11.72 II/H2 94 (125) 42
Mg,Al-Mo7O24 2.04 stirring r.t. 12.2 n.r. 27 (200) anion exchange of terephthalate 63, 64
Mg,Al-V10O28 2.14 stirring r.t. 11.8 n.r. 30 (200) anion exchange of terephthalate 63, 64
Mg,Al-V10O28 2.0 40°C/15 min 12.1 n.r. 64 (150) 65
Mg,Al-V10O28 2.29 HT/120°C/24 h 11.75 n.r. 74 (120) 28
Mg,Al-V10O28 1.98 65°C/14 h 11.8 II 56 (200) anion exchange of terephthalate 66
Mg,Al-V10O28 1.84 65°C/14 h 11.6 II 64 (200) ibid 66
Mg,Al-V10O28 1.90 r.t./4 h 11.8 II 75 (200) ibid in glycerol 66
Mg,Al-V10O28 1.23 65°C/ 3 days n.r. II 48 (200) reconstruction 66
Mg,Al-V10O28 2.17 r.t./2 h n.r. II 77 (200) reconstructed in glycerol 66
Mg,Al-V10O28 1.91 r.t./5 h n.r. II 89 (200) anion exchange at pH=4.5 66
Mg,Al-V10O28 2.27 r.t./5 h n.r. II 84 (200) ibid in glycerol 66
Ni,Al-CrO4 2.88 10.78 IV 47(100) 52
Ni,Al-Cr2O7 2.83 9.39 IV 53 (100) 52
Ni,Al-V10O28 2.31 r.t./drying 70°C 11.7 II 76 (150) prepared by ion exchange 53
Ni,Al-V10O28 2.03 HT/120°C/14 h 11.7 II 14 (150) prepared by reconstruction 53
NiCr-V10O28 2.0 r.t./96 h 11.7 II/H2 132 54
Zn,Al-Mo7O24 1.81 r.t./16 h 12.3 n.r. 65 (120) terephthalate preswelling/µP 67
Zn,Al-V10O28 1.5 HT/90°C/18 h 11.7 IV 32 (200) Cl- anionic exchange at pH=4 58
Zn,Al-V10O28,V4O12 1.8 HT/90°C/68 h 11.7+9.6 IV 21 (200) CO32- anionic exchange at pH=4 58
Zn,Al-V10O28 2.2 HT/90°C/18 h 9.6 IV 15 (200) CO32- anionic exchange at pH=4 58
Zn,Al-V10O28 2.15 r.t./16 h 12.0 n.r. 62 (120) terephthalate preswelling/µP 67
Zn,Cr-V10O28 1.75 r.t./48 h 11.72 II/H3 56 (125) 62
Table 3.-Specific surface areas of LDHs with intercalated oxometalates and polyoxometalates (cont.)
M2+/M3+ synthesis d(003) isotherm/ SBET(m2 g-1)/

LDH ratio treatment (Å) hysteresis outgassing comments Ref.
type temp. (°C)
Keggin-type and analogues
MgAl-[Co4(H2O)2(PW9O34)2] 2.46 100°C/30 min ≈14.7 n.r. 112 (130) adipate exchange/µP 16
MgAl-[H2W12O40] 3 14.8 I 107 adipate exchange/µP 68
MgAl-α[H2W12O40] 2.23 100°C/30 min ≈14.7 n.r. 120 (130) adipate exchange/µP 16
MgAl-α[P2W18O62] 1.88 100°C/30 min ≈14.7 n.r. 99 (130) adipate exchange/µP 16
MgAl-[PV3W9O40] 3.5 75°C/24 h 11-13 I 137 µP 69
MgAl-[SiW11O39] 3 I 155 adipate exchange/µP 68
Mg,Al-α[H2W12O40] 3.54 70°C/1 h 14.9 n.r. 83 (130) OH exchange/µP 15
Mg,Al-α[H2W12O40] 3.62 70°C/1 h 14.9 n.r. 159 (130) glycerolate exchange/µP 15
Mg,Al-α[H2W12O40] 3.30 70°C/1 h 14.9 n.r. 168 (130) trietilenglicolate exchange/µP 15
NiAl-[PV3W9O40] 1.5 75°C/24 h 11.8 I 134 µP 69
Zn,Al-α[H2W12O40] 2 r.t./90 min 14.5 I 63 (130) nitrate exchange/µP 8, 70
Zn,Al-[H2W12O40] 1.98 r.t./16 h n.r. n.r. 59 (120) terephthalate preswelling/µP 67
Zn,Al-[PV2W10O40] 1.87 r.t./16 h n.r. n.r. 98 (120) terephthalate preswelling/µP 67
Zn,Al-α[SiV3W9O40] 2 r.t./90 min I 155 (130) nitrate exchange/µP 8, 70
ZnAl-[SiV3W9O40] 2.03 stirring r.t./30 min 14.6 113 reconstruction 71
ZnAl-[SiW11O39] 1.7 stirring r.t./30 min 14.6 98 reconstruction 71
ZnAl-[SiW11O39] 3.35 stirring r.t./1 h 14.6 97 direct synthesis 72
µP=microporous
n.r.=not reported
272 Vincent Rives
The size of the hexacyanoferrate anions is also rather large, and so microporosity
development upon their incorporation in the interlayer space of LDHs is commonly observed.
The octahedron is usually oriented with one of its C3 axis perpendicular to the brucite-like
layers, thus giving rise to interlayer spacings close to 6.3 Å (d(003) ca. 11.12 Å).46
Miyata and Hirose have reported76 specific surface areas up to 419 m2/g for
Mg,Al-[FeII(CN)6] LDHs, depending on the outgassing temperature, a treatment leading to
removal of interlayer water, so making such a space accessible for N2 molecules.
One of the most interesting papers on the interlayer accessibility in hexacyanoferrate
intercalated LDHs was reported by Cavalcanti et al.18 The specific surface area calculated from
the size of the crystallites, as determined bt TEM, was ca. 12 m2/g, and 14 m2/g was the value
experimentally determined for the nitrate precursor (Mg/Al=3). However, the specific surface
areas of samples containing [FeII(CN)6] and [FeIII(CN)6] in the interlayers were 246 and 355
m2/g, respectively. The isotherms corresponded to type I in the IUPAC classification,11 clearly
indicating the presence of micropores. Then, as the geometric specific surface areas were very
close for both samples, as both hexacyanoferrate anions have similar sizes, the void region in
the interlayer is essentially determined by the density of anions in the interlayer space, which
depends on their respective charges; therefore, a larger interlayer void volume would be
expected for the tetravalent [FeII(CN)6] than for the three-valent [FeIII(CN)6], but the opposite is
experimentally found. This apparent inconsistency has been explained by these authors
assuming a partial oxidation of the [FeII(CN)6] species upon exposure to air, a process
afterwards also reported by several authors,75,79 which implies intercalation of additional
carbonate anions to attain the electric balance, and thus accounting for the decrease in the
specific surface area expected.
Cavalcanti et al.18 have studied the interlayer accessibility of hexacyanoferrate-containing
LDHs by adsorption of different size hydrocarbons: while identical amounts of n-pentane and
iso-pentane are adsorbed on a Mg,Al-[FeII(CN)6] LDH (Mg/Al=3), a lower amount of n-hexane
is adsorbed, whereas adsorption of n-heptane is small; in addition, adsorption of pentanes
follows a type I isotherm (adsorption in micropores), while adsorption of the other
hydrocarbons showed pronounced kinetic effects (the kinetic diameter of n-hexane is 6.2 Å,
almost coincident with the interlayer distance in the LDH).
Large surface areas, with microporosity development as well, have been reported by Besse
et al.23 for [FeIII(CN)6]-containing Mg,Al LDHs prepared after preswelling the chloride
precursor with different organic solvents; however, both the specific surface area and
micropore volume were always lower than when the exchange was carried out in water (311
m2/g and 0.141 cm3/g, respectively).
The positive effect of decreasing the M2+/M3+ ratio on microporosity development above
commented for POM-intercalated LDHs has been also found for [FeIII(CN)6]-intercalated
samples,74 Table 4. The optimum Mg2+/Al3+ ratio for largest Langmuir surface area (499 m2/g)
and micropore volume (0.158-0.177 cm3/g) was 3.3; larger values lead to a decrease in both
variables.
Vansant et al. have developed80 a model to explain the creation of microporosity in
III
[Fe (CN)6] and [PV2W10O40]-intercalated LDHs. From geometrical models, the maximum
micropore volumes were 0.3843 and 0.1497 cm3/g, respectively. By considering the size of the
pillars (the interlayer anions), pillars outside of the stacks, and the possibility of collapse, a
realistic picture of the microstructure of these solids was reached. Interpillar distances ranging
from 1.5 and 6.0 Å were found for the Mg,Al-[FeIII(CN)6] LDHs, depending on the layer charge,
Surface Texture and Electron Microscopy Studies… 273
and so pore blocking occurred, specially for high charge densities, and thus only parts of the
microstructure were accessible to the N2 molecules. On the contrary, for the
[PV2W10O40]-intercalated samples, the maximum porosity was not reached, probably due to
incomplete (direct) exchange and formation of a side phase (a polyoxometalate salt of the layer
cations due to their partial dissolution). This problem is, however, overcome by exchange with
the assistance of swelling agents, such as terephthalate.67
Upon comparison of the specific surface areas of samples with similar M2+/M+3 ratios, it is
generally found that the values are much larger for hexacyanoferrate compounds than for the
POMs LDHs. However, according to Vansant et al.67 this is actually an artifact, due to the high
“molecular” weight of the POM, in comparison with that of the hexacyanoferrate moiety.
Actually, if the surface area is referred per formula of compound, and not per gram, the
differences reported among Zn,Al LDHs containing [V10O28]6-, [Mo7O24]6-, and [H2W12O40]6-
disappear, although the behaviour displayed by the [PV2W10O40]5- LDH remains unexplained.
Table 4.-Specific surface areas of hexacyanoferrate LDHs
LDH M2+/M3+ synthesis d(003) isotherm/ SBET(m2 g-1)/ comments Ref.

ratio treatment (Å) hysteresis outgassing
type temp. (°C)
Mg,Al-[FeIII(CN)6] 3.89 75°C/16 h n.r. I 294 (150 vac. 16 h) contains CO32-/µP 74

Mg,Al-[FeIII(CN)6] 3.17 60°C 11.12 I 143 (125)µP 46
Mg,Al-[FeIII(CN)6] 3 11.0 I 355 (150 vac. 16 h) contains CO32-/µP 18
Mg,Al-[FeIII(CN)6] 3 r.t./1 h n.r. I 311 (80 vac. 4 h) µP 23
Mg,Al-[FeIII(CN)6] 3 r.t./1 h n.r. I 209 (80 vac. 4 h) prp’d. in H2O-C2H5OH/µP 23
Mg,Al-[FeIII(CN)6] 3 r.t./1 h n.r. I 216 (80 vac. 4 h) prp’d. in H2O-Ethyleneglycol/µP 23
Mg,Al-[FeIII(CN)6] 3 r.t./1 h n.r. I 58 (80 vac. 4 h) prp’d. in H2O-Glycerol/µP 23
Mg,Al-[FeIII(CN)6] 3 r.t./1 h n.r. I 132 (80 vac. 4 h) prp’d. in H2O-Acetone/µP 23
Mg,Al-[FeIII(CN)6] 2.16 r.t./3 h 10.43+7.60 IV/H1 133 (125 vac. 2 h) contains CO32-/µP 75
Mg,Al-[FeIII(CN)6] 1.75 r.t./24 h 10.44+7.54 IV/H1 125 (125 vac. 2 h) contains CO32-/µP 75
Mg,Al-[FeII(CN)6] 3 40°C 11.18 I 419 (150)contains CO32-/µP 76
Mg,Al-[FeII(CN)6] 3 11.0 I 246 (150 vac. 16 h) contains CO32-/µP 18
Mg,Al-[FeII(CN)6] 3 r.t. 10.5 n.r. 80 (200) 77
Mg,Al-[FeII(CN)6] 1.97 r.t./3 h 10.62+7.79 IV/H1 110 (125 vac. 2 h) contains CO32-/µP 75
Mg,Al-[FeII(CN)6] 1.73 r.t./24 h 10.77+7.79 IV/H1 144 (125 vac. 2 h) contains CO32-/µP 75
n.r.=not reported
µP=microporous; r.t.= room temperature
CALCINED LDHS
It is well established that calcination of LDHs gives rise to deep changes in their structure,
together with changes in their specific surface area and pore development. In most of the cases,
the layered structure collapses at temperatures ranging from 200 to 500 °C (depending mainly
on the particular nature of the layer cations and that of the interlayer anion), forming mostly
amorphous materials; above this temperature, crystallization of new phases (oxides of the metal
cations, or their salts, depending on the nature of the interlayer anion) takes place.
The changes observed in the specific surface area along these structural changes depend
mostly on the nature of the interlayer anion: if this forms a volatile species upon decomposition
(e. g., carbonate and nitrate, forming CO2 and NO/NO2, respectively), an increase in the
specific surface area is usually observed, which decreases when crystallization of new phases
takes place, Fig. 2.14 However, if the anion is a permanent species (e. g., a polyoxometalate),
then a steady decrease in the surface area is usually observed. The isotherms correspond to type
II24 or IV81 in the IUPAC classification, characteristic of mesoporous solids, a favourable point
for catalysis and adsorption applications, since diffusional limitations are restricted.81
Reichle et al.26 reported that CO2 and H2O vapour evolution during thermal decomposition
of a carbonate-containing LDH takes place through fines pores generated at the brucite-like
layers, thus accounting for the increase in specific surface area observed for the
medium-temperature calcined samples. However, this effect should correspond only to
escaping of water generated during collapsing of the layered structure through condensation of
hydroxyl groups, as very close values are measured for the specific surface areas of un-calcined
samples and those calcined at ca. 200 °C, Fig. 2, a treatment leading only to dehydration of the
interlayer space. The maximum specific surface area development is generally observed for
samples calcined at ca. 500-600 °C if the layer cations are Mg, Al, Ga, etc.21,22,27 Quite
surprisingly, although similar changes in the X-ray diffraction patterns have been described,
Yamaguchi et al.82 have reported a steady decrease in the specific surface area of a Mg,Al-LDH
prepared from alkoxides. On the other hand, with LDHs containing transition metal cations in
the layers, and interlayer carbonate, sintering of the amorphous material (and thereof,
decreasing of the specific surface area) is observed at lower temperatures (maximum surface
area development around 250-300 °C), probably because of the formation of highly stable
spinels.41,44,53,54,56
These effects can be clearly seen in Fig. 3. Changes in the specific surface area of
Co,Cr-carbonate and Co,Cr-[V10O28],42 (similar results are obtained for Zn,Cr analogues62),
follow the trends above commented: the surface area increases for the carbonate-containing
LDH, probably because of the formation of channels and chimneys through the brucite-like
layers, as proposed by Reichle et al.,24 and then decreases when crystalline products are formed.
Maximum surface area development is observed around 200-250 °C for the
carbonate-containing LDH (check the value for the Mg,Al-carbonate LDH in Fig. 2), due to
early crystallization of Co,Cr oxides. For the decavanadate-containing LDH, however, the SBET
remains almost constant up to ca. 200 °C, then decreasing; in this case, channels through the
brucite-like layers are formed, if any, only via dehydration, thus accounting for the lack of
surface area development for intermediate calcination temperatures.
276 Vincente Rives
Figure 2.-Left: Powder X-ray diffraction patterns of Mg,Aln,Sn-CO3 LDH calcined at the temperatures given
(Mg:Al:Sn = 3:0.70:0.29). LDH =layered double hydroxide; P = periclase (MgO), AS = spinel (MgAl2O4), TS
= spinel (Mg2SnO4). Right: Specific surface area evolution with temperature for (circles) Mg,Al,Sn-CO3
LDHs (Mg:Al:Sn = 3:0.70:0.29), (triangles) Mg,Al-CO3 LDH (Mg:Al = 3:0.70). Reprinted from S. Velu, K.
Suzuki, M. Okazaki, T. Osaki, S. Tomura and F. Ohashi, Synthesis of new Sn-incorporated layered double
hydroxides and their thermal evolution to mixed oxides. Chem. Mater., 11 (1999) 2163-2172, © 1999,with
permission from the American Chemical Society.
ELECTRON MICROSCOPY
Both Scaning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM)
have been applied in order to learn about the shape and size of the LDHs, and on changes upon
thermal activation.
LDHs usually present a hexagonal platelet morphology,40,83-85 Fig. 4, although in some
cases,86,87 as that of takovite, fibrous particles have been observed. The diameter of the particles
and their thickness depend on several factors, the main one being the ageing treatment given to
the sample during synthesis. In Cu,Al LDHs it has been reported that the thickness of the
platelets increases with the Cu content,88 and the sheet morphologies are also more crystalline
when the copper content is higher.
Figure 3.-Specific surface area evolution for Co,Cr-CO3 and Cr,Co-[V10O28] LDHs with temperature.
Adapted from [42].
Hexacyanoferrate-containing LDHs show a behaviour similar to that of systems with

volatile anions, because of pores formed during evolution of gases proceeding from
decomposition of the cyanide ligands: the surface area remains high, but microporosity is
cancelled, developing mesopores.
Figure 4.-Transmission electron micrograph of a Mg,Mn-CO3 LDH. Reprinted from J. M. Fernández, C.

Barriga, M. A. Ulibarri, F. M. Labajos and V. Rives, Preparation and Thermal Stability of
Manganese-containing hydrotalcite, [Mg0.75Mn(II)0.04Mn(III)0.21(OH)2](CO3)0.11.nH2O, J. Mater. Chem.,
4 (1994) 1117-1121, © 1994, with permission from the Royal Society of Chemistry.
Ageing of the precipitated LDHs gives rise to an increase in the size of the crystallites,27,34
as shown in Fig. 5 for Mg,Al-CO3 LDHs27 submitted to hydrothermal treatment for several
278 Vincente Rives
days at 125 °C. The crystallite size also increases with the ageing temperature: Reichle40 has
reported changes from 0.2 x 0.01 µm for a Mg,Al-CO3 LDH crystallized at 65-75 °C (18 h),
which increases to 1 x 0.1 µm if aged at 200 °C for the same time, and even to 15 x 0.1 µm at
300 °C; although for the sample aged at 65-75 °C the micrographs showed poorly crystallized
platelets, well defined hexagonal particles could be observed when the ageing temperature was
increased. Bhattacharyya and Hall89 have reported HREM images of the layered structure of a
Mg,Al-triborate LDH.
In some HREM images of Mg,Ga-CO3 LDHs, dislocations, stacking faults, weaving
planes and disruptions in planes have been reported;90 the interlayer spacing of the layers near
the edge of the laminate is larger than the interlayer spacing in the bulk of the crystallite,
suggesting that layers located near the outmost edges of the crystallite are more loosely bound
to each other than those found toward the bulk of the crystallite, where electrostatic attraction
among layers and interlayers brings about a smaller interlayer spacing. This could be attributed
to a non-homogeneous distribution of trivalent cations in the layers (the lower the M3+
concentration, the lower the electrostatic charge of the layers, and the lower the attraction
between layers and interlayers), or to different orientation of interlayer species (carbonate and
water molecules); however, no definitive conclusion is reached.
Figure 5.-Transmission electron micrographs of a Mg,Al-CO3 LDH; (a) untreated, and submitted to
hydrothermal treatment at 125 °C for (b) 4, (c) 8, and (d) 13 days. Reprinted from F. M. Labajos, V. Rives and
M. A. Ulibarri, Effect of hydrothermal and thermal treatments on the physicochemical properties of Mg-Al
hydrotalcite-like materials, J. Mater. Sci., 27 (1992) 1546-1552, © 1992, by kind permission from Kluwer
Academy Publishers.
After calcination at increasing temperatures, aggregates of very small particles are

observed, but with a lower crystallinity, Fig. 6;91 however, overall the general morphology of
the solids is mostly retained, the thermal decomposition proceeding topotactically,26,86,92 as

reported for Mg,Al and Ni,Al LDHs. In some cases, when the calcination temperature is further
increased, the particles show a nodular appearance, probably related to the oxides being formed
at these temperatures.25
(a) (b)
Figure 6.-Scanning electron micrographs of Zn,Al-NO3 LDH (above) air dried, and (b) calcined in vacuum at
450 °C 3 h. A. Reprinted from Béres, I. Pálinkó, I. Kiricsi, J. B. Nagy, Y. Kiyozumi and F. Mizukami, Layered
double hydroxides and their pillared derivatives - materials for solid base catalysis: synthesis and
characterization, Appl. Catal. A: General, 182 (1999) 237-247. © 1999, with permission from Elsevier Science.
CONCLUSIONS
Layered double hydroxides cyrstallize usually forming hexagonal-shaped platelet-like
crystals. The surface area development depends almost exclusively on the ageing treatment to
which the solid is submitted (e. g., heating, hydrothermal treatment, etc.). Access of the
nitrogen molecules to the interlayer space is only possible if the layers are appart enough, by
interlayer large anions, such as hexacyanoferrate or polyoxometalate; in these cases,
microporosity is observed, although also depending on the density population of these anions.
On calcination, the surface area increases at moderate temperatures, pores being formed by CO2
or NO2 molecules escaping through the brucite-like layers; at higher temperatures sintering is
observed, by crystallization of well defined species.
ACKNOWLEDGMENTS
Finantial support from DGICYT (grant PB96-1307-C03-01), DGI-MCyT (grant
MAT2000-1148-C02-01) and Junta de Castilla y León (Consejería de Educación y Cultura,
grant SA45/96) is greatly acknowledged.
280 Vincente Rives
REFERENCES
2. F. Trifirò and A. Vaccari, in “Comprehensive Supramolecular Chemistry. Volume 7.
Solid-State Supramolecular Chemistry: Two- and Three-Dimensional Inorganic
Networks”, eds. J. L. Atwood, J. E. D. Davies, D. D. MacNicol, F. Vögtle, J.-M. Lehn, G.
Alberti and T. Bein, Pergamon, Oxford, 1996, p. 251.
3. V. Rives and M. A. Ulibarri, Coord. Chem. Rev. 181 (1999) 61.
4. C. O. Oriakhi, I. V. Farr and M. M. Lerner, Clays Clay Miner. 45 (1997) 194.
5. S. Carlino, Chem. Brit., (1997) Sept., 59.
6. T. Sato, K. Kato, T. Endo and M. Shimada, Reactivity Solids 2 (1986) 253.
7. K. Chibwe and W. Jones, J. Chem. Soc., Chem. Comm. (1989) 926.
8. T. Kwon and T. J. Pinnavaia, Chem. Mater. 1 (1989), 381.
10. S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc. 60 (1938) 309.
11. K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. Pierotti, J. Rouquerol and J.
Sieminiewska, Pure Appl. Chem. 57 (1985) 603.
12. S. Lowell and J. E. Shields, “Powder Surface Area and Porosity”, Chapman and Hall,
London, 1984.
13. J. I. Di Cosimo, V. K. Díez, M. Xu, E. Iglesia and C. R. Apesteguía, J. Catal. 178 (1998)
499.
(1999) 2163.
15. S. K. Yun, V. R. L. Constantino and T. J. Pinnavaia, Microporous Mater. 4 (1995) 21.
16. S. K. Yun and T. J. Pinnavaia, Inorg. Chem. 35 (1996) 6853.
18. F. A. P. Cavalcanti, A. Schutz and P. Biloen, in “Preparation of Catalysts IV”, Eds. B.
Delmon, P. Grange, P. A. Jacobs and G. Poncelet, Elsevier Sci. Pub., Amsterdam (1987),
p. 165.
19. A. Elm’chaouri and M. H. Simonot-Grange, Thermochim. Acta 339 (1999) 117.
20. S. Velu, N. Shah, T. M. Jyothi and S. Sivasanker, Microporous Mesoporous Mater. 33
(1999) 61.
21. M. A. Aramendía, Y. Avilés, J. A. Benítez, V. Borau, C. Jiménez, J. M. Marinas, J. R. Ruiz
and F. J. Urbano, Microporous Mesoporous Mater. 29 (1999) 319.
22. M. A. Aramendía, Y. Avilés, V. Borau, J. M. Luque, J. M. Marinas, J. R. Ruiz and F. J.
23. F. Malherbe, C. Forano and J. P. Besse, Microporous Mater. 10 (1997) 67.
24. D. Tichit, F. Medina, B. Coq, R. Dutartre, Appl. Catal. A: General 159 (1997) 241.
25. F. Medina, R. Dutartre, D. Tichit, B. Coq, N. T. Dung, P. Salagre and J. E. Sueiras, J.
Molec. Catal. A: Chemical 119 (1997) 201.
26. W. T. Reichle, S. Y. Kang and D. S. Everhardt, J. Catal. 101 (1986) 352.
27. F. M. Labajos, V. Rives and M. A. Ulibarri, J. Mater. Sci. 27 (1992) 1546.
28. F. Kooli, I. Crespo, C. Barriga, M. A. Ulibarri and V. Rives, J. Mater. Chem. 6 (1996)
1199.
29. F. Basile, G. Fornasari, M. Gazzano and A. Vaccari, Appl. Clay Sci. 16 (2000) 185.
30. F. Kovanda, E. Kovácsova and D. Kolousek, Collect. Czech. Chem. Comm. 64 (1999)
1517.
31. L. Pesic, S. Salipurovic, V. Markovic, D. Vucelic, W. Kagunya and W. Jones, J. Mater.
Chem. 2 (1992) 1069.
32. U. Costantino, F. Marmottini, M. Nocchetti and R. Vivani, Eur. J. Inorg. Chem. (1998)
1439.
33. T. Hibino, Y. Yamashita, K. Kosuge and A. Tsunashima, Clays Clay Miner. 43 (1995) 427.
34. T. Hibino and A. Tsunashima, Chem. Mater. 10 (1998) 4055.
35. H. P. Klug and L. E. Alexander “X-ray Diffraction Procedure for Polycrystalline and
Amorphous Materials”, Wiley, New York, 1956, p. 49.
36. F. M. Labajos, Ph. D. Thesis, Universidad de Salamanca, Spain, 1993.
37. Joint Committe for Powder Diffraction Standards, International Centre for Diffraction
Data, Pennsylvania, USA, 1977, file 22-700.
38. J. R. Smyth and D. L. Bish, “Crystal Structures and Cation Sites of the Rock-forming
Minerals”, Allen and Unwin, London, 1988, p. 69.
39. Ts. Stanimirova, I. Vergilov, G. Kirov and N. Petrova, J. Mater. Sci. 34 (1999) 4153.
41. S. Kannan and C. S. Swamy, Catal. Today 53 (1999) 725.
42. M. del Arco, M. V. G. Galiano, V. Rives, R. Trujillano and P. Malet, Inorg. Chem. 35 (1996)
6362.
43. M. del Arco, R. Trujillano and V. Rives, J. Mater. Chem. 8 (1998) 761.
44. V. Rives and S. Kannan, J. Mater. Chem. 10 (2000) 489.
45. A. Ookubo, K. Ooi, F. Tani and H. Hayashi, Langmuir 10 (1994) 407.
46. J. M. Fernández, M. A.Ulibarri, F. M. Labajos and V. Rives, J. Mater. Chem. 8 (1998)
2507.
47. S. M. Auer, J.-D. Grunwaldt, R. A. Köppel and A. Baiker, J. Molec Catal. A: Chemical
139 (1999) 305.
48. J. M. Fernández, C. Barriga, M. A. Ulibarri, F. M. Labajos and V. Rives, Chem. Mater. 9
(1997) 312.
49. F. M. Labajos and V. Rives, Inorg. Chem. 35 (1996) 5313.
50. J. M. Fernández, C. Barriga, M. A. Ulibarri, F. M. Labajos and V. Rives, J. Mater. Chem. 4
(1994) 1117.
51. F. M. Labajos, V. Rives, P. Malet, M. A. Centeno and M. A. Ulibarri, Inorg. Chem. 35
(1996) 1154.
52. F. Malherbe, L. Bigey, C. Forano, A. de Roy and J. P. Besse, J. Chem. Soc., Dalton Trans.
(1999) 3831.
53. F. Kooli, V. Rives and M. A. Ulibarri, Inorg. Chem. 34 (1995) 5114.
54. F. Kooli, V. Rives and M. A. Ulibarri, Inorg. Chem. 34 (1995) 5122.
55. M. del Arco, P. Malet, R. Trujillano and V. Rives, Chem. Mater. 11 (1999) 624.
56. F. M. Labajos, M. D. Sastre, R. Trujillano and V. Rives, J. Mater. Chem. 9 (1999) 1033.
57. S. Velu, V. Ramkumar, A. Narayanan and C. S. Swamy, J. Mater. Sci. 32 (1997) 957.
58. C. Barriga, W. Jones, P. Malet, V. Rives and M. A. Ulibarri, Inorg. Chem. 37 (1998) 1812.
59. A. Fudala, I. Pálinkó, B. Hrivnák and I. Kiricsi, J. Thermal Anal. Calorimetry 56 (1999)
317.
60. A. Fudala, I. Pálinkó and I. Kiricsi, J. Molecular Struct. 482-483 (1999) 33.
282 Vincente Rives
62. M. del Arco, V. Rives, R. Trujillano and P. Malet, J. Mater. Chem. 6 (1996) 1419.
63. M. A. Drezdzon, in “Novel Materials in Heterogeneous Catalysis”, Eds. R. Terry, K.
Baker and L. L. Murrell, American Chemical Society, Washington DC, 1990, pp.
140-148.
64. M. A. Drezdzon, Inorg. Chem. 27 (1988) 4628.
65. E López Salinas and Y. Ono, Bull. Chem. Soc. Jpn. 65 (1992) 2465.
66. M. A. Ulibarri, F. M. Labajos, V. Rives, R. Trujillano, W. Kagunya and W. Jones, Inorg.
Chem. 33 (1994) 2592.
67. H. Nijs, M. de Bock and E. F. Vansant, J. Porous Mater. 6 (1999) 101.
68. E. D. Dimotakis and T. J. Pinnavaia, Inorg. Chem. 29 (1990) 2393
69. J. Wang, Y. Tian, R.-C. Wang and A. Clearfield, Chem. Mater. 4 (1992) 1276.
70. T. Kwon and T. J. Pinnavaia, J. Molec. Catal. 74 (1992) 23.
71. E. Narita, P. Kaviratna and T. J. Pinnavaia, Chem. Lett. (1991) 805.
72. E. Narita, P. D. Kaviratna and T. J. Pinnavaia, J. Chem. Soc., Chem. Comm. (1993) 60.
73. B. C. Lippens and J. H. de Boer, J. Catal. 4 (1965) 319.
74. H. Nijs, N. de Bock and E. F. Vansant, Microporous Mesoporous Mater. 30 (1999) 243.
75. M. J. Holgado, V. Rives, M. S. Sanromán and P. Malet, Solid State Ionics 92 (1996) 273.
76. S. Miyata and T. Hirose, Clays Clay Miner. 26 (1978) 441.
77. A. Beres, I. Palinko, A. Fudala, I. Kiricsi, Y. Kiyozumi, F. Mizukami and J. B. Nagy, J.
Thermal Anal. Calorimetry 56 (1999) 311.
79. C. B. H. Hansen and B. C. Koch, Clays Clay Miner. 42 (1994) 170.
80. H. Nijs, M. de Bock, N. Maes and E. F. Vansant, J. Porous Mater. 6 (1999) 307.
81. J Sánchez-Valente, F. Figueras, M. Gravelle, P. Kumbhar, J. López and J. P. Besse, J.
Catal. 189 (2000) 370.
82. O. Yamaguchi, H. Taguchi, Y. Miyata, M. Yoshinaka and K. Shimizu, Polyhedron 6 (1987)
1587
83. R. Szymanski, Ch. Travers, P. Chaumette, Ph. Courty and D. Durand, in “Preparation of
Catalysts IV”, eds. B. Delmon, P. Grange, P. A. Jacobs and G. Poncelet, Elsevier Sci.
Pub., Amsterdam, 1987, p. 739.
84. F. Thevenot, R. Szymanski and P. Chaumette, Clays Clay Miner. 37 (1989) 396.
85. J. M. Fernández, C. Barriga, M. A. Ulibarri, F. M. Labajos and V. Rives, J. Mater. Chem. 4
(1994) 1117.
86. O. Clause, B. Rebours, E. Merlen, F. Trifirò and A. Vaccari, J. Catal. 133 (1992) 231.
87. F. Prinetto, D. Tichit, R. Teissier and B. Coq, Catal. Today 55 (2000) 103.
88. A. Alejandre, F. Medina, P. Salagre, X. Correig and J. E. Sueiras, Chem. Mater. 11 (1999)
939.
89. A. Bhattacharyya and D. B. Hall, Inorg. Chem. 31 (1992) 3869.
90. E. López-Salinas, M. García-Sánchez, J. A. Montoya, D. R. Acosta, J. A. Abasolo and I.
Schifter, Langmuir 13 (1997) 4748.
91. A. Béres, I. Pálinkó, I. Kiricsi, J. B. Nagy, Y. Kiyozumi and F. Mizukami, Appl. Catal. A:
General 182 (1999) 237.
92. T. Sato, H. Fujita, T. Endo, M. Shimada and A. Tsunashima, Reactivity Solids 5 (1988)
219.
PART II: APPLICATIONS
Chapter 9
LAYERED DOUBLE HYDROXIDES IN

WATER DECONTAMINATION
María Ángeles Ulibarri1* and María del Carmen Hermosín2
1
Departamento de Química Inorgánica en Ingeniería Química, Universidad de Córdoba,
Campus de Rabanales, Edificio C-3, 14071-Córdoba, Spain
2
Instituto de Recursos Naturales y Agrobiología, Consejo Superior de Investigaciones
Científicas, C.S.I.C., Sevilla, P. O. Box 1052, 41080-Sevilla, Spain
INTRODUCTION
The increasing contamination of soils, sediments and water has its origin in several human
activities (industry, agriculture, domestic uses, urban activities, etc.). Thus, the chemical nature
of the contaminants is widely diverse and some examples of chemicals and its origin are given
in Table 1.1 The presence of these contaminants has raised a large concern because they may
affect human health, thus there is a need to develop new techniques to abate or to remove them
from soil, sediments or water. One of the most widely used process to remove contaminants
from water or soil or to confine or immobilize them in contaminated sites, is the adsorption or
entrapping in an appropriated sorbent. Hence an interesting current research topic is to look for
developing of new adsorbent materials. Although active carbon (in its diverse forms) is still the
most universal adsorbent to remove contaminants from water and soils,2 others are being
developed as advantageous such as clays, organic polymers, etc.
Hydrotalcite, HT, and hydrotalcite-like compounds, also called anionic clays or layered
double hydroxides (LDHs) have, as the traditional clays, adsorbing properties because of their
large interlayer space which may be accessible to molecular polar species and anions. Actually,
the layered structure of HT is the main fact that makes it a very attractive sorbent since that
interlayer may host very diverse chemicals such as contaminants. The structure of hydrotalcite
consists of brucite type layers positively charged because of the partial substitution of the
original divalent metal cations (Ca(II), Mg(II), Ni(II), Co(II), Zn(II), etc.) for trivalent ones
(Al(III), Fe(III), Cr(III), etc.). The positive charge is balanced by inorganic anions (Cl-, NO3-,
ClO4-, CO32-, SO42-, etc.) located in the interlayer with variable amounts of interlayer hydration
water molecules.3 The general formula is [M1-xIIMx III(OH)2]Xx/nn- · mH2O and the layer charge
286 María Ángeles Ulibarri and María del Carmen Hermosín
will depend on the M(II)/M(III) ratio. The first property inherent to this structure is the anion
exchange capacity4 that occurs through the reaction represented by Eqn. (1):
[M1-xIIMx III(OH)2]Xx/nn-· mH2O + (x/m)Yn- → [M1-xIIMx III(OH)2]Yx/nn-· mH2O + (x/m)Xn- (1)
Table 1.- Industrial and agricultural activities and possibilities of contamination
ACTIVITY CONTAMINATION IN WATER

Battery Industry Heavy Metals (Cd, Pb, Cr, Cu, Mg)
Mining Cd, Pb, Cr, Cu, Mg, Zn, As, Ni, Sc, Cyanides
Glass Industry F, Pb
Printing Industry Chlorinated Hydrocarbons, Aromatic Hydrocarbons
Mg, Ar
Painting, Varnish and Dyes Nitrophenols, Hydrocarbons, Metals, Alcohols
Plastic Residues
Wood Industry Aromatic Cyclic Hydrocarbons, Heavy Metals
Phenols
Textile Industry Hydrocarbons, Aromatic Hydrocarbons, Metals
Acids and Bases, Salts, Plastic Residues
Laundries Tetrachloroethylene
Pesticide Industry Halogenated Hydrocarbons, Hg, Ti, As
Phenols (Nitrophenols, Chlorophenols, etc.)
Crude Oil and Related Industry Aromatic and Polycyclic Aromatic Hydrocarbons,
Hydrocarbons (Oils), Metals (Pb, Zn, Cu, Ni, Cd)
Metallurgical and Galvanic Industry Aromatic Hydrocarbons, Heavy Metals, Cyanides
Detergent Industry Surfactants
Workshops Hydrocarbons, Acids, Pb
Tannery Hydrocarbons, Acids, Metals (Cu), Salts
Solvents, Cyanides, Colorant Residues
Plastic Aromatic Hydrocarbons, Metals (Co, Cd, Mg) Cyanides, Amines
Transformation Industry Hydrocarbons, Heavy Metals, Acids
Ship and Naval Industry Chlorinated Hydrocarbons, Phenols
Heavy Metals (Hg, Sn, As), Solvents
Microelectronic Factory Hydrocarbons, Chlorinated Hydrocarbons
Aromatic Hydrocarbons
Heavy Metals (Cu, Ni, As, Cd, Zn, Sb), Acids
Paper Manufacturing Organic Substances, Hg
Tobbac Industry Cd
Vine Industry Cyanides, Phenols
Solid Urban Residues Dumps Organic Substances, Inorganic Substances, Metals
Photograph Laboratories Organic Substances, Ag
Agriculture Pesticides, Fertilizers (Nitrates and Phosphates)
Heavy Metals
The progress of this reaction will be affected by the original anionic species in the
interlayer and the layer charge or M(II)/M(III) ratio of the hydrotalcite sheet. The interlayer
shows a high affinity for carbonate, and then it is very difficult to remove it; divalent anions are
usually more difficult to be removed than monovalent ones.5 With respect to the layer charge, a
general rule is that when the layer charge increases the exchange reaction may became difficult.
Layered Double Hydroxides in Water Decontamination 287
HT may be also intercalated with diverse anionic species by another way, making use of the
so-called “memory effect”:6 HT calcined (hererafter CHT) at 500ºC results in a mixed oxides
structure (Eqn. 2), which in the presence of water and anionic species reverts to the original
layered structure through the reconstruction reaction (Eqn. 3):
500ºC
[M1-xIIMx III(OH)2]Xx/nn-· mH2O → [M1-xIIMx IIIO] + (m+1)H2O + others (2)
[M1-xIIMx IIIO] + Yx/nn- + (m+1)H2O → [M1-xIIMx III(OH)2]Yx/nn-· mH2O (3)
These last reactions give one of the most attractive aspects of the hydrotalcite as adsorbent
for contaminants. The calcination allows the recycling and reuse of the sorbent and the
elimination of organic contaminants as CO2 and water simultaneously, as it will be shown
below.7,8
Thus, hydrotalcite-like compounds act as sorbent of anionic species through two types of
reactions, namely, anion exchange and reconstruction, which further adds the possiblity of
recycling and reuse. These facilities, besides the easy and low cost method to synthetize HT,
specially the MgAl-CO3 system, make these layered systems one of the most attractive sorbents
to remove or confine contaminants existing in water and soil. Summarizing, the type of
contaminant or “target species” to be adsorbed by HT are those of anionic character, inorganic
as well as organic. Although some polar organic molecules, by similarity with natural clays,
could be adsorbed in the interlayer hydration water, this type of reaction has been scarcely
described.4,9
ADSORPTION OF INORGANIC CONTAMINANTS ON HT AND CHT

The inorganic contaminants that can be adsorbed by HT and CHT are anionic species such
as oxoanions (NO3-, SO42-, PO43-, AsO43-, CrO42-, etc.) and monoatomic anions (F-, Cl-, Br-, I-,
etc.), including those radiactive. These anionic contaminants are adsorbed by anionic exchange
on HT or by reconstruction on CHT through reactions (1), and (2) and (3), respectively. Both
adsorption processes are affected by the structural characteristics of HT, mainly the origin and
value of charge layer, and the original and adsorbing anionic species. In fact, the first
applications of HT were developed as anionic exchangers.4,5 The main advantages of HT over
the traditional anionic exchange resins are their higher anionic exchange capacity (AEC) and
the fact that HT are resistant to high temperature treatments. HT is therefore used as ion
exchanger in some high temperature applications such as in the treatment of cooling water of
nuclear reactors.10 HT compounds have also been investigated for the immobilization of 129I- in
nuclear fuel wastes,11 although poor results were obtained because of the difficulty to displace
CO32- anions from the interlayer and the low selectivity to iodide anions. In fact, the most
important limiting factor for the exchange reaction (1) is the presence of CO32- as the interlayer
anion. For that reason, the most recent papers on anion adsorption on HT consider
simultaneously the possibility of both processes: anion exchange on HT and reconstruction
from CHT.
Anionic Species
The possibility of exploiting the anion sorption capacity of calcined Mg-Al-LDH by

reusing it in a cycle involving heat treatment, anion sorption, and carbonate exchange to
remove the sorbed anions has been investigated.8 The sorbed anions include F-, Br-, B(OH)4-,
NO3-, HPO42- and SO42-. The sorption experiments were carried out using samples of freshly
calcined (400ºC) hydrotalcite, and carbonate-free solutions, as former studies indicated that
these are the most favourable conditions to reach the maximum adsorption. The calcined
material slowly sorbs carbon dioxide and water from the atmosphere, reverting to hydrotalcite.
After 7 days of ambient exposure, X-ray diffraction peaks associated to hydrotalcite were
observed, although a large fraction of the calcined material remained unaltered. After 43 days,
hydrotalcite is the major phase. Similar results had been previously published by other
authors.12
The sorbed amounts, expressed as milliequivalents of anion sorbed per gram of original
hydrotalcite, are shown in Fig.1. An initial, fast sorption was observed for all the anions (except
for chloride), followed by a slower increase until the final resulting value was reached. After 24
h, the total amounts sorbed were in the order:
SO42- > F- > HPO42- > Cl- > B(OH)4- >NO3-
This order is similar to that given by Miyata5 for the ion exchange equilibrium constants.
The more strongly bound anions are those with the smaller ionic radii, which results in a
decrease of the spacing between the layers.
On the other hand, the maximum theoretical anion capacity of 3.6 mequiv/g was not
achieved. This has been explained assuming that hydroxide anions would also be present,
competing with the anion being studied to be adsorbed; actually, Sato et al.13 observed the pH
of solutions to increase to 9.5 soon after addition of CHT. Additionally, after the first cycle, the
full capacity of the HT was never restored. The sorption capacity is reduced by about 50% after
the first cycle, and then shows only a slight decline with further cycles.The conclusion is that
CHT is more effective than HT because carbonate interlayer anions in the last one are difficult
to be displaced at least with the anions tested in this study.
Figure 1.-Amount of anion sorbed by freshly fired hydrotalcite vs. time. The experiments for each anion were
carried out separately in decarbonated solutions. Reprinted from L. M. Parker, N. B. Milestone and R. H.
Newman, The use of hydrotalcite as an anion absorbent, Ind. & Eng. Chem. Res. 34 (1995) 1196, © 1995, with
permission from the American Chemical Society.
The different retention mechanisms of monovalent and divalent anions , such as Cl-, SO42-
and CrO42- , on HT and CHT, as well as the location of adsorption sites and the competition
effects between adsorbates, has been evaluated by Châtelet et al.14 On carbonate-saturated HT,
the adsorption of CrO42-, SO42- and Cl- is very weak, but on CHT the adsorption for divalent
anions is complete. In mixed solution of monovalent, (Cl-) and divalent (SO42- or CrO42-)
anions, the adsorption of divalent anions on CHT is not strongly affected by the presence of
monovalent anions. On the contrary, divalent anions inhibit the adsorption of the monovalent
ones.
With respect to the adsorption mechanism, the presence of two kinds of anion retention
sites on HT and CHT can be distinguished: (i) sites within the interlayer corresponding to the
structural AEC of the sorbent, and (ii) adsorption sites on the external surface. The nature of
these retention sites for different anions can be approached through the study of the variation of
zeta potential with pH in the presence of various electrolites. It is possible to conclude from
these studies that Cl- anions are not adsorbed on the external surface of HT but partial
adsorption of CrO42- and SO42- anions occurs on these external sites. Quantitative information
from the adsorption isotherms of anions on CHT is shown in Fig. 2. In the case of CrO42- and
SO42-, the adsorption stradily increases until the AEC is reached (2.1 meq·g-1), reaching a
plateau for an adsorbed amount of 4.5 meq·g-1 for CrO42- and 3.2 meq·g-1 for SO42-. The
discontinuity observed in the isotherms exactly corresponds to the AEC of CHT, and the second
part of the isotherm can then be assigned to the adsorption on external sites. For Cl-, the
maximum amount adsorbed is lower than the AEC, which confirms the absence of adsorbed Cl-
on the external surfaces. The affinity decreases in the order CrO42- > SO42- > Cl-.
Figure 2.-Adsorption isotherms of CrO42-, Cl- and SO42- onto CHT vs. Qi (meq g-1). Reprinted from L.
Châtelet, J. V. Bottero, J. Yvon and A. Bouchelaghem, Competition between monovalent and divalent anions
for calcined and uncalcined hydrotalcite: anion exchange and adsorption sites, Colloids & Surfaces, A:
Physicochem. Eng. Aspects 111 (1996) 167, © 1996, with permission from Elsevier Science.
Taking advantage of the property of HT-like compounds to keep the original capacity of
ion exchange after thermal treatment between 500-800ºC (that is, they can be recycled), Shin et
al.15 claimed the use of these compounds as an alternative process for removal of
phosphorus-containing compounds. They considered three different routes: (i) phosphate
removal with HT containing Cl- as the interlayer anion, by an ion exchange mechanism; (ii)
phosphate removal with HT-CO3 calcined at 600ºC (i.e., a magnesium aluminium CHT), and
(iii) the possibility of recycling through the “memory effect”. The pH value for all the
experiments during phosphate uptake was 7.5, because the phosphate anionic exchange
capacity by HT-Cl was maximum at a pH of 7-8;16 at pH 7.7 the ionic species of phosphates in
the solution phase are a mixture of HPO42- (70%) and H2PO4- (30%).
Fig. 3 shows the results of phosphate uptake by HT-CO3, HT-Cl and CHT. As expected,
HT-CO3 exhibits a negligible exchange capacity. CHT removed only 35% of phosphate at room
temperature, but the efficiency increased at 60ºC. The most promising results correspond to
HT-Cl, as it removed 91% of phosphate in 1 hour. The value of phosphate uptake was close to
the chloride content in LDH-Cl, suggesting that phosphate ions are mostly ion-exchanged with
interlayer chloride ions. The presence of a small excess of phosphate uptake was explained
assuming its adsorption on the external surface of the HT-Cl crystal. In addition, the effect of
competitive anions (NO3-, SO42- and HCO3-) on phosphate uptake was also studied. The results
indicate that bicarbonate efficiently inhibits phosphate uptake, but SO42- ions also gave rise to a
reduction in the phosphate removal efficiency.
Figure 3.-Phosphate uptake rate by LDHs and CLDH. Reprinted from H.-S. Shin, M. J. Kim S.-Y. Nam and
H.-C. Moon, Phosphorus removal by hydrotalcite-like compounds (HTLcs), Water Sci. Technol. 34 (1996)
161.
To test the recyclability of HT, calcined hydrotalcite, CHT, was repeatedly used for 6 times
for ion exchange and intermediate calcination. In recalcining at 600ºC, the intercalated
phosphate is removed as gaseous P2O5 and a phase closely similar to that of CHT is obtained.
The initial phosphate uptake rate decreases up to the fourth time the process is repeated, but the
total phosphate uptake capacity increases to some extent. From the sixth time onwards,
however, the phosphate uptake capacity decreases.
The influence of the layer composition was reported by Goswamee et al.17 These authors
studied the adsorption of Cr(VI) by various uncalcined and calcined HT of Mg-Al, Ni-Al and
Zn-Cr, with CO32- as the interlayer anion. They reported that the adsorption of Cr2O72- on
uncalcined HT through ion exchange is slower and smaller than on the calcined one, where the
adsorption occurs via rehydration. Secondly, they observed that the adsorption is higher on
Mg-Al than on Ni-Al or Zn-Cr -HT calcined at 450ºC (Fig. 4). According to Miyata,5 on
calcination of Mg-Al-HT below 800ºC, Al3+ ions remain inside of the MgO particles forming a
Mg-Al oxide solid solution which is able of forming back HT on rehydration. Although the
same is true for Ni-Al-HT, the 450ºC calcined product shows much lower adsorption ability
(Fig. 4). This can be attributed to the requirement of hydrothermal treatment for rehydration of
the calcined Ni-Al-HT.18 The low adsorption capacity of calcined Zn-Cr-HT, however, can be
explained considering that on calcination at 450ºC this compound decomposes by complete
segregation to ZnO and ZnCr2O4, which are unable to rehydrate and reconstruct the HT
structure.
Release of Cr2O72- from the adsorbed product has been also studied; it depends on the type
of anion present in the aqueous solution, CO32- resulting the most effective (Fig. 5). Calcination
up to 1250°C of the product (Mg-Al-LDH) containing adsorbed Cr2O72- did not result in the
formation of Cr-immobilized phases.
Figure 4.- Adsorption abilities of different calcined LDH. Reprinted from R. L. Goswamee, P. Senguta, K. G.
Bahattacharyya and D. K. Dutta, Adsorption of Cr(VI) in layered double hydroxides, Appl. Clay Sci. 13 (1998)
21, © 1998, with permission from Elsevier Science.
Removal of chromate ions from aqueous solutions by uncalcined HT with chloride as the
interlayer anion (Mg-Al-Cl, Zn-Al-Cl and Zn-Cr-Cl) has been also reported.19,20 The treatment
of solutions containing 15 to 300 ppm of CrO42- was successful, but according to X-ray
diffraction data, the Cl/CrO42- ion exchange does not take place to a noticeable extent.
Kovanda et al.21 used synthetic hydrotalcite calcined at 350-550ºC for removal of arsenate,
chromate and vanadate from water solutions. They found that hydrotalcite calcined at 450ºC
exhibited the best sorption ability for all the anions. The sorption selectivity of the calcined HT
decreases in the orden vanadate > arsenate > chromate, but the experimentally found values of
the sorption capacity were significantly lower than those theoretically calculated from the AEC
of the hydrotalcite used.
Figure 5.- Release of adsorbed Cr2O72- by Cl- and CO32- ion. Reprinted from R. L. Goswamee, P. Senguta, K.
G. Bahattacharyya and D. K. Dutta, Adsorption of Cr(VI) in layered double hydroxides, Appl. Clay Sci. 13
(1998) 21, © 1998, with permission from Elsevier Science.
The sorbed anions were released by anion exchange in a carbonate-containing solution and
after subsequent calcination, the hydrotalcite was used again for the removal of anions. During
repeated calcination – rehydration - anion exchange cycles the adsorption capacity of HT
steadily decreased. Kovanda et al.21 found that the sorption capacity was reduced to ca 80% in
the first cycle and to ca 50% after the second cycle when arsenate or vanadate anions were
sorbed. The subsequent cycles decreased the capacity only very slightly. These results are
similar to those previously reported by Parker et al.8 However, no decrease in the sorption
capacity was observed during repeated calcination - rehydration - anion exchange cycles when
the anion was chromate. The changes in the sorption capacity as a function of the number of
cycles are shown in Fig. 6.
The reduction in the sorption capacity probably depends on the retention of the hydrotalcite
lattice structure, and, therefore, the ability of the calcined hydrotalcite to regenerate as a layered
crystal structure during the rehydration process. Except for chromate, this ability is degraded
with every calcination- rehydration- anion exchange (in Na2CO3 solution) cycle, as it is shown
in Fig.7.
Figure 6.-Change in the sorption capacity of hydrotalcite for removal of arsenate, chromate and vanadate from
aqueous solutions with the number of cycles. Adapted from reference 21.
Figure 7.- Repeated sorption of vanadate: powder X-ray diffraction patterns of hydrotalcite after anion
exchange in carbonate solution in single calcination-rehydration-anion exchange cycles. Reprinted from F.
Kovanda, E. Kovávsová and D. Kolousek, Removal of anions from solution by calcined hydrotalcite and
regeneration of used sorbent in repeated calcination-rehydration-anion exchange processes, Collect. Czech.
Chem. Comm. 64 (1999) 1517, © 1999, with permission from Academy of Sciences of the Czech Republic.
Radiactive Anions
Decontamination of radiactive waste water is a complex problem; among radiactive anions,

iodine is one of the nuclides causing most concern. Furthermore, iodide, as I- is poorly sorbed
on most geological materials. HT compounds are some of the few inorganic anion exchangers
with relatively high exchange capacities and for that reason Fetter et al.22 have used HT to
remove 131I- from aquous solutions. The 131I- sorption by HT depends greatly on the thermal
treatment of the solid and does not take place by ion exchange removing CO32- or other ions
from the interlayer of HT. But if the anions have been previously removed from the solid by
calcination at 500ºC, 131I- ions can ocupy the anionic sites when HT crystallizes again by the
addition of the aqueous solution. The best results for adsoption of 131I- are found when the anion
removed from HT by calcination is CO32- instead of NO3- or SO42-.
The influence of the temperature of calcination of HT on the adsorption capacity for 131I-
has also been studied.23 The calcination temperature determines the surface area of the resulting
mixed oxides and that property seems to be the most important factor controlling the I- sorption.
The highest surface area is obtained for sample calcined at 500ºC and the solid exhibits the
maximum sorption of I- anions (63% of AEC), whereas calcination of HT at 700-800ºC
resulted in a low surface area and a low I- retention. It seems that the increase of the surface area
of the mixed oxides formed during calcination permits the free access of I- ions to the exchange
sites, reacting with the oxide and recovering the layered structure of HT.
On the other hand, the ion exchange sorption of 131I- on HT in the nitrate form in the
presence of microwave radiation, has been investigated.24 The microwave irradiation produces
purer solids whose crystallite size is small; iodide ions are then able to diffuse easily between
the layers and to reach the core of the HT crystallites. The influence of the [Al/(Mg+Al)] ratio
on the sorption of 131I- from aqueous solutions by HT-NO3 has been also discussed, concluding
that 131I- was more efficiently sorbed in high [Al/(Mg+Al)] ratio hydrotalcites.
The calcined product of hydrotalcite, CHT, has been used to remove 99Mo anionic species
from radiactive wastewater.25 The sorption measured was higher than that corresponding to the
anion exchange capacity of HT, which can be attributed to an additional adsorption on the
external surface of the HT crystallites. This effect was also observed by Châtelet et al. in the
sorption of CrO42- and SO42-.14 Likewise, the initial pH value of the molybdate solution controls
the molybdate sorption. The quantity of molybdate ions sorbed reached a maximum value
when the initial pH of the molybdate solution was 5, but was a minimum when the initial pH
was 13. This effect was also described by Hermosín et al.26 for the sorption of trinitrophenol
anion on calcined hydrotalcites, and it can be attributed to the competition with OH- anions at
pH 13.
In this paper25 it was shown that when the calcined hydrotalcite is packed in a column, it
can be useful as a support for 99MoO42-, from which 99mTc can be separated through an elution
process (99Mo is a radiactive isotope which decays to 99mTc, whose compounds are useful for
medical purposes). This study was conducted in the aim to obtain in the future a 99mTc generator
that would be prepared with low specific activity for 99Mo. The main species were identified by
electrophoresis at pH 5 as 99TcO4- and 99MoO42-, even if, according to Cotton and Wilkinson,27
the molybdate ions are partially polymerized at pH 5, with paramolybdate (Mo7O246-) and
molybdate ions coexisting in solution. During the elution process with a 0.5% NaCl aqueous
solution a very good separation of 99mTc and 99Mo was achieved (98% of 99mTc and < 0.01%
99
Mo). As shown in previous papers,5,14 divalent 99MoO42- ions were strongly attached to the
HT, but monovalent 99mTcO4- ions were easily removed; i.e., the chloride ions in the elution
solution preferentially replaced 99mTcO4-, but not 99MoO42-.
Miscellaneous Species
Organometallic compounds and oxides of heteroelements (e.g., Hg, As, Sb, Se, Pb, etc.)
are beneficially used in high-tech industry, some biomedical fields and agriculture product
industries.28 Dimethylarsenic acid (DMAA) is one of them, increasingly used in microbiology
an related fields, but it cannot be effectively separated from waste solutions by a conventional
coprecipitation method. Hydrotalcite (HT) was tested along with other ion exchangers for their
potential use in separation chemistry for dimethylarsenic acid; inorganic As(III) and As(V) ions
were also investigated.29 The predominant species at pH 8-11 are (CH3)2AsOO-, AsO3(OH)2-
and As(OH)4-. The largest adsorption was found for As(V) followed by As(III). DMAA showed
a low selectivity. These results can be related with the selectivity of HT for diverse anions as a
function of the charge and the size.5
Lehmann et al.30 compared the efficiency of various inorganic materials, including
hydrotalcite, as sorbents to remove chromate anions and zinc cations from dilute solutions. HT
sorbents have been specifically synthesized for the removal of anionic metal forms, and
therefore, the large percentage of Zn cations removal was not expected. Nevertheless,
considering the structure of HT, the CO32- and OH- groups can act as proton-acceptors. Hence,
a pH increase of aqueous HT dispersions can be provoked, leading to alkaline pH values and
subsequently, causing precipitation of cationic metal species. In the case of Zn(II), the removal
was very effective at low concentrations when the final pH was higher than 7 and the
precipitation of zinc hydroxides occurs. The addition of higher Zn(II) concentration was found
to reduce the alkaline behaviour of HT leading to a final pH value of 5.9, where precipitation of
Zn hydroxides does not happen.
Finally, it should be noted that the synthesis of HT itself can be directly applied to the
treatment of waste water31 and, related with this subject, Readon et al.32 reported the formation
of anionic clays (hydrotalcite) in the lime treatment of fly ash slurries for anion scavenging.
Lime and dolomite are minerals formed by stacked sequences of double metal hydroxide layers;
they have a net positive charge and, as a result, elements in an anionic form in fly ash leachate
waters are scavenged into the interlayer positions to balance the positive charge, resulting in the
formation of hydrotalcite like compounds. Leachate borate, sulphate and arsenate
concentrations were could be reduced by up to 2 orders of magnitude by this method.
In a short communication, Komarneni et al.33 report on a new function for anionic clays
which could be useful for the decontamination and immobilization of transition metals.
Mg-Al-CO3 and Mg-Al-NO3 LDHs show high and selective uptake of transition metal cations
such as Cu(II), Ni(II), Co(II) and Zn(II) in water solution. Both anionic clays selectively
remove 100% of all the transition metal cations, M(II), from diluted solutions (10-4 – 10-5 M).
When the concentration of the metal cation was increased, the uptake of cations changed with
the type of transition metal cation as well as the nature of the anion clay. They postulated that
this uptake follows a substitution mechanism for Mg (mainly) in the anionic clay crystal
structure, through a process known as diadochy. According to these authors, this substitution
should be facilitated by the easy access for the cations through the interlayer spaces and taking
into account that, in fact, anionic clays with these anions in the interlayer have been prepared by
many researchers.3,34,35 This discovery could find applications in the remediation of metal
contamination of drinking water as well as decontamination of waste waters.
ADSORPTION OF ORGANIC CONTAMINANTS ON HT AND CHT

The exchange and reconstruction reactions, according to eqs (1-3) showed in the
introduction section, are also useful for adsorption of organic contaminants of anionic character
on HT. In fact, many organic contaminants such as phenols, aromatic carboxylic acids, dyes,
pesticides, etc., have anionic character. In addition, natural polymers existing in water, such as
humic or fulvic acids, need sometimes to be removed for some water use. Here we will consider
the organic contaminants as divided in three groups, mainly clasified by their molecular size:
aromatic anions and pesticides, large organic anions as surfactants and dyes, and finally, natural
organic polymers or humic substances.
Aromatic Anions
The intercalation of benzenecarboxylate ions with different electric charge into the
interlayer of hydrotalcite by using magnesium aluminium oxide, CHT, as starting material, was
studied36 in order to clarify the effect of the electric charge density of the anion on the
intercalation behaviour in CHT. The sorbates used range from benzenemonocarboxylate to
benzenehexacarboxylate ions with calculated electric charge densities varying from 3.5 to 9.9
Q/nm2. The intercalation was carried out by adding a fixed amount of magnesium-aluminium
oxide into a solution of different concentrations of benzenecarboxylate. Except for
benzenemonocarboxylate, for which the adsorption was very low, more than 80% of
benzenecarboxylate was removed at low concentration of benzenecarboxylic acid. In the first
case, OH- seems to be simultaneously taken up into the interlayer, and the selectivity for OH-
intercalation is higher than that for benzenecarboxylate; these findings can be related to the
difference in anionic size.
The degree of saturation of the anionic exchange capacity by various benzenecarboxylate
ions is shown in Fig.8 as a function of the initial amount of benzenecarboxylate ion in the
solution. The dashed line is the theoretical maximum saturation percentage. The selectivity for
the intercalation of benzenecarboxylate ions with multielectric charges is higher than that of
OH-; however, the interlayer space of hydrotalcite was not large enough to incorporate these
large ions to balance all the positive layer charge. It seems that multielectric charge
benzenecarboxylate ions are incorporated at first, and then OH- of small size occupies the
remaining space to balance the residual layer charge. The selectivity of anion uptake by
hydrotalcite increases with increasing the electric charge of anions.
Phenols are another type of organic contaminants of industrial waters that have also
attracted the attention as adsorbates to be removed by HT and CHT. A very wide and deep study
has been done by Ulibarri and Hermosín and their co-workers7,26,37-43 by combining diverse
hydrotalcite characteristics for two different phenols: 2,4,5 trichlorophenol (TCP), weakly
acidic and slowly soluble in water, and 2,4,6-trinitrophenol (TNP) with higher solubility and
acidity. The sorption mechanisms of TCP from aqueous solution on a synthetic hydrotalcite
(HT) and its calcined product (HT500) have been studied37,38 to explore the potential use of
these solids as phenol sorbents. Using the batch equilibration technique, the kinetics of the
adsorption, the influence of different initial pH and the adsorption at different phenol
concentrations (isotherms) were determined. The variation of TCP adsorption on both sorbents
with TCP concentration is shown in Fig. 9. The adsorption isotherms were of the L type for HT
at pH 13 and of C type for HT500 at pH 13 and pH 4 (final pH 12), according to the
classification by Giles et al.44
TCP can be adsorbed on HT by an anion exchange reaction, but the low adsorption
capacity measured (Fig. 9) suggests that this adsorption occurred only on the external surface at
the edges of the interlayer spaces. This low adsorption is due to the high affinity of the HT by
CO32- as the interlayer anion. The calcined product, HT500, can adsorb anions by
reconstruction of the structure according to the equation:
Mg3AlO3(OH) + (4+x) H2O + PhO- → Mg3Al(OH)8(PhO) · xH2O + OH- (4)
Formation of OH- anions is in agreement with the higher TCP adsorption on HT500 from
an acidic initial pH solution (pH 4), Fig. 9. However, OH- should be also intercalated
simultaneously in addition to phenolate, PhO- anions, as the maximum amount of TCP
adsorbed represented only 12% of the anionic exchange capacity of HT500.
Figure 8.- Degree of saturation of the anion exchange capacity by various benzenecarboxylate ions in the
interlayer of hydrotalcite by uptake of benzenecarboxylate ions from 50 cm3 of aqueous solution by adding
0.75 meq of Mg0.61Al0.26O at 70ºC for 12 h: (a) benzenemonocarboxylate ion, (b) 1,4-benzenedicarboxylate
ion, (c) 1,3,5-benzenetricarboxylate ion, (d) 1,2,4,5-benzenetetracarboxylate ion, (e) benzenepentacarboxylate
ion, (f) benzenehexacarboxylate ion. Reprinted from T. Sato and A. Okuwaki, Intercalation of
benzenecarboxylate ions into the interlayer of hydrotalcite, Solid State Ionics 45 (1991) 43, © 1991, with
permission from Elsevier Science.
The sorption of TNP on HT and HT500 were also tested to select the best conditions for the
solid/solution ratio, initial pH, contact time, etc.40 The sorption on uncalcined HT is favoured at
acid pH (pH=2), and 2 h of contact time is enough to reach the maximum adsorption. However,
the sorption on HT500 is not greatly influenced by the pH, although at pH 2 the amount of TNP
removed is slighly higher, probably because of the competition between TNP and OH- anions at
high pH. The influence of pH on the adsorption on both sorbents is summarized in Figure 10.26
Since the acid dissociation constant of TNP is pKa= 3.8, it should exist in the phenolate form at
the pH reached at the end of the adsorption experiments. The high amount of TNP adsorbed by
HT at the lowest initial pH could be explained by the acidic conditions favouring the
displacement of interlayer CO32- by TNP anions into the interlayer by anionic exchange. Also
on HT500, the adsorption was favoured at low pH because the reconstruction reaction (4) is
proton consuming.
The reconstruction process is slower than the anion exchange and a higher contact time (24
h) is necessary in this case. As shown in Fig. 11, the kinetic profiles of TNP adsorption from
aqueous solutions on both sorbents is very different: In the first 30 min a large amount of TNP
was removed from the solution by HT, probably because the displacement of interlayer CO32- is
favoured at low pH. A simultaneous increase of pH occurs and once pH 7 is reached, some of
the initially adsorbed TNP seems to be displaced again by OH- or CO32- present in the solution,
and after 20 h the equilibrium is reached. Adsorption of TNP on HT500 is large and fast in the
first 5 h, followed by a slow adsorption from 5 to 72 h. The increase of pH in the solution was
instantaneous during the consumption of protons due to reconstruction of the layered structure
of HT. The slower second step seems to confirm the reconstruction mechanism.
Figure 9.- Adsorption isotherms of TCP on HT at pH 13(a) and on HT500 at pH 13(b) and pH 4 (c) with a
solid/solution ratio of 0.10g/5ml. Reprinted from M. C. Hermosín, I. Pavlovic, M. A. Ulibarri and J. Cornejo,
Trichlorophenol adsorption on layered double hydroxide: A potential adsorbent, J. Environ. Sci. Health
A28(1993) 1875.
Figure 10.-Effect of pH on the adsorption of TNP on (A) hydrotalcite and (B) hydrotalcite calcined at 500 °C.
Adapted from reference 26.
From the adsorption isotherms, the maximum adsorption of TNP on HT is 650 µmol/g,
which corresponds to 20% of the total AEC (3300 µmol/g) of the HT, suggesting the
coexistence of TNP, CO32- and/or OH- anions in the interlayer. The rather large maximum
adsorption measured on HT500, 2250 µmol/g, indicates that in this case 40% of the AEC of
HT500 (5800 µmol/g) was saturated with TNP anions.
X-ray diffractograms of compounds with TNP as the unique anion are compared in Fig. 12
with those of original HT or HT500, and with those of the products recovered after the
adsorption isotherm (hereafter “isotherm product”). Basal spacing of two phases, HT-CO3 and
HT-TNP, are observed in the diffractograms of the isotherm products, confirming the presence
of TNP anions in the HT interlayer.
Figure 11.-Left: (a) Evolution of the amount of TNP adsorbed on HT and (b) pH evolution. Right: (a) Evolution
of the amount of TNP adsorbed on HT500 and (b) pH evolution. Reprinted from M. C. Hermosín, I. Pavlovic,
M. A. Ulibarri and J. Cornejo, Hydrotalcite as sorbent for trinitrophenol: sorption capacity and mechanism,
Water Res. 30 (1996) 171, © 1996, with permission from Elsevier Science.
HT and HT500 can be recycled when they act as sorbents of trichloro- and trinitrophenols.7
DTA and TG diagrams of the products obtained after adsorption of TCP and TNP on either HT
or CHT, showed the elimination of these contaminants, through combustion to CO2 and water,
rendering the same final product, CHT. This is confirmed by X-ray diffraction and IR
spectroscopy.40 Hence, after adsorption of phenols, HT and HT500 compounds should be able
to undergo thermal recycling by combustion of the adsorbed contaminant, as illustrated

schematically in Fig. 13.7 Experiments performed calcining (500ºC, 2 h) the isotherm product
after TCP or TNP adsorption isotherm on CHT showed that they recovered the same adsorption
capacity as the original product,26 confirming the recyclability of CHT as adsorbent to remove
phenols from water.
The influence of the crystallinity and of the interlayer anion of the HT and CHT sorbents on
the adsorption of TNP has been reported by Ulibarri et al.41 The adsorption of TNP on HT by
anionic exchange is dramatically affected by the nature of the interlayer anion. On the basis of
the calculated anion exchange capacity, HTCO3 adsorbed 23% whereas HTCl adsorbed up to
100% of TNP. These exchange capacities were scarcely modified by the crystallinity, which
seems to be more important in the case of the carbonate samples. On the contrary, the
adsorption of TNP by reconstruction on HT500 was very much affected by the crystallinity;
however, HT500 derived from HTCO3 samples adsorbed better than those derived from HTCl
samples (Table 2).
Figure 12.-X-ray diffraction patterns of left: (a) original HT, (b) the anionic exchange product HT-TNP and (c)
the isotherm product (in the “plateau”); right: (a) HT500, (b) the reconstruction product HT-TNP and (c) the
isotherm product (in the “plateau”). Reprinted from M. C. Hermosín, I. Pavlovic, M. A. Ulibarri and J. Cornejo,
Hydrotalcite as sorbent for trinitrophenol: sorption capacity and mechanism, Water Res. 30 (1996) 171, © 1996,
with permission from Elsevier Science.
The above results indicate that HTCl was more effective than HTCO3 to adsorb TNP by
anionic exchange. However, HTCO3500 was more effective than HTCl500 to remove TNP by
reconstruction of the layer structure.
The increase in the crystallinity of the parent samples improved the “memory effect” and
enlarged the adsorption capacity, this effect being more noticeable for the HTCO3500 sorbent.
Figure 13.-Scheme of the thermal recycling of a hydrotalcite-like compound and its calcined product.
Reprinted from M. A. Ulibarri, I. Pavlovic, M. C. Hermosín and J. Cornejo, Hydrotalcite-like compound as
potential sorbents of phenols from water, Appl. Clay Sci. 10 (1995) 131, © 1995, with permission from
Elsevier Science.
Table 2. Langmuir model for TNP adsorption on HTCO3 and HTCl and on their calcined
products, HTCO3500 and HTCl500, adapted from reference 41
Adsorbent Temperature(°C) Cm(µmol/g) L

HTCO3 25 876 1 · 10-3
80 775 0.39
130 510 3.43
HTCO3500 25 2257 25 · 10-3
80 3030 2.06
130 4545 5.50
HTCl 25 3226 2.07
80 3226 2.07
130 3226 2.07
HTCl500 25 2564 0.20
80 2439 2.28
130 3030 2.54
The effect of other variables, such as the M(II)/M(III) ratio (layer charge) and the nature of
the trivalent cation (Al(III) or Fe(III)) on the sorption of TNP by HT and CHT were also
studied.42,43 TNP adsorption by anionic exchange on system MgAlCO3 is not affected by the
Mg/Al ratio, while it does on MgAlCl. In the case of the MgFeCl system, the higher polarizing
power of Fe(III) makes the exchange reaction less favorable.
On comparing the higher adsorption capacity of MgAlCl with Mg/Al=3 with respect to that
with Mg/Al=4, the high layer charge in the first case seems to favour the diffusion of TNP into
the layer, displacing the Cl- anion. The influence of the layer composition (Fe(III) or Al(III) ) is
shown in Fig. 14.
Figure 14.-Adsorption isotherms of TNP on MgAlCl, MgFeCl and MgFe500, with M(II)/M(III) =3 (0.05g/10
ml).
The substitution of Al(III) by Fe(III) increases the effective charge on the layer, which
attracts strongly the chloride anions and probably constrains its displacement from the
interlayer, reaching only about 50% of AEC saturated with TNP anions. The XRD diagrams of
the isotherm product in Fig. 15 confirms this, as they show the presence of two phases with
TNP anions (d003=13.6 Å) and chloride anions (d003=7.9 Å) in the interlayer. The
diffractograms for MgFeCl and for the fully anion exchanged reaction product, MgFeTNP, are
also included.
During the isotherm of TNP adsorption on the calcined product shown in Fig.14, only 31%
of AEC is reached. This value is very much lower than the expected one and those values
observed for other calcined HTs (MgAlCO3500, 100% of AEC; MgAlCl500, 68% of the AEC).
The explanation for this behaviour is given by the X-ray diffraction pattern of the calcination
product MgFe500 (Fig. 15), which shows the presence of a biphasic material, a spinel phase
MgFe2O4 and a MgO cubic phase. The X-ray diffraction patterns of the product in the isotherm
plateau show changes in the relative intensity of the spinel lines with respect to the MgFe500
patterns, and additional new lines corresponding to a layer phase with TNP as interlayer anion
(d003=13.2 Å) are also observed.
The reconstruction process is not complete because of the high stability of the spinel
phase18 and only the portion of the calcined product corresponding to the MgO cubic phase is
reconstructed. In general, spinels formed from hydrotalcites with transition metal cations in the
layer are formed at lower temperature than MgAl2O4.18,35
Figure 15.-X-ray diffraction paterns of (a) original MgFeCl, (b) the anionic exchange product MgFeCl-TNP,
and (c) the isothermal product (in the “plateau”); (a’) MgFe500 and (b’) the reconstruction product
MgFeCl500-TNP (in the “plateau”).
Pesticides
Pesticides are one of the main groups of organic contaminants whose presence in water is
increasing, because of their wide use, mainly in agriculture. Pesticides are a very wide group of
compounds of diverse chemical character (organophosphorous, organochlorine, triazines,
phenoxyacetic acid, ureas, carbamates, etc.). From the point of view of its high risks as
contaminants and as target model to be removed by HT or HTC, we will draw our attention on
those of acidic or anionic character, and additionally other compounds will be considered for
comparison.
The first work related to adsorption of a pesticide by HT was reported by Hermosín et al.,45
who compared diverse adsorbents for the herbicide 2,4-dichlorophenosyacetic acid (2,4-D).
They found that Ni,Al-CO3 hydrotalcite is a better adsorbent than natural smectite, sepiolite
and some organoclays with medium size organic cations. However, the adsorption of 2,4-D was
mainly limited to the external surface because of the lack of ability of the monovalent 2,4-D
anions to displace carbonate from the interlayer. Lakraimi et al.46 have recently reported on the
intercalation of the pesticide 2,4-D in Zn-Al-Cl hydrotalcite. The effect of 2,4-D concentration
in the solution and of the temperature on the ion exchange were studied. The sample with the
best crystallinity was obtained at 100ºC with a 2,4-D concentration corresponding to the
solubility limit of the ion in water, 0.004 M 2,4-D. The anion intercalation was achieved
without degradation of the pesticide anion.
In the two last years some papers have been reported about the adsorption of pesticides on
hydrotalcites. Celis et al.47 have compared the ability of two montmorillonites, one hydrotalcite
and some of their organoderivatives to sorb the ionizable pesticide IMAZAMOX
(2-[4,5-dihydro-4-methyl-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-(methoxymethyl)-3-pyr
idinecarboxylic acid) at different pH, to determine their potential use as sorbent materials for
ionizable organic pollutant.
At the pH of the sorbents (pH 6-7), the anionic form of imazamox is the predominant one,
and the calcined product of hydrotalcite, HT500, was found to be the best sorbent for the
imazamox anion. Imazamox sorption-desorption isotherms on HT500 show a very low
hysteresis, indicating that sorption could be an essentially reversible process. As expected,
negligible sorption of imazamox anion was, however, measured on hydrotalcite, because of the
high affinity of its layered structure by the CO32- anion.
The sorption capacity of hydrotalcite for a series of pesticides as a function of their
structure and their polar, hydrophobic or anionic nature has been also reported.48 Table 3 shows
some properties of the pesticides assayed. Glyphosate is a highly soluble anionic pesticide;
acephate is a polar pesticide and linuron, atrazine and diazinon are considered as hydrophobic
pesticides.
Table 3. Freundlich constants (K) and distribution coefficients (Kd) for the adsorption of
glyphosate by HT and HT500 at different pH values, adapted from reference 50.
Sorbent pH Adsorption constant

Initial Final K N Kd1
HT 2.0 5.0 55.54 0.80 36.82
3.9 7.2 9603 0.79 6252
5.5 7.2 4724 1.09 5372
11.5 11.5 762.1 0.72 408.8
HT500 2.0 7.5 17,822 1.06 19,428
3.9 8.4 23,242 0.99 22,820
5.5 9.5 19,997 1.22 26,558
11.5 12.0 10,106 1.54 17,801
1
Equilibrium concentration Ce= 0.2 µg/mL.
The large variations in the adsorption capacities shown in Table 2 must be related to the
properties of the pesticides. Linuron, atrazine and diazinon are neutral and therefore unable to
displace the CO32- anion from the interlayer space of HT. However, at the pH of the HT
suspension, glyphosate must be present as an anion and its sorption is fairly high, probably
because of partial substitution of the interlayer CO32- anions, although glyphosate is mainly
adsorbed is on the external surface of HT. This is confirmed by X-ray diffraction and IR spectra,
which suggest the formation of adsorption complexes through the interaction of the PO32- group
of the glyphosate with Mg and Al atoms of the surface of HT. The K values (Table 3) for the
adsorption of different pesticides by HT500 indicate that the adsorbing power for this sample is
lower than that of HT for the hydrophobic pesticides and higher than that of HT for the
organophosphorus compounds. The adsorption of glyphosate for HT500 was four times higher
than for HT, and for acephate 30-fold higher for HT500 than that measured with HT.
At the pH of the suspension of HT500 (pH 9.8), acephate must be mainly hydrolized,49 and
the mechanism of interaction of both pesticides must be the same, as suggested for the
adsorption of glyphosate on HT. IR spectra and X-ray diffraction patterns showed that
glyphosate molecules must coat the surface of the HT500, in such a way that they prevent the
reconstruction of the original HT (it is known that this reconstruction occurs spontaneously in
aqueous solution). In the case of acephate, a partial reconstruction during the adsorption takes
place.
In conclusion, these authors48 propose two mechanism for the adsorption of glyphosate on
HT and HT500: (i) electrostatic attraction between the surface of HT, positively charged below
pH 12, and the glyphosate anion, and (ii) ligand exchange between the P-OH and/or C = 0
groups of the herbicide and the Al and Mg atoms of the HT surface. They related the occurrence
of one or both mechanisms to the pH of the adsorption system.50 The adsorption isotherms on
HT and HT500 at different pHs are given in Fig. 16. In both cases, the lowest adsorption was
obtained for initial pH values of 2 and 11.5 of the glyphosate solution, when the molecule is
positively charged or trivalent negatively charged. The strongest adsorption corresponds to the
pH values where the molecule has a net negative charge of one or two, and more favourable
conditions prevail for electrostatic attraction.
Figure 16.-Adsorption isotherms of glyphosate on HT (A) and on HT500 (B) at different pH values. Reprinted
from M. J. Sánchez-Martín, M. V. Villa and M. Sánchez-Camazano, Glyphosate-hydrotalcite interactions as
influenced by pH, Clays Clay Min. 47 (1999) 777, © 1999, with permission from the Clays Mineral Society.
Anionic Surfactants and Dyes
Anionic surfactants are present in surface waters from their industrial and domestic use as
detergents or tensioactives and they are among the particularly important pollutans affecting
organisms living in water.51,52 Other large organic anions that can be found in waste water are
those used as colorants in textil and related industries. Pavlovic et al.38,53,54 have tested the
usefulness of hydrotalcite, HT, and of calcined hydrotalcite, HT500, for removing anionic
surfactants as dodecylsulfate (DDS) and dodecylbenzenesulfonate (DBS) from water.
As expected, the adsorption of DBS on HT was very low because of the steric hindrance
due to its bulky size to overcome the high affinity of HT by the carbonate anion.38 However, the
anionic exchange is complete when the interlayer anion is Cl-, reaching 100% of AEC for HTCl.
The anionic exchange reactions were scarcely modified by the crystallinity. On the contrary, the
adsorption of DBS on HT500 by reconstruction increases with the crystallinity. HT500 derived
from HTCO3 samples were better adsorbents than those derived from HTCl samples. The
adsorption on HT500 (from untreated samples) was about 50%,53 but DBS adsorption
increased up to 100% on HTCO3500 and only up to 70% on HTCl500 (from 130ºC
hydrothermally treated samples).41 Adsorption of DBS on untreated and hydrothermally treated
HTCO3500 is shown in Fig. 17. The increase in the crystallinity of the parent samples renders
probably a better ordered mixed oxide, improving the “memory effect” and enlarging the
adsorption capacity.
Figure 17.-DBS adsorption on HTCO3500 for untreated sample and hydrothermally treated at 80ºC and 130ºC
(0.05 g/30 ml, pH 6, 24 h). Reprinted from M. A. Ulibarri, I. Pavlovic, C. Barriga, M. C. Hermosín and J.
Cornejo, Adsorption of anionic species on hydrotalcite-like compounds: effect of interlayer anion and
crystallinity. Applied Clay Science 18 (2001) 17, © 2001, with permission from Elsevier Science.
The adsorption isotherm was found to be of the H-type, indicating a very strong
sorbate-sorbent interaction, typical for ionic sorbing species. In addition, the plateau of the
isotherm coincides with the anionic exchange capacity of HT500 (5800 µeq/g) suggesting the
adsorption of DBS as interlayer anion by reconstruction of the HT-layered structure. This was
confirmed by the X-ray diffraction pattern of the adsorption product, HT500-DBS, which
shows a basal spacing of d 003 = 30.8 Å.55 The sorbent, HT500, can be recycled by calcination of
the adsorption product HT500-DBS again at 500ºC.
The adsorption of dodecylsulfate on a magnesium aluminium layered double hydroxide

has been also studied by Pavan et al.56,57 The isotherms show two steps (Fig. 18): the first-one is
due to the electrostatic interaction of the positively charged HT particles with the negatively
charged sulfate groups of dodecylbenzylsulfate (region I); the other step being due to the
attraction between the surfactant hydrophobic tails, consisting mainly of van der Waals forces.
This step is constituted by three further regions in the isotherm, representing the formation of
an eventual monolayer or hemimicelle (region II), the formation of the second layer or
so-called admicelle (region III) and finally the saturation of the sorbent (region IV). Fig. 18
represents the different regions. The effect of temperature, pH and ionic strength on the
adsorption in the different steps has been also studied. The interlayer space of HT does not
change, indicating that the carbonate anions were not substituted by the dodecylsulfate, and
hence HT does not behave as a swelling layered material, but only the external surface is
available for adsorption. However, the adsorption of dodecylsulfate on HT500 is very large,
resulting in the reconstruction of the hydrotalcite structure with dodecylsulfate anion as the
unique interlayer anion (d003=26.8Å).54
Figure 18.-(a) Adsorption regions for surfactant adsorption on mineral oxide surfaces: (b) configuration of the
adsorbed surfactant unimers. Reprinted from P. C. Pavan, E. L. Crepaldi, G. De A. Gomes and J. B. Valim,
Adsorption of sodium dodecylsulfate on a hydrotalcite-like compound. Effect of temperature, pH and ionic
strength, Colloids & Surfaces, A: Physicochem. Eng. Aspects 154 (1999) 399, © 1999, with permission from
Elsevier Science.
Finally, on the basis of several reports on the intercalation of organic anions into the HT,6,34
the intercalation and characterization of two anionic dyes, naphtol yellows, indigo carmine, and
potasium indigo tetrasulphonate have demonstrated the potential use of HT in the recovery of
anionic dyes from waste water.58
Natural Humic Substances
Humic substances constitute a major fraction of organic polymers naturally occurring in

water and effluents, whose presence has been a problem in the water industry and drinking
treatment plants.59-62 The humic substances in water are mainly constituted by humic and fulvic
acids (HA and FA), which also caused additional problems in the removal of other
contaminants such as heavy metals, because either their adsorption causes the reduction of the
adsorbent efficiency, or the formation of stable compounds with the target contaminants.63
Amin et al.64 found that synthetic hydrotalcites result very effective for removing humic
substances from upland surface water due to their anionic nature. On the contrary, the uptake of
humic substances by pillared interlayer clays (PILCs) is much lower, and this was related to the
negative charge of the layer or their cationic exchange character. Hydrotalcites are more
effective, making use of their anionic exchange capacity, as well as adsorption of humic species
onto their external surface. However, in the PILCs, with negatively charged layers, the uptake
of humic species is limited to displacement of water molecules associated to the pillared
interlayer and/or the external surface. Then, the uptake is favoured at low pH where humic
acids behave like uncharged molecules and can penetrate into the interlamellar spaces. For
hydrotalcites, nevertheless, pH does not appear to be much influenced in the humic acid uptake.
The effectivity of hydrotalcite, Mg-Al-CO3, and some hydrotalcite- like compounds
including Mg-Al-Cl, Ca-Al-Cl, Ca-Fe-Cl and calcined Mg-Al-CO3, to remove humic acid has
been compared with the surfactant-treated montmorillonite.65 As expected, the lowest uptake
was observed with Mg-Al-CO3 because of the high selectivity of hydrotalcite for the carbonate
ion, restricting the access to the interlayer region by other substances. However, Cl-, a
monovalent anion, can be easily exchanged with other ions existing in the solution. Likewise,
calcined Mg-Al-CO3, HT500, shows a removal effectivity for humic acid of the same order of
hydrotalcite- like compounds with Cl- as the interlayer anion. For economic reasons, Ca-Fe-Cl
should be chosen among hydrotalcite- like compounds in the case of industrial purposes.
Hydrotalcite-like compounds containing iron have been successfully used to remove
humic substances from water66 and they have resulted more effective than similar Mg,Al-HT.
Together with the adorption by anion exchange,the contribution of the surface hydroxyl groups
of the hydrotalcite-like compounds to the adsorption of the large size of humic substances has
been also suggested (Fig. 19).
In the first phase, the adsorption occurs rapidly within a few hours. The pH of the solutions
increases gradually up to 8-9 during the first phase. In the second phase, the small amount of
hydroxides produced by a slight dissolution of the compounds promotes the coagulation of
humic substances onto the compounds. The second phase occurred over a long period of time
(few days or even longer).
The amount adsorbed increases on decreasing the iron content in the compounds. These
results are similar to those found by Barriga et al.43 during removal of trinitrophenol. However,
calcined hydrotalcite-like compounds show a larger adsorption capacity, which increases with
the Fe(III) content.
Adsorbed humic substances were almost completely expelled by heat-treatment above
500ºC, and the resulting calcined products showed, again, an adsorption capacity almost
equivalent to that of the initial ones in the second adsorption cycle.66
Figure 19.-Schematic diagram of adsorption mechanism. Reprinted from Y. Seida and Y. Nakano, Removal of
humic substances by layered double hydroxide containing iron, Water Res. 34 (2000) 1487, © 2000, with
permission from Elsevier Science.
ADSORPTION PROPERTIES OF ORGANOHYDROTALCITES

FOR CONTAMINANTS
Similarly to organoclays (Ocl), organohydrotalcites (OHT) may find applications as

sorbents for organic contaminants and thus they could be applied as immobilising barriers in
soils and as filters for water decontamination.67 The anionic exchange of HT could be
advantageously used to introduce large organic anions in the interlayer, which impart
hydrophobic properties to the original HT, and make these OHTs good sorbents for diverse
organic contaminants, even for inorganic ones such as heavy metals. Although several ionic
species have been thus intercalated into the interlayer or gallery region of HT, those imparting
properties as scavengers for organic contaminants are mainly the large anions which expanded
the interlamellar spacing, such as anionic surfactants,55,68-70 several organic acids and
polymers68,71-74 and, very recently, cyclodextrins.75,76 Even the intercalation of dodecylamine
has been reported and the scavenging properties of the corresponding OHT for heavy metals
have been shown.76 On the other hand OHTs, instead of being used directly as adsorbent, are
also precursors to obtain microporous composite materials by calcination, which in turn can be
used as sorbents.73
Synthesis of OHT
The large organic anion may be adsorbed on external and/or internal surfaces, but we here
will refer to the actual intercalation or interlayer adsorption which is the process that leads to
the synthesis of OHT, with the aim to be used as adsorbents for contaminants. The intercalation
of these large organic anions may be achieved mainly by three ways: (i) direct synthesis of OHT,
(ii) direct anionic exchange on non-carbonate HT, and (iii) hydrothermal reconstruction from
the mixed oxides. The most common and easiest method is the hydrothermal reconstruction
from the mixed oxide, since it is the best way to avoid the competition of carbonate by the
charged sites;36,68,76,77 however, the exchange method has been successfully attained when Cl-
or NO3- anions are initially in the interlayer;53,55,68,69,73,78 even the pseudosynthesis by the
simultaneous presence of Cl- and the anionic surfactant in the reaction solution has rendered
OHT.68
Less frequently, the direct synthesis of OHT has been successfully used by Moggridge et
al.78 for the intercalation of benzoate, and by Carlino and Hudson for sebacic71 and capric72 acid
intercalation. These authors reported also the partial intercalation of the capric acid by thermal
reaction of LDH and capric acid mixture at 150°C, above the melting point of the organic
acid.72
Interlayer Structure of OHT
Similarly to OCl, the resulting OHT has an organic interlayer whose width and density will
determine its adsorptive properties.80,81 The orientation of the interlayer anion, as well as their
packing density, will depend mainly on the layer charge of the HT, and on the size of the
organic anions. According to Lagaly and co-workers,55,68,70 linear alkylsurfactant molecules lay
as a monolayer with their alkylchains oriented almost perpendicular to the HT layer in solution,
but tilted up to 55º upon drying (Fig. 20). As the length of the alkylchains increased from 9 to
18 carbon atoms, the interlayer distance in the resulting OHT expanded from 17 to 32 Å. Hence,
increasing the length of the alkylchains is a way to increase the size of the hydrophobic face of
the OHT.
Clearfield et al.69 have reported the formation of OHT with monolayer and bilayer
distribution depending of the method followed to synthesize OHT, the main factor being the pH
during the exchange, Fig. 21.
Figure 20.-A monolayer of alkyl sulfate ions between the hydroxide sheets of double metal hydroxides. =
chain tilt. Reprinted from H. Kopka, K. Beneke and G. Lagaly, Anionic surfactants between layered douyble
hydroxides, J. Colloid Interface Sci. 132 (1988) 427, © 1988, with permission from Academic Press.
These authors reported69 dodecylsulfonate-OHT systems with basal spacings of 26, 30, 36,
and 47 Å which, except the first one with the same structure than that proposed by Kopka et al.
(Fig. 20), have DDS concentrations above the anion-exchange capacity of the solid, concluding
that the DDS in excess is associated to Na ions and adsorbed as neutral molecules. The same
fact was found by Carlino and Hudson,72 who suggested diverse interlayer arrangements for the
capric acid-OHT system, Fig. 22.
Figure 21.-Computer simulated representation of a bilayer arrangement of dodecyl sulfate chains in an LDH
showing the degree of overlap to achieve a basal spacing of 36.4 Å when the chains are perpendicular to the
layers. Reprinted from A. Clearfield, M. Kieke, J. Kwan, J. L. Colon and R. C. Wang, Intercalation of
dodecylsulfate into layered double hydroxidess, J. Inclusion Phenomena & Molec. Recogn. Chem. 11 (1991)
361, © 1991, with permission from Kluwer Academic Publishers.
Figure 22.-Schematic representation of possible arrangements of intercalated caprate anionic species: (a) flat or
parallel bilayer, (b) dehydrated perpendicular monolayer, (c) hydrated perpendicular monolayer, and (d) tilted
bilayer. Reprinted from S. Carlino and M. J. Hudson, Thermal intercalation of layered double hydroxides:
capric acid into MgAl-LDH, J. Mater. Chem. 5 (1995) 1443, © 1995, with permission from the Royal Society
of Chemistry.
The structures of these OHT are shown in Fig.22, the precise structure depending on the
amount of DDS adsorbed in the interlayer, which in turns depends more on the pH of the
solution than on the layer charge of the original HT. Although the adsorption of organic
contaminants in the interlayer of OHT may be favoured by the large expansion originated by
the organic interlayer,80,81 it must be taken into account that as the amount of DDS increases,
their packing density in the interlayer increases and thus the space available to host other
molecules may decrease (see below). Adsorption of large organic ions on clays above the
cation exchange capacity is very well documented in the literature.80,82,83
A similar pseudo bilayer structure or herring-bone type has been proposed for benzoate
anions intercalated in HT79 and from NEXAFS studies for intercalated caprate anions.72 An
OHT having cyclodextrine(CD) as the interlayer organic species develops different
arrangements because the pseudocylindrical shape of the CD. Zhao and Vance75 described three
possible CD-OHT structures, depending on the amount of carboxymethyl substituents on the
cyclodextrine molecule which, in turn, determines its effective volume and the basal spacing of
the resulting material, Fig. 23.
The rather bulk CD14 (with 14 carboxymethyl substituents) renders a final spacings of
15.5 Å, which matched with a monolayer of cyclodextrine (truncated cone) with its edge
perpendicular to the layer and with a low packing density (Fig. 23a). CD3 with only 3
carboxymethyl substituents and thus of lower "effective" size, rendered an OHT with a larger
basal spacing of 22 Å, which matches with two possible structures: (i) a monolayer of CD with
its edge parallel to the HT layer (Fig. 23b), and (ii) a perpendicular bilayer, both with low
packing density, based on the number of CD molecules in the OHT and on their surface area.
Figure 23.-Schematic representation (not to scale) of the possible arrangements for (a) a perpendicular
monolayer CMCD(14)-Mg/Al LDH complex, (b) a parallel-monolayer CMCD(3)-Mg/Al LDH complex, and
(c) a perpendicular-bilayer CMCD(3)-Mg/Al LDH complex. Reprinted from H. Zhao and G. F. Vance,
Intercalation of carboxymethyl- -cyclodextrin into magnesium-aluminium-layered double hydroxide, J.
Chem. Soc. Dalton Trans. (1997) 1961, © 1997, with permission from the Royal Society of Chemistry.
Adsorption of Organic Contaminant
The adsorption of organic contaminants on OHT is mainly due to the hydrophobic

character of the interlayer which acts as a partition medium with water, attracting the organic
molecules. Eusimi and Yamamoto78 have shown the efficiency of OHT obtained in situ, with
intercalated dodecylsulfate (DDS), to remove 2-naphtol from water. Actually, 2-naphtol was
not adsorbed on HT in the absence of DDS, but the amount of 2-naphtol adsorbed or
adsolubilized increased by the addition of DDS, reached a maximum and then decreased. This
steady further decrease was interpreted as due to some ionisation of 2-naphtol molecules (the
pH of the solution was close to the pK of 2-naphtol), and to some repulsive interactions with
DDS, although this low adsorption capacity could be due to a closer packing of DDS, which
decreases the interlayer room available to host naphtol molecules. Fluorescence data showed
that 2-naphtol molecules are adsorbed in the DDS interlayer of OHT by hydrophobic
interaction or adsolubilization. These same authors84 reported a higher adsorption of 2-naphtol
in similar OCl: dodecyltrimethylammonium-laponite, which adsorbed more naphtol even with
lower interlayer expansion, but it could be due to the much lower packing density of the
cationic surfactant in laponite.
Celis et al.47,85 and Villa et al.48 showed that OHT may adsorb diverse pesticides from water
thus revealing an interesting field of applications of OHT. The influence of the type and
distribution of the organic anions in the interlayer was studied by Celis et al.,47,85 showing that
ionizable pesticide imazamox does not adsorb on DDS-HT, whereas it does on
dodecylbenzenesulfate(DBS)-OHT, as summarised in Table 4. The bulky and irregular size of
DBS caused a lower saturation degree of the OHT, and thus a loosely distribution of these
anions in the interlayer allows polar interlayer room where imazamox molecules find
adsorption sites. However this behaviour also depends on the type of pesticide, as triadimefom
(a less polar fungicide in comparison with imazamox) was largerly adsorbed on DDS-OHT
than on DBS-OHT, because the higher hydrophobicity of the former sorbents. Both pesticides,
imazamox and triadimefom, were adsorbed by OCl in larger amounts than on OHT but
imazamox was adsorbed in a larger extent on the more polar OCl with primary alkylamonium
such as octadecylammonium (A-ODA) in the interlayer than in quaternary alkylammonium
such as hexadecyltrimethylammonium Ocl (A-HDTMA), whereas triadimefom behaved the
opposite way (Table 4).
Table 4. Freundlich adsorption parameters of two organic pesticides in organohydrotalcites

(OHT) and organoclays (OCl), adapted from references 47 and 85.
OHT or OCl Imazamox Triadimefom

Kf (mg/Kg) nf Kf (mg/Kg) nf
(OHT) DDS-HT 0 0 4150 0.99
(OHT) DBS-HT 13 1.07 1630 1.01
(OCl) ODA-A 115 1.05 1400 1.28
(OCl) HDTMA-A 92 1.01 17340 1.02
A=Arizone smectite; HT=Hydrotalcite; Freundlich isotherm: Cs = Kf·Cc·nf, where Cs=amount adsorbed,
Cc=equilibrium concentration, Kf = adsorption capacity; nf = adsorption intensity
The same effect was observed by Villa et al.48 on comparing the adsorption of hydrophobic
and polar pesticides on OHT and OCl. OHT adsorbed the most hydrophobic pesticides linuron,
atrazine and diazinon, whereas acephate and glyphosate having higher water solubility only
adsorbed at very low rates. The adsorption of almost all pesticides studied was higher on OHT
than on OCl, except those of polar and anionic character, such as acephate and glyphosate. The
low adsorption of acephate and glyphosate could be due, not only to their higher polarity, but
also to some repulsion between the ionised acephate and glyphosate anion with DDS in the
interlayer. The resulting Kom (distribution coefficient of the organic compound on an organic
matter basis) of the hydrophobic pesticides on OHT were very similar to the octanol/water
partition coefficient (Kow), suggesting a hydrophobic interaction with the organic interlayer as
the driving force for the adsorption process. The higher Kom of the DDS-OHT, with lower
charge density, suggests that low packing of DDS in the interlayer favours the adsorption of
pesticides. The OHT-adsorbed pesticides may act as carriers for the preparation of slow or
controlled release formulations85 which is a very promising way to avoid or to prevent the
pesticide contamination of water. The ability of OCl as carriers to decrease water
contamination by herbicide leaching and runoff losses has been recently demonstrated.86
Perhaps the most attractive role of OHT as adsorbents for organic contaminants is the
cyclodextrine-OHT system (CD-OHT), because of their very recent development and its wide
possibilities, as reported by Zhao and Vance .76 The interlayered cyclodextrine (CD) molecules
act as a typical "host" species which can entrap a great variety of molecules in their inner
pseudo cylindrical space, with the only limitations of their inner room (equivalent as much as
two benzene rings) or even larger compounds having side chains of comparable size to render
inclusion complexes.87 Zhao and Vance76 have shown that CD-OHT was a very good adsorbent
for trichloroethylene, tetrachloroethylene, benzene, toluene, p-,o-, m-xylene, ethylbenzene,
1,2,3-trichlorobenzene and naphtalene. The interactions between CD-OHT and these
contaminants have mainly a hydrophobic character, as shown from the very good linear
correlations between the distribution coefficients Kom and Kow, Fig. 24.
Figure 24.-Linear relationship between (log Kom) and (log Kow) for organic compounds trichloroethylene,
tetrachloroethylene, benzene, toluene, o-xylene, ethylbenzene, 1,2,3-trichlorobenzene and naphthalene, sorbed
on CMCD(3)-Mg/Al LDH. Both m- and p-xylene were not included in determining the linear relationship.
Reprinted from H. Zhao and G. F. Vance, Molecular inclusion properties of hydrophobic organic compounds by
a modified β-cyclodextrin intercalated within a layered double hydroxide, J. Inclusion Phenomena & Molec.
Recogn. Chem. 31 (1998) 305, © 1998, with permission from Kluwer Academic Publishers.
The adsorption of the selected organic contaminants in CD-OHT occurs through a partition
process where cyclodextrin cavities are the major adsorption sites. However, for those
compounds carrying a certain polarity, such as benzene and trichloroethylene, with higher
water solubility, the adsorption in the intercyclodextrine pores in the interlayer has been also
suggested, Fig. 25, resulting in a contaminant/cyclodextrin ratio higher than unity.
The lower hydrophobic affinity revealed from Fig. 25 for o- and p-xylene could be due to
some stereoselectivity of these compounds to reach the CD cavities in the interlayer. However,
the adsorption capacities of the CD-OHT for the organic compounds selected76 were lower than
those of the organoclays for the same compounds.80
An example of the use of OHT as a precursor for obtaining microporous composite

materials has been reported by Putyera et al.73 when studying calcined OHT as adsorbents for
alkanes. The OHT was obtained by incorporating 4-styrenesulfonate through the hydrothermal
reconstruction from the mixed magnesium-aluminum oxide previously prepared by calcination
of HT and microporous composites were prepared from these OHT by further calcination.
These microporous composites behaved as very good adsorbents for alkenes as related to their
interlayer spacings and the water holding capacity, but no relationship was found between the
adsorption capacity and the amount of carbon present.
Figure 25.-Schematic representation of guest inclusion towards the CMCD(3)-Mg/Al LDH intercalate in
aqueous solution: (a) an expanded parallel-monolayer arrangement and (b) an expanded perpendicular-bilayer
arrangement. Reprinted from H. Zhao and G. F. Vance, Molecular inclusion properties of hydrophobic organic
compounds by a modified β-cyclodextrin intercalated within a layered double hydroxide, J. Inclusion
Phenomena & Molec. Recogn. Chem. 31 (1998) 305, © 1998, with permission from Kluwer Academic
Publishers.
Adsorption of Inorganic Contaminants
There are not many studies on the adsorption of inorganic contaminants, typically cationic
forms of heavy metals, on OHT. To our knowledge, only the work of Qureshi et al.77 shows a
very important adsorption capacity of two OHT for diverse heavy metals (Mn2+, Co2+, Ni2+,
Cu2+, Zn2+, Cd2+, Pb2+ and Hg2+), as summarized in Table 5.
Table 5. Adsorption capacity (mmol/g) of Sebacic acid-OHT and dodecylamine-OHT for

diverse metal ions
Metal ion Sebacic acid-OHT Dodecylamine-OHT

Mn2+ 0.13 0.24
Co2+ 0.32 0.35
Ni2+ 0.20 0.25
Cu2+ 0.14 0.26
Zn2+ 0.05 0.25
Cd2+ 0.15 0.19
Hg2+ -- 0.06
Pb2+ 0.20 0.23
Mg2+ 0.13 0.25
Ba2+ 0.18 0.20
The OHT tested were prepared from the calcined product, and intercalated with sebacic
acid and dodecylamine, reporting expanded basal spacings of 16.2 and 13.3 Å, respectively,
although IR revealed the simultaneous presence of NO3- in the interlayer of both materials. The
adsorption of these cations must be associated to the carboxylic and amino group of the organic
interlayer species of these OHTs, as suggested in the case of dodecylamine-OHT, which turned
from white to blue after adsorption of Cu2+.
Taking into account that aminocarboxylic acids, such as EDTA or similar organic
compounds, could form complexes with heavy metals which could be supported on HT, this is
a very attractive research field in introducing these species in the HT to obtain powerful
sorbents for heavy metals, as recently shown for organic smectites.88,89 Thus OHT intercalated
with guest species containing organic functions with metal chelating properties may find
applications in remediation of mine sites and contaminated soil, sediment and water, even as
barrier for mining residue ponds.
ACKNOWLEDGEMENTS
This study has been partially supported by CICYT project no. AMB96-0445-C02 and
Junta de Andalucía through Research Groups RMN-124 and FQM-214.
REFERENCES
1. J.W. Moore and S. Ramamorthy, in “Organic Chemicals in Natural Waters”,
Springer-Verlag, New York, 1984.
2. C. Anselme, A. Bruchet and J. Mallevialle, in “Influence and Removal of Organics in
Drinking water”. J. P.Duguet and J. Mallevialle (Eds.), Lewis, Chelsea, MI, 1992.
4. D.L. Bish, Bull. Mineral. 103 (1980) 170.
6. K. Chibwe and W. Jones, J. Chem.Soc., Chem.Comm. (1989) 926.
7. M.A Ulibarri, I. Pavlovic, M.C. Hermosín and J. Cornejo, Appl.Clay Sci. 10 (1995) 131.
8. L.M. Parker, N.B. Milestone and R.H. Newman, Ind. Eng. Chem. Res. 34 (1995) 1196.
9. E.D. Dimotakis and T.J. Pinnavaia, Inorg.Chem. 29 (1990) 2393.

10. S. Miyata, Eur.Patent 152,010 (1985), to Kyowa Chem.Ind.Co.
11. D.W. Oscarson, M.G. Miller and R.L. Watson, An evaluation of potential additive to a
clay- based buffer material for the immobilization of I-129, Atomic Energy of Canada
Ltd., Pinawa (C), 1986.
12. F. Rey, V. Fornés and J.M. Rojo, J. Chem. Soc., Faraday Trans. 88 (1992) 2233.
13. T. Sato, T. Wakabayashi and M. Simada, Ind. Eng. Chem. Prod. Res. Dev. 25 (1986) 89.
14. L. Châtelet, J.V. Bottero, J. Yvon and A. Bouchelaghem, Colloids Surfaces A:
Physicochem. Eng. Aspects 111 (1996) 167.
15. H.-S. Shin, M.J. Kim, S.-Y. Nam and H.-C. Moon., Water Sci. Technol. 34 (1996) 161.
16. A. Ookubo, K. Ooi and H. Hayashi, Langmuir 9 (1993) 1418.
17. R.L. Goswamee, P. Sengupta, K.G. Bahattacharyya and D.K. Dutta, Appl. Clay Sci. 13
(1998) 21.
19. B. Houri, A. Legrouri, A. Barroug, C. Forano and J.-P. Besse, J. Chim. Phys. 96 (1999)
455.
20. B. Houri, A. Legrouri, A. Barroug, C. Forano and J.-P. Besse, Collect. Czech. Chem.
Comm. 63 (1998) 732.
21. F. Kovanda, E. Kovácsová and D. Kolousek, Collect. Czech. Chem. Comm. 64 (1999),
1517.
22. G. Fetter, E. Ramos, M.T. Olguín, P. Bosch, T. López and S. Bulbulian, J. Radioanal. Nucl.
Chem. 221 (1997) 63.
23. M.T. Olguín, P. Bosch, D. Acosta and S. Bulbulian, Clays Clay Miner. 46 (1998) 567.
24. G. Fetter, M.T. Olguín, P. Bosch, V.H. Lara and S. Bulbulian, J. Radioanal. Nucl. Chem.
241 (1999) 595.
25. J. Serrano, V. Bertin and S. Bulbulian, Langmuir 16 (2000) 3355.
26. M.C. Hermosín, I. Paulovic, M.A. Ulibarri and J. Cornejo, Water Res. 30 (1996) 171.
27. F.A. Cotton and G. Wilkinson “Advanced Inorganic Chemistry”, 5th ed.; Wiley, New York,
1988.
28. J.M. Wood, Science 183 (1974) 1049.
29. Y. Tamaka, M. Tsufi and M. Abe, Chem. Lett. (1990) 661.
30. M. Lehmann, A.I. Zouboulis and K.A.Matis, Chemosphere 39 (1999) 881.
31. P. Ulmgren, Nordic Pulp Paper Research J. 1 (1987) 4.
32. E.J. Reardon and S. Della Valle, Environ. Sci. Technol. 31 (1997) 1218.
33. S. Komarneni, N. Kozai and R. Roy, J. Mater. Chem. 8 (1998) 1329.
34. A. de Roy, C. Forano, K. El Malki and J.P. Besse, in “Expanded Clays and other
Microporous Solids, Synthesis of Microporous Materials”, M.L. Occeli and H. Robson
(Eds.), van Nostrand Reinhold, New York, 1992, chapter 7, p. 108.
36. T. Sato and A. Okuwaki, Solid State Ionics 45 (1991) 43.
37. M.C. Hermosín, I. Pavlovic, M.A. Ulibarri and J. Cornejo, J. Environ. Sci. Health A28
(1993) 1875.
38. I. Pavlovic, M.A. Ulibarri, M.C. Hermosín and C.J. Cornejo, in Los Minerales de la
Arcilla ante el Reto del Nuevo Milenio, (J. Pascual, editor), Soc. Esp. de Arcillas,
University of Malaga (in press).
39. M.C. Hermosín, I. Pavlovic, M.A. Ulibarri and J. Cornejo, Fresenius Envir. Bull. 4 (1995)
41.
40. J. Cornejo, R. Celis, I. Pavlovic, M.A. Ulibarri and M.C. Hermosín, Clay Miner. 35 (2000)
771.
41. M.A. Ulibarri, I. Pavlovic, C. Barriga, M.C. Hermosín and J. Cornejo, Appl.Clay Sci. 18
(2001) 17.
42. M. Gaitán, C. Barriga, I. Pavlovic, M.A. Ulibarri, M.C. Hermosín and J. Cornejo, Adv.
Clay Miner. (1996) 30.
43. C. Barriga, M. Gaitán, I. Pavlovic, M.A. Ulibarri, M.C. Hermosín and J. Cornejo,
unpublished.
44. G.H. Giles, T.H. MacEwan, S.N. Nakhwa and D. Smith, J. Chem.Soc. (1960) 3973.
45. M.C. Hermosín, M.A. Ulibarri, M. Mansour and J. Cornejo, Fresenius Envir. Bull. 1 (1992)
472.
46. M. Lakraimi, A. Legrouri, A. Barroug, A. de Roy and J.-P. Besse, J.Chim.Phys. 96 (1999)
470.
47. R. Celis, W.C. Koskinen, A.M. Cecchi, G.A. Bresnahaw; M.J. Carrizosa, M.A. Ulibarri, I.
Pavlovic and M.C. Hermosín, J.Environ.Sci.Health B34 (1999) 929.
48. M.V. Villa, M.J. Sánchez-Martín and M. Sánchez-Camazano, J.Environ.Sci.Health B34
(1999) 509.
49. C. Tomlin, “The Pesticide Manual”, The Royal Society of Chemistry, Cambridge (1995).
50. M.J. Sánchez-Martín, M.V. Villa and M. Sánchez-Camazano, Clays Clay Miner. 47 (1999)
777.
51. J.M. Quiroga, D. Sales and A. Gomez-Parra, Water Res. 23 (1989) 803.
52. J. Patoczka and G.W. Pulliam, Water Res. 24 (1990) 965.
53. I. Pavlovic, M.A. Ulibarri M.C. Hermosín and J. Cornejo, Fresenius Envir. Bull. 6 (1997)
266.
54. I. Pavlovic, Ph. D. Thesis, University of Córdoba (Spain), 1998.
55. M. Meyn, K. Beneke and G. Lagaly, Inorg. Chem. 29 (1990) 5201.
56. P.C. Pavan, G. de A. Gomes and J.B. Valim, Microporous Mesoporous Mater. 21 (1998)
659.
57. P.C. Pavan, E.L.Crepaldi, G. de A. Gomes and J.B. Valim, Colloids and Surfaces A:
Physicochem. Eng. Aspects 154 (1999) 399.
58. W.-Ch. Jung and Y.-D. Huh, Bull. Korean Chem. Soc. 17 (1996) 547.
59. L. Zhou, S. Rowland, R.F.C. Mantoura and J. Braven, Water Res. 28 (1994) 571.
60. L. Jelinek, K. Inoue and T. Miyajima, Proc. 31st Ann. Meet. Chem. Eng. Jpn. (1998) 71.
61. J. Ellis and W. Korth, Water Res. 27 (1993) 535.
62. Guidelines for drinking-water quality (1998), 2nd, edition, Addendum to Vol. 1,
Recommendations, World Health Organization, Geneva, pp. 3-4.
63. C. Rav-Acha and M. Rebhn, Water Res. 26 (1992) 1645.
64. S. Amin and G.G. Jayson, Wat.Res. 30 (1996) 299.
65. G. Önkal-Engin, R. Wibulswas and D.A. White, Environ.Technol. 21 (2000) 167.
66. Y. Seida and Y. Nakano, Wat. Res. 34 (2000) 1487.
67. S. Xu, G. Sheng G. And S.A. Boyd, Adv. Agronomy 59 (1997) 25.
68. M. Meyn, K. Beneke, and G. Lagaly G., Inorg. Chem. 32 (1993) 109.
69. A. Clearfield , M. Kieke, J. Kwan, J.L. Colon and R.C. Wang, J. Inclusion Phenom. Molec.
Recogn. Chem. 11 (1991) 361.
70. H. Kopka, K. Beneke and G. Lagaly, J. Colloid Interface Sci. 132 (1988) 427.
71. S. Carlino and M. J. Hudson, J. Mater. Chem. 4 (1994) 99.
72. S. Carlino and M. J. Hudson, J. Mater. Chem. 5 (1995) 1443.
73. K. Putyera, T.J. Bandosz, J. Jagiekko and J.A. Schwarz, Clays Clay Miner. 42 (1994) 1.
74. C.O. Oriakhi, I.V. Farr and M.M. Lerner, J. Mater. Chem. 6 (1996) 103.
75. H. Zhao and G.F. Vance, J. Chem. Soc., Dalton Trans. (1997) 1961.
76. H. Zhao and G.F. Vance, J. Inclusion Phenom. Molec. Recognit. 31 (1998) 305.
77. S.Z. Qhreshi, R.M.A.Q. Jamhour and N. Rahman, Ann. Chim. Fr. 21 (1996) 231.
78. K. Eusimi K and S. Yamamoto, Colloids Surfaces 137 (1998) 385.
79. G.D. Moggridge, P. Parent and G. Tourillon, Clays Clay Miner. 42 (1994) 462.
80. W.F. Jaynes and J. A. Boyd Soil Sci. Soc. Am. J. 55 (1991) 43.
81. M.C. Hermosín M.C.and J. Cornejo, J. Environ. Qual. 22 (1993) 325.
82. K.R. Srinavasan and H.S. Fogler, Clays Clay Miner. 38 (1990) 277.
83. M.C. Hermosín, P. Martín and J. Cornejo, Environ. Sci. Technol. 27 (1993) 2606.
84. K. Eusimi, M. Takeda, K. Goino, Y. Ishiduki and Y. Kolde, Langmuir 13 (1997) 2585.
85. R. Celis, W. C. Koskinen, M.C. Hermosín, M.A. Ulibarri and J. Cornejo , Soil Sci. Soc.
Am. J. 64 (2000) 36.
86. M.C. Hermosín, M.J. Calderón, J.P. Aguer and J. Cornejo, Pest Manag. Sci. accepted for
publication.
87. J. Szejtli, "Cyclodextrins and their Inclusion Complexes”, Akademiak Kiadó, Budapest,
1982.
88. G. Sheng, S. Xu and S.A.Boyd, Soil Sci. Soc. Amer. J. 63 (2000) 73.
89. R. Celis, M.C. Hermosín and J. Cornejo, Environ. Sci. Technol. 34 (2000) 4593.
Chapter 10
APPLICATIONS OF HYDROTALCITE-TYPE ANIONIC

CLAYS (LAYERED DOUBLE HYDROXIDES)
IN CATALYSIS
Francesco Basile and Angelo Vaccari*

Dipartimento di Chimica Industriale e dei Materiali, Università degli Studi di Bologna,
Viale del Risorgimento 4, 40136 BOLOGNA (Italy)
Phone: +39 051 2093683; Fax; +39 051 2093680; e.mail: vacange@ms.fci.unibo.it
INTRODUCTION
Hydrotalcite-type (HT) anionic clays [also called layered double hydroxides (LDHs)] are
natural or synthetic lamellar mixed hydroxides with interlayer spaces containing exchangeable
anions, relatively simple and inexpensive to synthetize on both laboratory and industrial
scales.1-8 These materials are described by the general formula: [Mz+1-x M3+x (OH)2]b+ [An-b/n]
mH2O (M= metal, A= interlayer anion, and b= x or 2x-1, for z = 2 or 1, respectively) and many
names are used depending on the composition and polytype.9 The general term HT compounds
is probably due to the extensive characterization carried out on natural or synthetic hydrotalcite
(a Mg/Al hydroxycarbonate), while the term “anionic clays” has also been used (first by
Reichle10) to underline the complementarity with the properties of cationic clays (or clay
minerals), thus offering the possibility to cover a wide number of applications of scientific and
industrial interest and to transfer the knowledge acquired from one class of materials to the
other, with the necessary adaptations. None of these terms however are generally accepted,
considering that HT refers strictly to a specific mineral and that these compounds do not fulfill
some clay requirements, for example a particle size ≤ 2.0 nm. On the other hand, the reference
name LDH is derived from the early work of Feitknecht,11,12 who hypothesized a structure with
intercalated hydroxide layers. This hypothesis was refuted many years later on the basis of
single crystal XRD analysis,13,14 which showed that all cations are localized in the same layer,
with the anions and water molecules located in the interlayer region.
HT anionic clays can be considered promising materials for a large number of possible
applications due to their high versatility, easily manipulated properties, wide range of
composition and/or preparation variables, low cost, etc. Only a few of these possible variations
324 Francesco Basile and Angelo Vaccari
occur in nature; on the contrary, a very large number of variables has been reported for
synthetic HT compounds (Fig. 1) which make it possible to produce tailor-made materials to
fulfill specific requirements. Thus it is not surprising that synthetic HT anionic clays, as such or
after thermal decomposition, find many industrial applications; indeed, over the past few years
there has been an exponential increase in such applications in both the open and patent
literature.1-3,5-8 Furthermore, the possibility of technological upgrading, i.e., the transition from
two- to three-dimensional structures by pillaring or intercalation processes, opens new
prospects for the preparation of materials with unusual properties.5,8
Figure 1. Structural and preparation variables in the synthesis of HT anionic clays.1-7
Although the highest amounts of HT compounds are used in the polymer industry, mainly
to stabilize PVC,1,5-7,15 one of the most promising applications is as precursors of catalysts or
catalyst supports, because of the specific features of the mixed oxides obtained by controlled
thermal decomposition: i) high surface area (100-300m2/g), ii) homogeneous and thermally
stable interdispersion of the elements, that by reduction can form small and stable metal
crystallites, iii) synergetic effects between the elements which favour, for example, unusual
basic or hydrogenating properties, and iv) memory effect, with structure reconstruction under
mild conditions. However, research on HT compounds and catalysis followed separate paths up
to 1970, when the first patent appeared that referred specifically to them as optimal precursors
for the preparation of hydrogenation catalysts (Table 1).16
Established catalytic applications of the mixed oxides obtained by controlled calcination of
HT precursors (polymerization of alkene oxides, aldol condensation of aldehydes and ketones,
methane or hydrocarbon steam reforming, methanation, methanol synthesis, higher-alcohols or
hydrocarbons synthesis, etc.) have been extensively treated in previous reviews.1-3,5-7,17,18 Thus,
the attention here is focused on more recent applications, other than hydrogenation reactions
treated in another chapter of this book, [catalyst supports (as such or after calcination),
intermediates or fine chemical synthesis and organic reactions, air decontamination, advances
in natural gas conversion, and three-dimensional HT compounds (pillared or intercalated)] as
promising areas of research with a wide range of possible developments. Moreover, there is still
room for further study of already widely studied subjects and new results have been recently
reported, such as for example the reexamination of the HT crystal chemistry,19 the phases
Applications of Hydrotalcite-Type Anionic Clays… 325
responsible for the high thermal stability of Ni/Al and Ni/Mg/Al catalysts20-22 and the
stereospecific polymerization of propylene oxide (PO), with formation of a crystalline,
isotactic polymer fraction attributable to the ring opening of a coordinated PO monomer on the
heterogeneous surface of Mg/Al mixed oxides.23-24
Upgrading also refers to new compositions or preparation methods. New compositions
include HT phases without trivalent cations25 or those containing unstable V3+ ions,26
noble-metal ions27-32 or tetravalent ions such as Ti4+, Zr4+or Sn4+.33-37 Examples of new
preparations include HT compounds exhibiting sheet broadness to thickness ratios ranging
from 100 to 2000 38-40 and recent syntheses claiming significant material or process
improvements.41-44
Table 1. Examples of compositions of HT catalyst precursors and their catalytic applications

after calcination.16
Mg6Al2CO3(OH)16 · 4H2O Dehydration, catalyst support

Ni6Al2CO3(OH)16 · 4H2O Hydrogenation, dealkylation
Ni3Mg3Al2CO3(OH)16 · 4H2O Hydrogenation, dealkylation, cracking
Co3Mg3Al2CO3(OH)16 · 4H2O Hydrogenation
Co6Al2CO3(OH)16 · 4H2O Hydrogenation
Ni0.90Co0.75Cu0.35Mg4Al2CO3(OH)16 · 4H2O Hydrogenation, dehydrogenation
Cu3Mg3Al2CO3(OH)16 · 4H2O Dehydrogenation of sec-alcohols to ketones, hydrogenation
of nitro groups
Cu6Al2CO3(OH)16 · 4H2O Isomerization, hydrogenation of nitro groups,
dehydrogenation of sec-alcohols to ketones
Cu3Zn3Al2CO3(OH)16 · 4H2O Dehydrogenation of sec-alcohols to ketones,
low-temperature water gas shift conversion
Ni3Zn3Al2CO3(OH)16 · 4H2O Hydrogenation
Ni3Mg3Al1.8Cr0.2CO3(OH)16 · 4H2O Hydrogenation
APPLICATIONS AS CATALYST SUPPORTS

HT anionic clays with different compositions, calcined at 523-723 K and partially or
completely chlorinated, have been claimed as supports for Ziegler catalysts for the
polymerization of olefins, showing higher activities than catalysts prepared from
(MgCO3)4·Mg(OH)2·H2O and better control of the molecular weight (Table 2).45 More recently,
calcined Mg/Al HT compounds have been reported to support CeO2 for SOx removal from the
emissions of fluid catalytic cracking units (FCCU) (see also section below on “Air
decontamination”), with maximum activity for the CeO2/MgAl2O4·MgO system.46,47 These
catalysts are very stable even after severe steam treatment (Fig. 2), showing hardness values
very close to those of typical FCC catalysts, and good catalytic properties, as well as catalyst
regeneration.
Table 2. Activity of TiCl4 (VCl4)/AlR3 catalysts supported on mixed oxides obtained by

calcination of different HT anionic clays (anions always carbonates).45
HT composition Calcination time Calcination Active phase Catalytic activity (g of polyethylene)

(h) temperature (K)
Ni/Al 15 563 TiCl4/AlR3 130
Mg/Zn/Al 10 523 TiCl4/AlR3 135
Mg/Cr 30 603 TiCl4/AlR3 165
Mg/Mn/Al 5 473 TiCl4/AlR3 180
Mg/Co/Mn/Cu/ 10 503 VCl4/AlR3 130
Al
Co/Cr 20 593 VCl4/AlR3 135
Mg/Al/Cr 40 593 TiCl4/AlR3 160
Mg/Al 3 723 ZrCl4/AlR3 130
Mg/Al mixed oxides have also been successfully used as supports for transition metal
oxides for the selective catalytic reduction (SCR) of NO by NH3, as alternatives to less
thermally stable supports such as active carbons.48 Among the three supported transition metal
oxides, the best catalytic performances were obtained with CuO, while Cr2O3 formed high
amounts of N2O and Fe2O3 exhibited low NO conversion, unlike that observed on active
carbons at lower temperature.49
Figure 2. SO2 activity as a function of the composition of virgin (O) and steamed (V) MgAl2O2 • yMgO solid
solutions.47
New applications continuously appear, such as for example that of vanadium oxides
supported on calcined Mg/Al HT precursors for the oxidative dehydrogenation of n-butane50-51
or the vapour phase synthesis of isobutyraldehyde from methanol and n-propanol.52 In the
former reaction, the activity was always lower than those of analogous MgO- or
Al2O3-supported vanadium oxide catalysts, while high selectivity to C4-alkenes, especially
1-butene and butadiene, was achieved for V-contents of about 30 wt% (as V2O5). In the second
case, since the synthesis of isobutyraldehyde took place through metal enolates as
intermediates, the activity depended mainly on the acid-base properties, while the selectivity
was strongly influenced by the method of vanadium oxide loading (impregnation or
intercalation).
Calcined HT compounds have also been reported as useful supports of noble metals. The
conversion of n-hexane to aromatic hydrocarbons has been claimed using calcined HT
precursors (typically for 12 h at 873 K) prior to Pt or Pd impregnation.53,54 For this process,
catalysts obtained by calcination of precursors containing noble metal ions inside the HT
structure also have been claimed.27 Chemisorption techniques have shown that nanometric
sized Pt particles supported on Mg/Al mixed oxides prepared from HT anionic clays compared
with those supported on Al2O3 (with similar Pt dispersion) exhibited particular properties, such
as a higher differential heat of H2 adsorption or the presence of additional CO species,
bridge-bonded on Pt through the C atom and with Mg2+ ions by the O atom, most stable upon
desorption at high temperature.55
Ni- and Pd-supported catalysts prepared by impregnation of Mg/Al hydrotalcites calcined
at 823 K for 18 h, followed by drying and further calcination at 673 K for 4 h, have been
successfully employed in the one-step synthesis of methyl isobutyl ketone (MIBK) from
acetone and hydrogen at atmospheric pressure.56 Basic properties of the support and density of
metal sites were key factors for activity and product distribution obtained with these catalysts,
which gave better results than those reported for previous catalysts, although stability problems
in the reaction conditions still remained. The same reaction also has been investigated using
Ni/Mg/Al, Co/Mg/Al and Fe/Mg/Al mixed oxides obtained by calcination of HT precursors at
673 K for 15 h and successive reduction at 723 K for 24 h.57 Ni/Mg/Al gave selectively MIBK,
whereas Co/Mg/Al gave methyl isobutyl carbinol (MIBC) and Fe/Mg/Al produced mesityl
oxide (MSO), which are all valuable chemicals (Fig. 3). The activity and selectivity obtained is
related to the bifunctional nature of the catalysts involving both metallic and acid-base sites.
In other cases the noble-metal supported catalysts have been prepared by direct
impregnation of HT compounds followed by reduction, and unusual behaviours were found.
For example, Ru crystallites obtained by reduction at 548 K of carbonyl complexes supported
on Mg/Al HT anionic clays dried at 338 K, formed by CO hydrogenation high fractions of
oxygenates (mainly methanol and lower amounts of C2-C4 alcohols), unlike analogous
catalysts prepared using acid supports, that were very selective for isomerized hydrocarbons
(branched alkanes and internal alkenes).58,59 The high alcohol selectivity, which is atypical for
CO hydrogenation over Ru, has been partially attributed to the decoration of metal crystallites
by the basic support, that (i) blocks metallic surface sites, inhibiting CO dissociation, and (ii)
stabilizes partially oxidized Run+ sites, responsible for methanol formation. Catalysts obtained
by impregnating RuCl3·xH2O on some commercial hydrotalcites have also been claimed, after
reduction at 423 K under 5.0 MPa of hydrogen, for the partial reduction of monocyclic
aromatic hydrocarbons to cycloolefins, with a key role of the support on the dispersion and
stability of Ru crystallites.60
Figure 3. Mechanism of acetone conversion in the presence of H2 over different mixed oxides obtained by
calcination of HT precursors at 673 K for 15 h and successive reduction in an 80 ml/min flow of H2 at 723 K for
24 h (MIBK = methyl isobutyl ketone; MIBC = methyl isobutyl carbinol; MSO = mesityl oxide).57
More recently, catalysts prepared by impregnation of different Mg/Al hydrotalcites with

various Pd anionic precursors and following reduction at 573 K for 3 h, have been investigated
in CO chemisorption at room temperature and phenol hydrogenation at 453 K as a function of
preparation parameters.61-63 These catalysts showed better performances than Pd/Al2O3 and
Pd/MgO in phenol hydrogenation, with selectivity to cyclohexanone always > 90%, although
the conversion varied with available Pd area. The best values were obtained with HT
compounds prepared by the high-supersaturation method, with interlayer CO32- anions and
impregnated with acidified PdCl2 (Table 3). It has been proposed that acidification of PdCl2 led
to PdCl42- , which at first replaced the CO3 2- anions on the external edge surface, leading to fine
dispersion and, after reduction, small Pd particles. Intercalation of Pd precursors in the HT
structure was ruled out because no shift was observed in the basal reflection in the Pd/HT
catalysts. Higher metal amounts or HT phases with the largest particle sizes gave rise to
deposits mainly on the external surface and, after reduction, poor metal dispersion.
Table 3. Effect of Pd precursor on CO adsorption at room temperature and activity in vapour

phase phenol hydrogenation of 1 wt% Pd catalysts, previously reduced in H2 at 573 K for 3 h
(reaction temperature = 453 K; catalyst = 0.200 g).62
Pd precursor Support Pt dispersion Pd crystallite CO Phenol Activity (mol g-1 h-1 x 10-2)
(%) size (nm) uptake convers.
(cm3 g-1) (%)
PdCl2 HT a 64 1.7 1.35 90 3.5
Pd(NH3)4Cl2 HT a 14 7.4 0.29 41 1.5
Pd(CH3COO)2 HT a 27 4.1 0.57 30 1.1
K2PdCl4 b HT a 67 1.6 1.40 78 7.7
PdCl2 Al2O3 12 9.3 0.26 27 1.1
K2PdCl4 Al2O3 10 11.2 0.22 34 1.3
a
Mg/Al (2:1) HT precursor prepared at a high supersaturation level, with CO32- as interlayer anions (surface
area = 60 m2 g-1).
b
Catalyst = 0.075 g.
INTERMEDIATE OR FINE CHEMICAL SYNTHESIS AND

ORGANIC REACTIONS
HT anionic clays as such exhibit generally poor basic properties, sensibly lower than those
of the mixed oxides obtained by their thermal decomposition.2,3,5,6,64 However, good basic
properties have been recently claimed for meixnerite, obtained by combining decarbonation
and controlled rehydration.65-68 High activity and selectivity have been reported in the
aldolisation of acetone (Fig. 4), already widely investigated using calcined HT precursors.69-72
as well as in the aldolic condensation of benzaldehyde on acetone or acetophenone, although in
this last reaction KF supported on alumina preliminarily treated at 723 K, was most active at
423 K, reaching 90% selectivity in chalcone at 80% conversion.73
The presence of strong basic sites has also been claimed for HT precursors activated below
the structural decomposition temperature (≤ 523K),74 suggesting that adsorbed water can
inhibit the access to these basic sites on the surface, although the nature and strength of the
basic sites in dried precipitates require further clarification. However, most applications refer to
the mixed oxides obtained by thermal decomposition in the range between the decomposition
temperature of the HT structure and that of formation of stoichiometric phases, in which
metastable poorly crystallized mixed oxides form, characterized by high surface area and
non-stoichiometric compositions, with an excess of divalent cations.3,5,6
Mg/Al mixed oxides offer the possibility to no longer use liquid bases, such as ammonia,
ammonium salts or amine, replacing them with environmentally sound catalysts that can be
easily separated and recycled . The textural and surface properties of the Mg/Al mixed oxides
as well as their activity may be modulated by an appropriate selection of the composition and
preparation conditions.75-81 For example, with increasing Mg/Al ratio, the number of basic sites
with 9.0 ≤ pK ≤ 13.3 increases, whereas that of the stronger basic sites (13.3 ≤ pK ≤ 16.5), that
catalyze for example Michael addition or aldol condensation reactions, decreases (Fig. 5).82
Figure 4 . Reaction pathway for the aldol condensation of acetone.69
The acid-base properties depend significantly on composition; for example, Zn/Al, Zn/Cr
or Ni/Al HT compounds are less basic than Mg/Al hydrotalcite3,5 while HT precursors pillared
with polyoxometalate (POM) anions may be strongly acidic.83 Catalysts obtained by
calcination of B-containing HT precursors84-87 have been recently investigated for the vapour
phase Beckmann rearrangement of cyclohexanone oxime to caprolactam, key step in the
synthesis of Naylon 6,88,89 since basic sites promote desorption of lactam without impairing the
acid function.90
Other interesting applications have been recently reported in the field of intermediates,
such as the vapour phase alkylation of phenol or m-cresol to produce gasoline additives or
chemical intermediates using calcined Mg/Al, Mg/Cr or Mg/Fe HT compounds, with a direct
correlation between composition and acid-base properties of the catalyst and the activity and
selectivity between O- and C-alkylated products (Table 4),91-93 the already mentioned synthesis
of diacetone alcohol at 273 K using meixnerite as the catalyst,65-67 that of glycol ethers by
reaction of olefin oxides and alcohols94-99 or the recently reported production of
monoglycerides (food emulsifiers) by transesterification between glycerol and triglycerides,
using MgO or calcined hydrotalcites with a low Al-content (Table 5).100 By optimizing the
temperature and glycerol/oil ratio, it was possible to obtain high yields in monoglycerides as
well as to meet the quality requirements established by the European Union, with significant
economic and environmental advantages in comparison with the processes reported in the
patent literature. Finally, in a very recent paper Cosimo et al. reported the structural
requirements and reaction pathways in condensation reactions of alcohols, key step in the
synthesis of linear or branched alcohols (mainly isobutanol) from synthesis gas (syngas),
investigating Mg/Al mixed oxides obtained by decomposition in N2 at 673 K for 4 h of HT
precursors with a wide range of composition.101
With regard to fine chemicals, the synthesis of 5-phenyl-3-methyl-2-pentenenitrile
(citronitril) is of commercial interest in the perfume industry as well as for detergents and soap
(Fig. 6).102 For the first step maximum activity was observed for a Mg/Al (3:1) hydrotalcite
calcined at 723 K for 18 h, for which the total number and strength distribution of the basic sites
were optimum. The second step is a more demanding reaction from the catalyst point of view,
with important roles played by the amount of water present and reaction temperature. When
they were optimized, high conversion with selectivity in citronitril close to 50% was obtained
in a one-pot reaction.
Figure 5. Possible reaction pathways between benzaldehyde and ethyl acetonate82.
Table 4. Alkylation of m-cresol with 2-propanol over Mg/Al (3:1) HT anionic clay calcined at
723 K and activated before the catalytic tests for 3 h at 773 K in 1.5 l h-1 N2 flow [m-cresol /
2-propanol = 1:4 mol/mol; catalyst = 1.5 g; WHSV = 8.6 mol h-1 kg-1; N2 as carrier gas (1.5 l
h-1)].93
Reaction temperature m-Cresol conversion Product selectivity (mol %)

(K) (mol %) I II III IV
523 1.4 57.1 42.9 -- --
573 8.7 41.4 47.2 5.7 5.7
623 20.2 17.3 68.3 3.5 10.9
648 32.6 6.7 77.3 3.4 12.6
673 36.4 3.6 79.9 2.5 14.0
698 38.0 1.6 74.5 1.1 22.8
723 40.9 2.0 28.4 10.8 58.8
Products: I) isopropyl-3-methylphenylether; II) thymol (2-isopropyl-5methylphenol); III) 4-isopropyl-3-methylphenol; IV)
higher alkylated products.
Table 5. Role of the chemical composition of the mixed oxides obtained by calcining Mg/Al HT
precursors at 723 K in determining the total conversion, yields, and selectivity to monoesters
in the trans esterification reaction of rapeseed oil with glycerol (reaction temperature = 513 K;
reaction time = 5 h; glycerol / rapeseed oil = 12 mol/mol; catalyst = 4 wt% of the different
oxides).100
Catalyst Mg/Al Total convers. Yield (%) Selectivity to

(atomic ratio) (%) Monoesters Diesters monoesters (%)
MgO 100:0 96 65 31 68
HT1 80:20 95 64 31 67
HT2 75:25 89 52 37 58
HT3 70:30 84 53 31 63
HT4 67:33 70 39 31 56
Figure 6. Reaction pathway for the synthesis of 5-phenyl-3-methyl-2-pentenenitrile (citronitril).102
Another interesting example is the Claisen-Schmidt condensation for the synthesis of

chalcones and flavonoids (products of interest for the pharmaceutical industry), with
significantly better results for calcined Mg/Al HT precursors than with acid or base-exchanged
zeolites or sepiolite.103-104 The reaction rate went through a maximum as a function of the
composition, crystal size and calcination temperature or the water content in the solvent
(although a too high amount of water in the reaction medium had an inhibiting effect probably
due to the competition of water with the reactants), suggesting a key role of strong basic sites:
oxygens with a low coordination number 102 and/or surface hydroxyl groups.104 An optimized
catalyst (Mg/Al = 3:1, calcined at 723 K for 18 h) was investigated in the synthesis of
2’,4’,4-trimethoxychalcone (vesidryl) (Fig. 7), product of pharmacological interest owing to its
diuretic and choleretic properties.103 Yields of 55 and 85 %, after 20 h of reaction at 423 and
443 K, respectively, were obtained, values much higher than those obtained using a HY zeolite.
Finally, a very interesting example reported in the recent literature, is the use of
multicomponent mixed oxides obtained from HT anionic clays and containing at least one
oxide of Fe, Al, V, Cr and/or Ga, for the selective permethylation under near- or super-critical
conditions of β-, γ-, δ-tocopherol or their mixtures into α-tocopherol, the most valuable product
having the highest vitamin E activity.105
Figure7. Reaction pathway for the synthesis of 2’,4’,4-trimethoxychalcone (vesidryl).103
In the field of organic chemistry interesting applications also appear continuously: for
example Mg/Al HT anionic clays heated in N2 up to 823 K are highly active, selective and
regenerable catalysts for the liquid phase Meerwein-Ponndorf-Verley reduction of carbonyl
compounds using 2- propanol as the hydrogen donor.106 A Mg/Al (3:1) mixed oxide obtained
by calcination at 723 K showed better activity in comparison with alumina, silica-alumina or
Y-zeolite, attributed to a synergetic effect between strong Lewis basicity and mild acidity
(Table 6). On the other hand, the same HT precursor after thermal decarbonation and
rehydratation has been reported for other reactions of industrial interest, such as the
cyanoethylation of alcohols,107 with a high activity and air stability (unlike that occurring for
other solid base catalysts), or the synthesis of pseudoionones from citral and acetone, although
in the latter case with a low activity attributed to poor accessibility of the interlayer basic
sites108 Finally, a similar calcined/rehydrated Mg/Al (2.5:1) catalyst has been reported in the
selective Michael addition (Fig. 8) on methyl vinyl ketone, methyl acrylate, and simple and
substituted chalcones by donors such as nitroalkane, malononitrile, diethyl malonate,
cyanoacetamide and thiols, with quantitative yields under mild reaction conditions.109
Table 6. Meerwein-Ponndorf-Verley reduction of unsaturated aldehydes to the

corresponding unsaturated alcohols using a Mg/Al (3:1) HT anionic clay heated in N2 at 723
K.106
Aldehyde Reaction time (h) Conversion (%) Selectivity (%)

Citronellal 4 90 95 a
Cinnamaldehyde 5 75 92 b
Citral 5 83 70 c
Catalyst = 0.140 g; reaction temperature = 355 K; aldehyde = 1 mmol; 2-propanol = 10 ml; stirring speed = 900 rpm.
(a) Citronellol; (b) Cinnamyl alcohol; (c) Nerol + geraniol
Figure 8. Reaction pathway in the 1,4-addition (Michael reaction).109

Ueno et al.110 have shown the use of Mg/Al anionic clays as efficient base catalysts for the
epoxidation at low remperature of various olefins using H2O2 in the presence of benzonitrile
and with MeOH as the solvent (Fig. 9a). Analogously, Mg/MIII (MIII = Al, Ga or In) mixed
oxides obtained at 773 K in N2 from HT precursors have been reported in the epoxidation of
limonene to limonene oxide in the presence of acetonitrile, butyronitrile or benzonitrile,
observing maximum activity for the latter nitrile and the Mg/Al catalyst.111 Moreover, Kaneda
et al.112-114 have applied HT anionic clays in the heterogeneous Baeyer-Villiger oxidation of
various ketones using a combination oxidant system of molecular oxygen and benzaldehyde,
depending on the basic character of the precursor. Multicomponent HT anionic clays
containing a small amount of Fe, Ni or Cu led to higher yield values, due to cooperative action
between the basic and the transition metal sites (Fig. 9b). Interesting reviews on the
applications of HT anionic clays and their derivatives in the oxidation of organic compounds,
with special emphasis on the ecofriendly options for the production of speciality and fine
chemicals, have recently been published by Mayoral and coworkers115 and Choudary et al.116
Multicomponent mixed oxides have also been reported in the vapour or liquid phase
hydrogenation of nitriles, evidencing the requirement for a compromise between
metal-reducibility (that affects the activity) and the acido-basicity of the catalyst (that affects
the selectivity).117-119 Both these functions can be finely tuned through the nature and amount of
the cations in the layers and the activation conditions. High activity and selectivity have also
been reported for a Mg/Fe mixed oxide obtained from an HT precursor in the reduction in mild
reaction conditions of aromatic nitrocompounds using hydrazine hydrate; the catalyst was
regenerable, reusable and formed only N2 and H2O as by-products.120
Figure 9. Activity of different HT anionic clays in (a) the epoxidation of olefins using H2O2 110 and (b) the
Baeyer-Villiger oxidation of ketones.112-114
Finally, in a recent and innovative paper, Indian researchers have reported that Mg/Al
mixed oxides catalyze the diasteroselective synthesis from aldehydes and nitroalkanes of
nitroalkanols, that can be easily hydrogenated with retention of configuration forming
pharmacologically important derivatives.121 Maximum activity was observed for a Mg/Al (3:1)
mixed oxide, that could be reused after new activation at 723 K. A wide range of aldehydes and
nitroalkanes were investigated (Table 7), without any effect of the catalyst/substrate ratio and,
very relevant, formation predominantly of the threo isomers, i.e. the most energetically
favoured on the basis of a transition state model based on chair-like structures involving
coordination between the two oxygen atoms and the Mg atoms (Fig. 10).
Table 7. Heterogeneous diasteroselective synthesis of nitroalcohol derivatives (Henry reaction)

catalyzed by a Mg/Al (3:1) HT anionic clay calcined at 723 K (reaction conditions: aldehyde =
5 mmol; nitroalkane = 5 mmol; catalyst = 20 wt%; THF = 10 ml; reflux temperature).121
Substrate Nitroalkane Reaction Product Yield a threo:erytro b

time (h)
Benzaldehyde Nitroethane 6 1-Phenyl-2-nitropropan- 87 3.25:1
1-ol
3-Nitro-benzaldehyde Nitroethane 6 1-(3-Nitrophenyl)-2-nitr 95 12.5:1
opropan-1-ol
4-Methoxy-benzaldehyde Nitroethane 8 1-(4-Methoxyphenyl)-2- 62 1.23:1
nitropropan-1-ol
2-Chloro-benzaldehyde 1-Nitro-propane 6 1-(2-Chlorophenyl)-2-nit 89 1.53:1
robutan-1-ol
4-Nitro-benzaldehyde Nitroethane 6 1-(4-Nitrophenyl)-2-nitr 84 100:0
opropan-1-ol
2-Chloro-benzaldehyde Nitroethane 6 1-(2-Chlorophenyl)-2-nit 82 100:0
ropropan-1-ol
Furan-2-carboxaldehyde Nitroethane 6 1-(2-Furyl)-2-nitropropa 74 1.5:1
n-1-ol
2-Chloroquinoline-3-carbo Nitroethane 8 1-(2-Chloro-3-quinoline) 88 100:0
xaldehyde -2-nitropropan-1-ol
Cynnamaldehyde Nitroethane 6 1-Styryl-2- 41 1.25:1
nitropropan-1-ol
(a) Isolated after column chromatography; (b) average ratios calculated from 13C-NMR signals (50.3 MHz).
Figure 10. Transition state structures for the diasteroselective synthesis of nitroalcohol derivatives over Mg/Al
HT compounds calcined at 723 K for 8 h.121
AIR DECONTAMINATION
Calcined HT anionic clays have found application as catalysts in many reactions of high
environmental relevance, such as SOx and NOx removal, N2O decomposition and, recently, the
combustion of organic vapours. In the former case, they were investigated to reduce the
emissions from FCCU, that represent the most relevant SOx source in petroleum refineries and
for which severe restrictions are established by the different countries.46,47,122,123 These catalysts
have to be able to oxidize SO2 to SO3 (also using CeO2 as co-catalyst) and to fix it as sulphate in
the regenerator, while in the reducing atmosphere of the cracking zone the sulphate is
decomposed to H2S, which can be recovered by available techniques (Fig. 11). As previously
reported,46,47 compounds of intermediate basicity, such as Mg/Al mixed oxides obtained by
calcination of HT precursors, have been proposed as supports to achieve better compromises
between SOx uptake and catalyst regeneration. The insufficient regeneration of the earlier
Ce/MgAl2O4·MgO catalysts was overcome by partial substitution of Al3+ ions by Fe3+, V3+ or
Cr3+ ions, obtaining active and stable catalysts, which, furthermore, allowed the simultaneous
control of SOx and NOx emissions from the FCC regenerating units.122
The above catalysts were Al-rich, thus with limited amounts of SOx captured, especially in
high-temperature regenerators. Therefore, Mg-Al mixed oxides with higher Mg-contents were
successively investigated,123 observing after impregnation with 5 wt% of CeO2 very good SOx
adsorption associated with a limited regeneration capacity. To overcome this constraint, the
catalysts were further impregnated with 1 wt% (as transition metal oxide) of Co, Cu, Zn, Ni, Fe,
Cr, V or Ti, obtaining better regenerability for V, Fe and Cu (Fig. 12). Because of the constraints
in the use of V and Fe in FCCU, attention was focused on Cu/Mg/Al mixed oxides obtained
from HT precursors (always impregnated with 5wt% of CeO2) observing good adsorption and
regeneration capacity for 5 wt% CuO, while higher amounts led to a decrease in the SOx
adsorption, with a corresponding increase in regeneration capacity.
Figure 11. SOx removal reaction pathway.46
Figure 12. Effect of the co-catalyst on regeneration of Mg/Al catalysts obtained from HT precursors: (+)
without co-catalyst, (O) V, (P) Co, Ni, (Q) Cu, Fe, (V) Zn, Cr, (X) Ti.123
Operating with an O2 excess ≤ 0.6 %, Cu/Mg/Al HT anionic clays calcined at 1023 K for 3
h and activated under H2 at 823 K for 30 min, can simultaneously remove SOx (by an oxidation
and/or reducing reaction) and NOx (by a reducing and/or decomposition reaction).124 The active
centers for the reactions have been identified as Cu0 or Cu+1 species and it was observed that the
catalytic activity was not affected by the presence of coke and the formation of
“copper-sulfured species”. Similar results have been obtained with an analogous Co/Mg/Al
catalyst, which was able to reduce NOx even in the presence of a higher O2 excess, although
with a lower activity in SOx removal than the Cu-containing catalyst, which could be improved
by adding CeO2. Again, reduced cobalt species have been proposed as the active sites, as
evidenced by the absence of activity in the presence of a high O2 excess or if the catalyst was
not previously reduced.125
Fe/Mg/Al, Cr/Mg/Al and Cu/Mg/Al catalysts obtained from HT precursors have been
investigated in the selective catalytic reduction (SCR) of NO.48,126 A general improvement in
the catalytic performances in comparison with the analogous catalysts prepared by incipient
wetness impregnation of a Mg/Al mixed oxide was observed, related to better dispersion of the
transition oxides.48 Considering the best behaviour of Cu-containing catalysts, Cu/Mg/Al HT
anionic clays were thoroughly investigated as a possible inexpensive alternative to Cu-zeolites
for NO reduction by NH3.127 While no significant differences were observed in the absence of
O2, it was found that the presence of stabilized copper ions improved the catalytic
performances in the presence of excess O2 (such as present in flue gases), with interesting
catalytic performances obtained for Cu-contents in the range 12 to 25 wt% ca. (as CuO) (Fig.
13), associated with good stability with time-on-stream (Fig. 14). The reaction mechanism and
the nature of the active sites involved either in SCR of NO or ammonia oxidation (main
side-reaction at high temperature), have been investigated using FT-IR spectroscopy, showing
that the SCR reaction occurs between gas-phase NO and NH3 strongly adsorbed on
Cu-containing phases and/or highly dispersed CuO clusters.128 Moreover, the SCR activity of
these catalysts did not involve Brönsted acid sites, absent on the surface of these samples, thus
evidencing that Brönsted acidity is not always a key requirement for SCR activity.
A thermally decomposed Mg/Fe HT anionic clay has been reported to decompose NO at
673 K, probably via N2O, although with conversion values (< 27%) and experimental
conditions very far from those of practical interest.129 On the other hand, a Cu/Mg/Al HT
precursor, containing 9 wt% ca. of CuO, calcined at 1023 K and activated under H2 at 773 K for
30 min catalysed both NO decomposition and its reduction by propane.130 In the NO
decomposition the good initial conversion (95% ca.) decreased rapidly with time-on-stream,
for example to 80% ca. at 973 K and to lower values when the reaction temperature was further
decreased. The catalytic activity increased with increasing temperature up to ca. 1023 K, while
higher temperatures yielded lower conversions, due to thermodynamic limitations by the
exothermic character of the reaction. On the contrary, in the reduction with propane, total
conversion of NO was obtained at T ≥ 873 K, indicating that the reaction was not
thermodynamically limited. Using EXAFS spectroscopy and combined EXAFS/XRD under
the operating conditions, the active species were identified as Cu+1 for NO decomposition and
Cu0 for its reduction.
The reduction of NO with propane in the presence of different contents of O2 has been
recently investigated,131,132 observing complete NO conversion at T ≥ 723 K and with O2/O2st <
1.0 in the feed (i.e for O2-contents lower than the stoichiometric amount required for the
complete oxidation of propane). The catalytic behaviour depended significantly on the catalyst
composition, with better performances for the Cu/Cr mixed oxides obtained by calcination at
873 K for 3 h131 in comparison with those obtained with a decavanadate-exchanged Mg/Al (2:1)
HT precursor calcined at 823 K for 3 h.132 The best performances for the Cu/Cr mixed oxides
were observed for the catalyst with an intermediate Cu/Cr ratio (2:1), which also withstood
higher O2-contents in the feed. Operating at O2/O2st = 0.8, this catalyst showed 100%
conversion of NO and 75% conversion of propane at 723 K, and an almost negligible formation
of N2O above 623 K. Some of these authors133 have also recently claimed the use of
multicomponent mixed oxides in the total oxidation of N-containing organic vapours, using
dimethylformamide (DMF) as a probe molecule, widely used as an industrial solvent. The
catalytic performances depended on the composition and calcination temperature. For example,
the best results were observed for Cu/Zn/Cr/Al/V or Cu/Cr/V HT precursors calcined for 3 h at
673 K or 823 K, respectively.
Figure 13. Selective catalytic reduction of NO with NH3 and O2 using mixed oxides having different
Cu-contents (as CuO wt%) obtained by calcination for 14 h at 923 or 1173 K (*) of Cu/Mg/Al HT anionic clays.
(Reaction conditions: atmospheric pressure; NO = 0.60 %, NH3 = 0.75%, O2 = 3 % and the remainder He;
GHSV = 10,000 h-1).127
Figure 14. Catalytic activity as a function of time-on-stream at 653 K in NO reduction with NH3 and O2 of a
Cu/Mg/Al mixed oxide (CuO = 12.5 wt%) obtained from a HT precursor by calcination for 14 h at 923 K [(+)
NO conversion; (Q) N2 selectivity)]. (Reactions conditions: atmospheric pressure; NO = 0.60 %, NH3 = 0.75
%, O2 = 3 % and the remainder He; GHSV = 10,000 h-1).127
Calcined HT anionic clays have been widely investigated in the decomposition of N2O, a
greenhouse pollutant (270 times ca. more powerful than CO2 on a weight basis), which
furthermore, contributes to catalytic destruction of stratospheric ozone. N2O continues to
increase in the atmosphere and this increase appears to be caused mainly by anthropogenic
activities, such as cultivated soil, biomass burning, stationary (mainly in circulating fluidized
beds) and mobile combustion and chemical processes (for example adipic acid for Nylon 6,6).
However, the only emissions that can be reduced in the short term are those associated with
combustion and chemical processes, with a reasonable goal of achieving about 60-90%
reduction by 2010.134
Kannan and Swamy135,136 claimed calcined Co/Al, Cu/Al or Ni/Al HT compounds as
effective catalysts in the decomposition of N2O, although they used a recirculating static
reactor with 6.7 kPa of N2O, i.e. with experimental conditions very far from those of practical
interest. In fact, using a flow reactor and feeding a 1% N2O/He gas mixture, both Cu/Al and
Ni/Al mixed oxides were found to have very low activity with appreciable conversion only
above 773 K (Fig. 15).134 Even worse performances were observed for a calcined HT
containing both elements, while a relatively higher activity was obtained by CuO supported on
a Mg/Al mixed oxide prepared by calcining a HT precursor. A significant increase in activity
was observed when the Ni/Al sample was prereduced at 773 K for 30 min in a 20% H2/He flow
and then reoxidized with N2O before beginning the catalytic tests. The best performances were
obtained using a Mg/Al mixed oxide containing a small amount of Rh, for which the change
from 10 to 90% of N2O conversion occurred in a temperature range of 100 K, with a behaviour
intermediate between those of Rh/TiO2 and Rh/Al2O3.134
The role of the composition of the precursors, containing both transition and noble metals
(Rh, Ru or Pd), was jointly investigated by US and Indian researchers as a function of the
reaction conditions and feed composition (mainly presence of O2 and/or H2O), with the aim to
optimize these materials in a simulated process stream (Table 8).28,137,138 Maximum surface
area values were obtained by calcining the precursors at temperatures below 593 K, optimum
activity and life was obtained at 723-773 K, while calcination at 1073 K was too severe. The
tests were at first carried out with a low N2O concentration in the feed; the N2O conversion
increased with increasing the reaction temperature and for the Co/Al mixed oxides a maximum
for an atomic ratio of 3.0 was found, although the conversion significantly worsened by
co-feeding O2 or, mainly, O2 and steam. Improved activity at low temperatures was reported for
a Co/Al/La (4:1:1) catalyst, although in this case the material did not reveal any HT structure by
XRD analysis. Using the latter catalyst Dandl and Emig139 determined the reaction rate at
various partial pressures of N2O, O2 and H2O in a temperature range from 573 K to 823 K. The
kinetic simulation resulted in a mechanistic model and the energies of activation and rate
coefficients were estimated for the main step of the reaction. However, the best
performances137,138 were obtained with Co/Rh/Al catalysts, in particular with the 0.7 wt% of Rh,
which was also active at 573 K and did not show any deactivation effect due to O2 or steam.
Large beds of Co/Al catalyst (with an atomic ratio equal to 2.2) calcined at 773 K were shown
to perform effectively for long times-on-stream under a simulated wet N2O process stream
(10-15% N2O, 2% H2O and/or 2% O2), without any hydrothermally induced deactivation effect.
Finally, in comparison with the already known Co-ZSM5 catalyst, the Co/Al catalyst showed a
75 K lower light-off temperature (corresponding to 50% conversion of N2O), i.e. reducing
energy requirements and placing less wear and stress upon process equipment (Fig. 16).137
In a recent paper140 calcined HT anionic clays containing different combinations of
bivalent (Co,Pd and Mg) and trivalent (Al, La, Rh) cations, previously calcined at 723 K for
18h, were studied with the aim to obtain less expensive systems with activity approaching those
of Rh- containing catalysts. These authors claimed the formation of pure HT compounds also
for an Al/La = 1 ratio, in contrast with that previously reported137 and the significantly higher
ionic radius of the La3+ ions (117.2 pm in comparison to 67.5 and 80.5 pm, for Al3+ and Rh3+
ions, respectively, in octahedral coordination).141 Furthermore, the thermal decomposition of
the La-containing samples was different from that of the HT anionic clays and the calcined
samples were characterized by the presence of segregated La-containing phases. The catalytic
tests were carried out with a diluted feed (0.1% N2O in He, with the addition in the deactivation
tests of 0.01% ca SO2 and 3% O2 for 1 h), i. e., in conditions far from those of industrial interest.
A significant increase in activity was observed in comparison with the Co/Al catalyst due to the
presence of Rh (Co/Rh/Al = 3/0.02/1 as atomic ratio) or La (Co/La/Al = 3/1/1). In the case of
La, the increase in activity was attributed to the high activity of La2O3 in N2O
decomposition.142
Figure 15. Comparison of the activity in the conversion of N2O for various mixed oxides obtained from HT
precursors by calcination at 923 K for 14 h. (Reaction conditions: atmospheric pressure; N2O = 1 % and the
remainder He, GHSV = 1,800 h-1).134
Table 8. Catalytic activity in N2O decomposition of different mixed oxides obtained by

calcination of HT precursors.28,137,138
Sample Atomic ratio Calc. temp (K) N2O conversion (%)

Co/Al 2.2:1.0 773 99a 96b 54c
a
Co/Al 2.2:1.0 1073 12 n.d. n.d.
Cu/Al 2.0:1.0 823 48a n.d. n.d.
Co/Al 3.0:1.0 773 84a 67b 25c
a b
Ni/Al 3.0:1.0:1.0 773 95 92 99c
a b
Co/Mg/Al 2.0:0.94:1.0 773 100 97 79c
a b
Rh/Co//Al 0.3 wt% Rh 773 100 99 88c
Rh/Co/Al 0.7wt% Rh 773 100a 100b 100c
Rh/Co/Al 1.0 wt% Rh 773 71a 42b 12c
-1
Reaction conditions: pressure = 101.5 kPa; temperature = 723 K; GHSV= 30,000 h ; gas mixtures = (a)
N2O 985 ppm and the remainder He; (b) N2O 985 ppm, O2 = 25,000 ppm and the remainder He; (c) N2O
985 ppm, O2 = 25,000 ppm, H2O = 20,000 ppm and the remainder He.
Figure 16. Comparison of the catalytic activity in N2O decomposition of (V) Co/Al (2.2, as molar ratio) HT
anionic clay calcined at 773 K, (x) Co-ZSM-5 (trilobe) and (O) Co-ZSM-5 (extrudate) catalysts (Reaction
conditions: pressure = 0.07 MPa; N2O = 10 %, H2O = 2 %, O2 = 2 % and the remainder N2; GHSV =
16,000-18,000 h-1).137
The addition of Pd to the Co/La/Al catalyst led to results comparable to those of the
Rh-containing catalyst only for a Pd content 50 times higher than that of Rh. This effect is
attributed to an increase in the rate of desorption of O2 from the catalyst surface, the most
difficult step in N2O decomposition.143 Significant increases in stability in SO2 and O2 mixtures
were found mainly with the addition of Mg, which plays a key role although it is not itself
active in the reaction. For example, a Co/Mg/Rh/Al catalyst did not show any deactivation even
after 80 h of reaction, while for the corresponding Co/Rh/Al catalyst, conversion dropped from
80 to 60% during the first 10 h. However, there is an optimum amount of Mg for these catalysts,
since it exerts an important influence on the catalytic behaviour. Indeed, the presence of Mg
leads to an increase in the surface area of the calcined materials, provides stability against SO2
inhibition at low temperature and eliminates the initial deactivation, but at the same time
decreases the specific activity.144
Recently, some of the above authors145 proposed a dual-bed catalytic system by which
NOx and N2O may be successively removed from flue gases simulating lean-burn engine
conditions. NOx is removed in the first stage by SCR with propene over a Pt supported on
activated carbon catalyst. The second bed decomposes the N2O formed in the first bed into N2
and O2 using Co/Rh/Al and Co/Pd/La/Al mixed oxides obtained from HT precursors or ion
exchanged Fe-ZSM-5 and Pd-ZSM-5 zeolites. The Co/Rh/Al mixed oxide proved to be the
most active and stable catalyst and at 475 K and 700 K in the first and second stage,
respectively, molar conversions of 90% and 100% for NOx and N2O were achieved in a stable
operation lasting 50 h.
ADVANCES IN NATURAL GAS CONVERSION

Exploitation of natural gas is an important goal from both the industrial and academic
points of view, considering the low price and high availability of this raw material. Activation
of CH4, its main component, is a key factor to promote the utilization of natural gas and
currently the indirect way [i.e. the preliminary formation of CO and H2 (synthesis gas or
syngas)] appears to be more promising146-148 than the direct partial oxidation to CH3OH or
coupling reaction to C2, which so far have shown low yields.149,150 Furthermore, many
important chemical processes require syngas, in various H2 to CO ratios (production of
ammonia, hydroformylation reactions, CH3OH, hydrocarbons, CH3COOH, etc.).
The syngas production technologies (steam reforming, autothermal reforming, combined
reforming and noncatalytic partial oxidation),151-155 are well established and have a high
thermal efficiency, but being capital and energy intensive, are still being continuously studied
and improved by careful investigations of the complex links between catalytic activity, material
constraints and process schemes. The catalytic processes operate at significantly lower
temperatures than the noncatalytic partial oxidation process (1623-1873 K) and Ni-containing
catalysts very often prepared via HT precursors have been widely employed, starting from the
pionering work of Ross et al. on steam reforming of CH4, in which HT anionic clays were
claimed for the first time as optimum catalyst precursors.156
CH4 + H2O → CO + 3 H2 ∆H0298 = 206 kJ/mol (1)

CH4 + 0.5 O2 → CO + 2 H2 ∆H0298 = - 36 kJ/mol (2)
CH4 + CO2 → 2CO + 2 H2 ∆H0298 = 248 kJ/mol (3)
CO + H2O → CO2 + H2 ∆H0298 = - 41 kJ/mol (4)
Steam reforming is strongly endothermic (Eq. 1) and produces higher H2 to CO ratios (3 or

more since an excess of steam is generally used to reduce coke formation) than those required
in current downstream processes. Energy may be supplied by heating the reactor externally or
by other means. Another way of making syngas from CH4 is direct catalytic partial oxidation
(CPO) (Eq. 2), which is exothermic and gives rise to a more desirable H2 to CO ratio. Steam or
O2 may be replaced by CO2 (Eq. 3), this reaction being of industrial interest because of the low
H2 to CO ratio in the product gas;157,158 furthermore, this process is also attractive as a CO2
consuming reaction.159 These three reactions may be combined to achieve the most suitable H2
to CO ratios. However, all the above processes are complex and involve many other reactions,
the most relevant of them being the water gas shift reaction (Eq. 4), which has a considerable
effect on the ratio between CO and H2.
All three syngas syntheses can be catalyzed by Ni-supported catalysts161-165 or noble metal
containing catalysts.30-32,166-168 With Ni-containing catalysts, the main problem is the particle
size growth as a function of time-on-stream. The larger particle size promotes coke formation
and catalyst deactivation. A possible solution may be the addition of small amounts of H2S to
the process feed, blocking the sites for coke formation while maintaining sufficient sites for the
reforming reaction (H. Topsoe SPARG process). Very interesting active and stable catalysts
have been obtained starting from HT precursors, which slow down the growth of the Ni
particles and hence excessive coke formation is avoided without using H2S. Since Ni2+ ions are
randomly distributed in the layered structure of the precursor and somewhat insulated by Mg2+
and Al3+ ions, it was believed that Ni aggregation will be minimized in HT-derived catalysts.
This effect, however, is not a general effect of the HT structure, but depends on the composition
such as evidenced by comparing the behaviors of Ni/Cr and Ni/Al HT anionic clays.169
The preparation and application of Ni/Al or Ni/Mg/Al catalysts obtained from HT
precursors in the preparation of syngas by CPO of CH4, with or without steam (T = 973-1073K;
GHSV = 103-104 h-1), have been widely investigated showing excellent results.29,170-176
Bhattacharyya and coworkers attributed the superior stability and higher activity of the
catalysts obtained by calcination of HT precursors in comparison with commercial
Ni-supported catalysts to the fact that in the former samples the Ni particles are surrounded or
“decorated” by crystallites of a spinel-type phase, in agreement with a structural model
previously proposed by Clause et al.177 Sintering and coke formation are less and there is a
corresponding significant increase in the service life of the catalyst. Even though no specific
example was reported in all the above patents, the possible application of noble metals (Rh, Ru,
Pt or Pd) has also been claimed. Furthermore, alternative preparation methods have been
recently reported for Ni and Co containing catalysts, to obtain a sheet-like morphology39 or to
use salt-free reactants, thus reducing the amount of co-products which have to be removed and
sent to disposal.178
The CPO reaction received increased interest after it was shown that high yields in CO and
H2 can be achieved by operating at very high GHSV values (105-106 h-1), even in the absence of
steam and/or CO2 in the feed.161,162,166 In comparison to current technologies, this leads to the
introduction of small CPO reactors (that may be further reduced in size by operating under
pressure) and advantageous process conditions. Again in this case, catalysts obtained by
calcination of HT precursors can be usefully employed because of their specific properties,
although for the Ni/Mg/Al catalysts some differences arise in comparison with the previous
data obtained at lower GHSV values. In particular in these conditions catalysts with high
Ni-contents require mild activation conditions, but deactivate rapidly with time-on-stream,
while those with low Ni-contents require severe reduction conditions, but show high stability
during the reaction.179,180 Using a stable catalyst with low Ni-content, the roles of various feed
compositions (CH4/O2/He = 2:1:4 or 2:1:20 v/v) and reaction temperatures (873-1273 K) were
investigated. The best catalytic performance was observed at high temperature, approaching
the thermodynamic equilibrium, while at lower reaction temperatures the specific effects of
GHSV and feed composition were evidenced.
At high GHSV values, the best catalytic performances have been observed with catalysts
obtained from HT precursors containing small amounts of noble metals. Detailed investigations
of the synthesis and thermal evolution of Rh-, Ir, Ru, Pd and Pt-containing HT have been
carried out.30-32,181 Key factors in the synthesis are the ionic radius and preferential coordination,
with the latter playing the more important role. Furthermore, regardless of the calcination
temperature (923 or 1173 K) the following tendency to segregate as side metal and/or oxide
phases was detected: Pt > Pd > Ru > Ir > Rh, with Rh not showing any segregation phenomena.
This behavior is related to the oxidation state and preferential structure of the noble metal
ions.32 In the CPO reaction, the syngas formation decreased according to the order Rh > Ru ≅ Ir
>> Pt > Pd. The best catalytic performances were observed for a 1% Rh content (as atomic ratio)
and higher Rh contents did not increase the activity, unlike that observed for Ru-based catalysts
(Fig.17).181 Some of these catalysts have been used in the catalytic total oxidation (CTO) of
methane;182 in this case, the lower light-off temperatures were observed for Pd, Rh and Ir based
catalysts, but good performances at high methane conversion were observed only for the Pd
based catalyst, while Rh and Ir based catalysts deactivated with time-on-stream due to
oxidation or sintering phenomena. It has been reported that in the CTO of methane a mixture of
PdO and Pd0 was more active at low temperatures, while at higher temperatures (i.e. high
conversion values) Pd0 was the active species, showing a maximum for an intermediate crystal
size.
Key points in the CPO of CH4 at high GHSV values are the high exothermicity of the
reaction and the presence of hot spot phenomena, that do not allow accurate determination of
the catalyst surface temperature and heat distribution along the catalytic bed. However,
operating in autothermal conditions the gas and surface temperatures for Ni, Rh and Rh/Ni
catalysts obtained from HT precursors have been determined simultaneously using a
thermocouple and IR thermography,183,184 evidencing very different heat distributions as a
function of the catalyst composition. The catalytic tests showed best activity and selectivity for
the bimetallic Rh/Ni catalyst, suggesting the presence of synergetic effects.183 Detailed
investigations of the thermal profile of the catalytic bed and the gas/solid heat distribution as a
function of the catalyst composition, GHSV values and reagent concentration have also been
recently reported for these catalysts.184,185 It was observed that Rh prevented the oxidation of
the Ni in the first part of the catalytic bed (Fig.18) and that the temperature at the end of the
catalytic bed controlled both CH4 conversion and syngas selectivity.
Figure 17. Activity in the CPO of methane as a function of the Ru- or Rh-content for catalysts obtained from
HT precursors by calcination at 1173 K for 14 h. The catalysts were previously reduced at 1023 K for 5 h in a 7
l/h flow of an equimolar H2/N2 mixture (Reaction conditions: oven temperature = 1023 K; GHSV = 500,000
h-1; CH4/O2/He = 2:1:4 v/v).181
Figure 18. Thermography of the top of the catalytic bed during partial oxidation of methane carried out in
autothermal conditions (GHSV = 300.000 h-1, CH4/O2/He = 2:1:4 (v/v)): catalyst: a) Ni/Mg/Al (10/61/29, as
atomic ratio), b) Rh/Ni/Mg/Al (0.1/6/59/35, as atomic ratio) .185
Ni/Al, Rh/Mg/Al and Rh/Ni/Mg/Al catalysts obtained from HT precursors have also been
investigated in CO2-reforming of CH4.186,187 Under severe operating conditions (T= 1133 K; P=
2.1 MPa and GHSV= 14,400 h-1) Ni/Al catalysts showed performances identical to those of
commercial catalysts, with coke formation and pressure buildup across the catalytic bed after a
short period of time.186 Under less severe operating conditions the HT-derived catalysts
exhibited higher activity and stability than commercial catalysts, with very low coke formation
(Fig.19). No significant differences were observed in the HT-derived catalyst as a function of a
preliminary reducing treatment, while for lower Ni-contents, a longer induction time (ca. 24 h)
was required to reach full activity.
Figure 19. Conversion as a function of time-on-stream in the CO2-reforming of CH4 for a virgin (V) or
prereduced (Q) Ni/Al catalyst obtained from a HT precursor and a commercial catalyst (X). The latter showed
indication of coke formation after one week on stream (Reaction conditions: T= 1133-1163 K; P= 0.7 MPa;
CO2/CH4 = 1.0 and H2O/CH4 = 0.5).186
Ni/Mg/Al, Rh/Mg/Al, and Rh/Ni/Mg/Al catalysts obtained by calcining the corresponding

HT precursors at 1173 K also have been investigated in CO2-reforming at high GHSV values
(150-300,000 h-1, T= 945-960 K, P= 0.1 MPa), to evidence the contribution of the
CO2-reforming reaction in the CPO of CH4 in these conditions and check the possibility of
using smaller reactors.187 Higher activity of Ni towards CO2 and of Rh towards CH4 was
observed. The bimetallic catalysts Rh/Ni/Mg/Al exhibited enhanced conversion of both CO2
and CH4, confirming the existence of synergetic effects in the catalysts obtained from HT
precursors. These catalysts did not show any structural and/or physical modification after the
catalytic tests, with, furthermore, no deactivation phenomena.
Ni-containing catalysts obtained from HT precursors have been reported as very active and
selective also in the methanation of CO (inverse reaction of steam reforming).3 The Ni/Al
catalysts obtained form HT containing CO32- as interlayer anions showed good stability under
hydrothermal conditions together with high activity and selectivity also in the absence of alkali
ions,188 generally added to improve activity. Active and stable catalysts for methanation
reaction have been also prepared from ternary Ni/Mg/Al HT precursors.189
The role of HT anionic clays as precursors of catalysts for the conversion of syngas to more
valuable intermediates, such as CH3OH, higher alcohols and/or hydrocarbons, has already been
reviewed,3 thus here only the main features affecting the catalytic behaviour and some recent
investigations are reported. HT anionic clays may be synthesized to prepare Zn/Cr catalysts for
the synthesis of methanol at high temperature and pressure.190 Moreover, Cu/M(II)/Cr [M(II) =
Zn, Mg, Co or Mn] and, mainly, Cu/Zn/Al mixed oxides obtained by calcining HT precursors
were widely investigated in the synthesis of CH3OH at low temperature and pressure (523 K
and 5.0 MPa),3 although using Cu/Zn/Al catalysts the highest activity was obtained with
catalysts with low Al-content, i.e. obtained from mixtures of hydroxycarbonate and HT
phases.191-194 It has been reported that aurichalcite and HT phases gave rise to more active
catalysts than rosasite.194,195 Keeping constant de composition, Li and Inui195 have varied the
relative amounts of the HT and rosasite phases using an ultrasonic generator during the
precipitation and aging steps. The amount of HT phase increased as a function of the ultrasound
frequency with a corresponding increase in the catalytic activity, attributed to the formation of
highly dispersed Cu (Cu+), ZnO and Al2O3 particles. On the other hand, Herman et al.,194 in
conditions near to those of reaction, showed the presence in the most active Cu/Zn/Al catalyst
of well dispersed Cu0 and an amorphous dehydrated (Cu,Zn)6Al2(OH)16CO3 phase.
Among the Cu/M(II)/Cr systems, it was evidenced that, unlike Mg, the addition of Co or
Zn considerably modified the activity and/or selectivity of the Cu/Cr catalyst, due to the
formation of cubic nonstoichiometric spinel-type mixed phases, that by reduction gave rise to
highly dispersed Cu0 not detectable by XRD analysis and probably characterised by
low-Miller-index surface planes 196,197. Formation of segregated cobalt oxides and/or metallic
cobalt was never detected, regardless of the Co- content. Zn promoted significantly the
synthesis of methanol, while Co exhibited a dramatic poisoning effect when present in amounts
up to 2% (as atomic ratio), and further Co additions resulted in an increase in the activity with a
change in selectivity in hydrocarbons. The low amounts of Co destroyed the catalytic activity
by poisoning the oxidizing capacity of the catalyst surface, while for higher Co-contents a
synergetic effect occurred between the well-dispersed metallic copper and the Co-containing
cubic spinel-type phase.197
The nature and the catalytic activity in the Fischer-Tropsch synthesis of Co/Cu/Zn/Cr
mixed oxides, mainly obtained from HT precursors, have been investigated for a wide range of
compositions.198 For all catalysts the hydrocarbons were the main products and presented
typical Schulz-Flory distributions. While the Co/Cr catalysts showed very low activity, a
maximum was obtained for catalysts containing comparable amounts of Co and Cu, in
agreement with the above hypothesis on the role of synergetic effects between these elements.
More recently,199 a high selectivity in C2-C4 paraffins [useful in obtaining liquefied petroleum
gas (LPG) from syngas] has been achieved using an hybrid catalyst prepared by mixing in the
weight ratio 1:1 a Cu/Zn/Al (38/38/24) catalyst for CH3OH, obtained by calcination at 633 K
for 24 h and successive reduction at 633 K for 8 h of a HT precursor, with a Mn(4.65
wt%)-exchanged H-ZSM-5 zeolite. Up to 523 K CH3OH was the main product, which,
however converted to hydrocarbons with increasing temperature; the best C2-C4 selectivity was
observed at 548 K. The relative rate of formation of carbenium ions of various chain lengths on
the zeolite determines the selectivity in C2-C4 olefins, that undergo rapid hydrogenation to the
corresponding paraffins on the CH3OH catalyst, thus preventing the formation of aromatics.
Different classes of catalysts obtained by calcination of HT precursors have been claimed
for the synthesis of mixtures of CH3OH and higher molecular weight (HMW) alcohols, which
may be used as high octane blending stock for gasoline. In some cases the claimed catalysts are
those active in the synthesis of CH3OH at high (Zn/Cr) or low [Cu,Zn,Al(Cr)] temperature and
require the presence of an alkali promoter to form mainly branched alcohols.3 In the latter case,
the most selective and stable catalysts were obtained from homogeneous HT precursors and
required lower amounts of an alkali promoter, with a key role of the catalyst composition and
reaction parameters.200 In other cases the catalyst contained Fischer-Tropsch elements together
with copper and produced mainly linear primary alcohols. These systems also required the
presence of small amounts of an alkali element to enhance the synthesis in HMW alcohols and
avoid uncontrolled methanation. A chain growth scheme for the synthesis of HMW alcohols
from syngas has been proposed by Smith and Anderson,201 assuming one or two carbon
additions at the α- or β-carbon atom of the growing alcohol.
Figure 20 shows the selectivity in the different classes of products as a function of the
precursor composition for the alkalized ternary Co/Cu/Cr systems.202 Intermediate
compositions, especially in the range 1.0 < Cu/Co < 3.0, with Co/Cr > 0.5, gave rise to active
and selective catalysts for the synthesis of C1-C6 alcohols, with high purity of the alcohol phase,
since the presence of Co lowered the formation of esters, ketones and aldehydes, C1-C6
hydrocarbons being the main by-products obtained. It must be noted that for compositions
typical of HT precursors [i.e. M(II)/M(III) ratios ranging from 2.0 and 3.0] methanol was the
main product, while the HMW alcohol synthesis required a ratio ranging between 0.5 and 1.0,
suggesting the formation also of an amorphous phase containing part of the Cr3+ ions. An
interesting review by Borodko and Somorjai203 of the most recent trends and developments in
the science and technology of catalyzed hydrogenation of carbon oxides (CO and CO2) has
been published recently.
Among the most recent applications of CH3OH, the production of H2-rich gaseous fuels
has been investigated for spark ignition engines and coupled-fuel-cells electric engines.204,205
This latter application requires a CO-free H2 stream, since CO irreversibly poisons the Ru/Pt
electrocatalyst in polymer electrolyte CH3OH fuel cells and dramatically diminishes their
performances. H2 can be obtained from CH3OH via three different processes: a) decomposition
(Eq. 5); b) steam reforming (Eq. 6); and c) partial oxidation (Eq. 7):
CH3OH →2 H2 + CO ∆H0298 = - 92 kJ/mol (5)

CH3OH + H2O → 3 H2 + CO2 ∆H0298 = 49 KJ/MOL (6)
CH3OH + 0.5 O2 → 2 H2 + CO2 ∆H0298 = - 192 kJ/mol (7)
To date, the steam reforming reaction of CH3OH has been the only process used for H2
production for fuel cell applications;206 however, the reaction produces a considerable amount
of CO as a by-product, that may be removed in a second-stage catalytic reactor via the water
gas shift reaction (Eq. 4) or even CO oxidation.207 For fuel cell technology, the partial oxidation
reaction of CH3OH becomes advantageous in comparison with steam reforming reaction
because it uses air instead of steam and does not require an external heat.
HT precursors have been claimed for the preparation of catalysts active in all the above
processes.208-211 For example, Pd and Rh-based catalysts obtained by calcination of HT
precursors for 3 h at 723 or 923K and following reduction for 1 h at 673 K have been
investigated in the decomposition of CH3OH in order to decrease the temperature of H2
production. Higher metal dispersion and activity was obtained with a Pd/Mg/Cr catalyst,
sigificantly better than those of analogous impregnated catalysts (Fig. 21).208 Recently,209 a
novel catalyst with high activity and selectivity to syngas, due to the large surface area and Pd
dispersion, was prepared from a composite obtained by synthesizing the HT precursor in a
suspension of hexagonal mesopouros silica (HMS).
Cu/Zn/Cr and/or Cu/Zn/Al catalysts, obtained either from pure HT precursors or mixtures
of HT and hydroxycarbonate phases, have been widely employed in the steam reforming and
partial oxidation of CH3OH.205,210,211 A Cu/Zn/Cr HT precursor calcined at 573 K showed a
high activity in the steam reforming at 523 K, with negligible deactivation with time-on-stream,
and, furthermore, optimum activity and stability also in the tests carried out at high pressure.210
Cu/Zn/Al catalysts derived from precursors containing mainly a HT phase exhibited good
catalytic activity in the partial oxidation reaction, with a CH3OH conversion at 573 K of
40-60% and high selectivity (>90%) in H2 and (>95%) CO2,211 although the possible presence
of hot spot phenomena should be considered, with higher temperatures on the catalyst surface.
The catalytic activity decreased with increasing the (Cu+Zn)/Al atomic ratio in the precursor,
while increasing amounts of hydroxycarbonates favoured the formation of considerable
amounts of dimethyl ether as a by-product.
A way to reduce significantly the hot spot phenomena is to combine the steam reforming
and partial oxidation processes by simultaneously cofeeding O2, steam and CH3OH to obtain
oxidative CH3OH reforming. Furthermore, the ratio of three reactants can be chosen in order to
supply the heat necessary to maintain the steam reforming reaction by the partial oxidation
reaction, with an overall reaction heat near to zero.204,205 Velu et al.212 have recently reported
HT-derived Cu/Zn/Al catalysts very active in oxidative reforming, producing CO-free H2
suitable for fuel cells, with up to 100% CH3OH conversion after 25 h of on-stream operation at
503 K. During the partial oxidation reaction, levels of CO above 3% are usually obtained, but
the temperature and excess water present in the oxidative CH3OH reforming process gives
favourable conditions to transform CO into CO2 by the water gas shift reaction (Eq. 4).205
Figure 20. Main products obtained as a function of the composition of the Cu/Co/Cr system.202
Figure 21. Arrhenius plot of the methanol decomposition rate over various Pd catalysts, reduced at 673 K: (Q)
Pd (3.0 wt%) impregnated on MgO, (X) Pd-Cr (2.9/2.9 wt%) impregnated on MgO, (P) Pd (3.0 wt%)
impregnated on Mg/Cr HT anionic clay calcined 698 K for 3 h, (∆) Pd (3.8wt%)/Mg/Cr HT anionic clay
calcined at 698 K for 3 h. 208
Catalysts always obtained from HT precursors (containing mainly Ni2+, Zn2+ and/or Cu2+)
have also been claimed for the steam reforming of dimethyl ether213 or other oxygenated
compounds (ethers, alcohols, C2-C4 aldehydes or ketones, although examples have been
reported only for methanol)214,215 to produce H2, together with other products (for example
acetic acid), without the use of excess steam (T= 473-573 K; P = 0.5-2.5 MPa; GHSV=
2000-3000 h-1). Finally, Cu/Zn/Cr catalysts obtained from HT precursors have been
investigated in the application of MeOH for H2 storage and as a H2 carrier, showing high
stability in MeOH dehydrogenation to methyl formate. In these catalysts the formation of
spinel-type mixed oxides avoided the severe deactivation observed with the Cu/ZnO based
catalysts, due to the reduction of ZnO in the vicinity of Cu.216
PILLARED OR INTERCALATED HT ANIONIC CLAYS

Pillared or intercalated HT anionic clays (the two terms refer to the accessibility or not of
the interlayer space) have been claimed: i) to obtain shape-selective catalysts, ii) to stabilize
homogeneous or biomimetic catalysts to increase their service life and allow easy recovery and
recycling, and iii) to prepare supported catalysts with concentration of the active phase,
stability and activity higher than those obtained with conventional supports.3,5 Unusual
molecules, as for example sulphonated indolinespirobenzopyran217 or C60 218 have also been
incorporated in Mg/Al HT anionic clays to obtain special materials for photoresponsive and
electronic devices, respectively.
Pillared HT anionic clays may be prepared by different methods: 1) exchange of inorganic
anions, 2) exchange of organic anions, 3) structure reconstruction of the mixed oxides calcined
at T < 773-873 K, and 4) direct coprecipitation. In some cases, these methods have been
combined in order to obtain more crystalline and ordered phases, for example with first
reconstruction of the HT structure in the presence of glycerol to insert long-chain organic
anions, followed by their exchange with the polyanions.219 However, their preparation is not
simple for several reasons: 1) Anion exchange is difficult because of the high charge density (≥
4 e-/nm2 ),220,221 with strong electrostatic forces between the brucite-like sheets and the anions
and consequent “stuffing” of the interlayer space for anion charges ≤ –3.221 2) Hydrolysis of the
pillaring anions can be caused by the precursors as a function of the brucite-like-sheet
compositions. 3) HT anionic clays may decompose in the synthesis conditions chosen on the
basis of the stability of the pillaring agents. 4) The HT structure is stable only at relatively low
temperatures. 5) CO32- competes with pillaring anions to give mixed phases, owing to their high
affinity with the positively charged sheets. For more detailed information on the specific
properties of pillared or intercalated HT anionic clays and their different preparation methods,
reference should be made to previous reviews.3,5,8
The presence of a free and accessible interlayer space and the thermal stability of the
pillared compounds in most cases have not been sufficiently investigated. Further studies are
required to determine if these materials have practical applications and if they can be used as
such and not only in the form of oxides obtained by thermal decomposition. Referring to the
interlayer accessibility, only a small fraction of the claimed pillared HT compounds can be
considered correctly as such. The main examples are those containing polyoxometalate (POM)
anions, which were first described in the patent literature by Wolterman.222 However,
notwithstanding the relatively low negative charge, also Fe(CN6)4- or Fe(CN6)3- anions give
pillared HT compounds, since the requirements for an increase in basal spacing, surface area
and interlayer accessibility are fulfilled5,223,224 (Table 9). Other compounds, containing
low-charge anions, metal complexes, etc. should be more properly defined as intercalated, to
emphasize that the interlayer space is not accessible, and reaction occurs on the external
edge-sites of the crystallites, such as recently confirmed by Pinnavaia and coworkers.225
Table 9. Values of the basal spacing and surface area for some pillared HT anionic
clays.3,5,220-224, 226,239
HT precursor Pillaring agent Basal spacing (Å) Surface area (m2 g-1)
Zn/Al V10O286-, 11.9-12.3 169
Li/Al V4O124- 10.8 n.d.
Mg/Al Mo7O266- 12.2 71
Mg/Al α-(H2W12O40)6- 14.8 107
Zn/Al α-(H2W12O40)6- 14.5 63
Zn/Al α-(SiV3W9O40)7- 14.5 155
Mg/Al PV3W9O409- 12.0 136
Mg/Al Fe(CN)64- 11.0 246
Mg/Al Fe(CN)63- 11.0 235
There is little information in the literature on the thermal evolution of pillared HT anionic
clays and the few data reported are not always in agreement. Different interpretations and/or
hypotheses have been made, probably because of the different techniques employed or
insufficient characterization.5 Until now, only the thermal evolution of pillared HT precursors
containing iso or heteropolyanions has been sufficiently investigated, showing for example that
the interlayer space provides a reactive environment for oxovanadates, which upon thermal
treatment at 373-573 K initially form cyclic or chain-like metavanadate species.226-229 A further
increase in temperature gives rise to layer structure decomposition, while chemical reactions
between the vanadate and cations of the brucite-type sheets occur only above 723 K. This low
thermal stability has been explained on the basis of the higher charge density of the HT
framework. Moreover, pillared heteropolyanions show decomposition temperatures
significantly lower than those of the corresponding salts with large counterions, that may
attributed to the reaction of the mixed oxides obtained by dehydroxylation of the brucite-type
sheets with the Keggin ions.230,231
It is evident that the thermal stability of anions such as metal complexes,
phtalocyaninetetrasulphonate, prophyryntetrasulphonate or other organic anions is not
significantly modified by intercalation in the HT structure and such materials may be used only
at T ≤ 373 K ca. On the basis of the above considerations, pillared or intercalated HT anionic
clays have only low temperature applications,3,5,232,233 while for other applications claimed at
higher temperatures serious doubt exists regarding their stability and they have to be more
correctly considered as an alternative way to prepare homogeneous mixed
oxides.3,5,222,226,234-238 Furthermore, to date pillared or intercalated HT compounds (as such or
after thermal decomposition) have been investigated only on a laboratory scale.
HT compounds pillared with iso or heteropolyanions showed significant photocatalytic
activity in the oxidation of isopropanol to acetone in the presence of oxygen, despite scattering
of the host particles.230,239 Such results indicate that it may be possible to realize shape selective
photochemical processes by controlling the distance between the pillars, i.e. the pore size, such
as in zeolites. The ability of HT compounds to incorporate anionic molecular species while
preserving their photochemical excited-state lifetimes has been reported for
Ru(4,7-diphenyl-1,10-phenanthrolinedisulphonate)4- ions, and the use of layered host systems
for the intercrystal immobilization of anionic photocatalysts was proposed.240
In the shape selective epoxidation of alkene with H2O2, different selectivities have been
observed for 2-hexene or cyclohexene and attributed to different accessibility obtained via
intercalating POM’s with different sizes.241 In addition, it was concluded that (i) the basic
nature of the brucite-like sheets of the HT host favoured high selectivity for epoxides over diols,
and (ii) a steric constraint imposed by the interstitial environment in the pillared catalysts
improved the cis to trans ratio in the oxidation of 2-hexane in comparison to the homogeneous
reaction. However, these conclusions have successively been refuted by Pinnavaia et al.,232
who showed that the enhanced substrate selectivity cannot be attributed to molecular sieving
based on the substrate size or shape, because in many cases the pillared structure was lost under
the conditions used to dry the samples prior to catalytic tests (393 K), while structurally stable
samples showed a limited access to the solvated pillared POM’s under reaction conditions.
Thus, other factors such as selective adsorption based on substrate polarity may be responsible
for the observed selectivity.
More recently, H2O2 has been investigated by Hu et al.242 in the liquid phase oxidation of
acetaldehyde catalized by HT compounds pillared by Keggin-type heteropolyanions.
Selectivity in acetic acid nearly 100% and productivity values in the range 20-53 mmol/gcat h
were reported. In addition, the catalytic activity per mmol of heteropolyanion was in many
cases from 3 to 9 times higher than that obtained using the potassium salts of the POM. The
authors claimed stabilization of the pillared heteropolyanions against decomposition resulting
from H2O2 and specific effects on the catalytic activity related to the brucite-like sheet and,
mainly, heteropolyanion composition. However, surprisingly, dried (≤ 443 K) and calcined
samples (> 723 K) showed the same activity, which decreased dramatically for intermediate
temperatures, with the minimum depending on the POM composition. The authors attributed
the two ranges of high activity to POM-HT compounds or complex spinel-type oxides obtained
by their calcination, respectively, although the hypotheses reported by Pinnavaia et al. should
also be considered.232
There is considerable interest to increase the longevity of intercalated HT anionic clays
through immobilization of systems that possess biomimetic catalytic properties although
associated with very limited stability as homogeneous catalysts. As previously mentioned,
since the interlayer space in not accessible, the reaction occurs on the external edge-sites of the
crystallites.225 HT compounds intercalated with Mn-porphyrins have been reported as suitable
catalysts for many reactions,243 such as, for example, the epoxidation of cyclohexene using
PhIO, while very poor activity was observed in the hydroxylation of heptane, suggesting that
the accessibility of the metal centers may depend on substrate polarity.244
Interesting results have been obtained using intercalated phatalocyanines in the catalytic
oxidation of 1-decanethiol or 2,6-di-t-buthylphenol, probe molecules to check the potential use
of intercalated phatalocyanines as immobilized catalysts for remediation of contaminated
ground water and industrial effluents at ambient conditions225,232,245-247 (Fig. 21) For both probe
molecules, a significant increase in both activity and stability was observed in comparison with
the homogeneous catalysts, together with the possibility to recover the catalyst by simple
filtration. The increase in stability was attributed to the inhibition of the phthalocyanine
dimerization through intercalation in the HT structure. The elimination of thiols has been
investigated by oxidation with oxygen at ambient conditions using intercalated MoVI
complexes.248,249 The authors claimed that water solutions could be used, although the results
referred only to tests carried out with ethanol as the solvent.
Finally, mention has to be made of the application as biomimetic catalysts of Mg/Al or
Ni/Al HT precursors exchanged with tungstates (to an extent of 12% and with the WO42- anions
mainly located in edge positions).250 These catalysts were used in selective oxidative
bromination and bromide-assisted epoxidation reactions with an activity 100 times higher than
the homogeneous analogue (Fig. 22). The low cost and heterogeneous nature of this system,
together with its ability to operate under mild reaction conditions (298 K; 6 < pH < 8 ) using
bromides rather than Br2, suggest interesting environmentally friendly routes to produce
brominated chemicals and drugs and epoxide intermediates. As recently reported, the latter
may be considered an interesting example of “enginered solid catalysts” based on ion exchange
properties of cationic or anionic clays.251 The polarity of these supports can be varied by an
appropriate ion exchange, tailoring the catalytic activity, such as has been reported for tungstate
(hydrophilic) or tungstate/p-toluensolphonate (hydrophobic) exchanged Mg/Al HT compounds
in the olefin epoxidation with H2O2 as a function of the nature of the organic substrate.252
Figure 22. O2 uptake plots for the autoxidation of 1.5 x 10-2 M 1-decanethiol in the presence of
Co(II)-phthalocyaninetetrasulphonates: (R) homogeneous catalyst (deactivated after one reaction cycle), (Q)
catalyst intercalated in a Mg/Al HT compound (no loss in activity after five consecutive reaction cycles)
(reaction conditions: T = 308 K, pH = 9.25, substrate/cobalt ratio = 154).246
Figure 23. Catalytic cycle in bromination with WO42- HT anionic clay. H2O2 binds to tungstate to form
peroxotungstate at the surface. Electrostatic attraction brings bromide to the surface, facilitating transfer of the
activated oxygen atom from peroxotungstate to Br-. Reaction of 2-electron-oxidized Br species in solution:
electrophilic bromination of phenol red into phenol blue (1), and bromide-assisted 1O2 generation from H2O2
(2).250
CONCLUSIONS
For the hydrotalcite-type (HT) anionic clays [also called layered double hydroxides
(LDH’s)] a broad spectrum of catalytic applications already exists and even more will probably
be found in the future in unexpected areas, due to the possibilities of designing catalysts
tailored for specific reactions and/or substrates. Thus, the exponential increase in recent years
of the number of publications referring to HT anionic clays is not surprising. Even more
significant, is the percentage of these papers reporting catalytic applications (as such or, mainly,
after thermal decomposition), evidencing the increasing academic and industrial interest for
these materials and their relevance in catalysis.253 In all cases, to be noted is the high flexibility
and potential of synthetic HT compounds as precursors of multicomponent catalysts, due to the
large number of composition and preparation variables that may be adopted. Further industrial
interest may arise from the possibility of synthesizing large amounts of products in the vapour
phase, with continuous production and economic advantages.
The term HT anionic clays has been used here to emphasize the complementarity between
the properties and applications of cationic and anionic clays, covering a wide number of
reactions of scientific and industrial interest and allowing the transfer of scientific knowledge
acquired for one class of clays to the other, with the necessary adaptations. This is in particular
relevant for the synthesis and applications of pillared or intercalated HT catalysts, for which,
however, interlayer accessibility and thermal stability have first to be more thoroughly
investigated to define their properties, reaction conditions and possible applications. Of
particular importance are the applications in mild reaction conditions to develop cleaner and
more efficient industrial syntheses or decontamination processes for gas or liquid industrial
effluents. Further examples of novel and promising catalytic applications, are those in
stereoselective,23,24,121 biomimetic219,225-227 or electrochemical reactions.254
ACKNOWLEDGMENTS
Financial support from the Ministero per l’ Università e la Ricerca Scientifica e
Tecnologica [MURST, Roma (I)] and the Consiglio Nazionale delle Ricerche [CNR, Roma (I)]
is gratefully acknowledged.
REFERENCES
1. S. Miyata, Kagaku Gijutsushi MOL 15 (1977) 32 (Chem. Abstr. 93 (1980) 49473).
2. W.T. Reichle, Chemtech 16 (1986) 58.
4. A. de Roy, C. Forano, K. El Malki and J.-P. Besse, in Expanded Clays and Other
Microporous Solids, Occelli, M. L., Robson, H. E., Eds., Synthesis of Macroporous
Materials, Van Nostrand Reinhold, New York, 1992, Vol. II, 108.
5. F. Trifirò and A. Vaccari, in Comprehensive Supramolecular Chemistry, Atwood, J. L.,
Davies, J. E. D., MacNicol, D. D., Vögtle, F., Eds., Pergamon, Oxford, 1996, Vol. 7, 251.
6. A. Vaccari, Catal. Today 41 (1998) 53.
7. A. Vaccari, Appl. Clay Sci. 14 (1999) 161.
9. V.A.Drits, T.N. Sokolova, G.V. Sokolova and V.I. Cherkashin, Clays Clay Miner. 35 (1987)
401.
10. W.T. Reichle, Solid State Ionics 22 (1986) 135.
13. R. Allmann, Acta Crystallogr. B24 (1968) 972.
14. H.F.W. Taylor, Miner. Mag. 37 (1969) 338.
15. L. Van der Ven, M.L.M. van Gemert, L.F: Batenburg, J.J. Keern, L.H. Gielgens, T.P.M.
Koster and H.R. Fischer, Appl. Clay Sci. 17 (2000) 25.
16. F.J. Bröcker and L. Marosi, German Pat. 2,024,282 1970 to BASF AG.
17. W. Kagunya, Z. Hassan and W. Jones, Inorg. Chem. 35 (1996) 5970.
18. S. Carlino, Chemistry in Britain 33(9) (1997) 59.
19. M. Bellotto, B. Rebours, O. Clause, J. Lynch, D. Bazin and E. Elkaim, J. Phys. Chem. 100
(1996) 8527.
20. F. Trifirò, A. Vaccari and O. Clause, Catal. Today 21 (1994) 185.
21. F. Gornasari, M. Gazzano, D. Matteuzzi, F. Trifirò and A. Vaccari, Appl. Clay Sci. 10 (1995)
69.
22. M. Gazzano, W. Kagunya, D. Matteuzzi and A. Vaccari, J. Phys. Chem. B101 (1997) 4514.
23. D.E. Laycock, US Pat. 4,962,281 1990 to Dow Chemical Co.
24. D.E. Laycock, R.J. Collacott, D.A. Skelton and M.F. Tchir, J. Catal. 130 (1991) 354.
25. P.V. Kamath, G.H.A. Therese and J. Gopalakrishnan, J. Solid Sate Chem. 128 (1997) 38.
26. V. Rives, F.M. Labajos, M.A. Ulibarri and P. Malet, Inorg. Chem. 32 (1993) 5000.
27. N.J. Blom and E.G. Derouane, Eur. Pat. Appl. 475,357 1992 to H. Topsoe A/S.
28. C.S. Swamy, S. Kannan, Y. Li, J.N. Armorand T.A. Braymer, Eur. Pat. Appl. 640,379 1994
to Air Products and Chemicals Inc.
29. A. Bhattacharyya, M.S. Kleefisch and C.A. Udovich, US Pat. 5,439,861 1995 to Amoco
Co.
30. L. Basini, G. Fornasari, F. Trifirò and A. Vaccari, Eur. Pat. Appl. 101,059 1996 to
Snamprogetti SpA.
31. F. Basile, L. Basini, G. Fornasari, M. Gazzano, F. Trifirò and A. Vaccari, J. Chem. Soc.,
Chem. Comm. (1996) 2453.
32. F. Basile, G. Fornasari, M. Gazzano and A. Vaccari, Appl. Clay Sci. 16 (2000) 185.
33. R.M. Taylor, Clay Miner. 19 (1984) 591.
34. S. Velu, V. Ramaswamy, A. Ramani, B.M. Chanda and S. Sivasanker, J. Chem. Soc., Chem.
Comm. (1997) 2107.
35. S. Velu, D.P. Sabde, N. Shah and S. Sisvasanker, Chem. Mater. 10 (1998) 3451.
36. S.Velu, K. Suzuki, M. Okazaki, T. Osaki, S. Tomura and F. Ohasashi, Chem. Mater. 11
(1999) 2163.
37. S. Velu, K. Suzuki, M.P. Kapoor, S. Tomura, F. Ohashi and T. Osaki, Chem. Mater. 12
(2000) 719.
38. A.A. Schutz, L.A. Cullo and C.P. Kelkar, US Pat. 5,399,329 1995 to Aristech Chemical Co.
39. C.P. Kelkar, A.A. Schutz and L.A. Cullo, US Pat. 5,518,704 1996 to Aristech Chemical Co.
40. C.P. Kelkar and A.A. Schutz, Microporous Mater. 10 (1997) 163.
41. K. Diblitz, K. Noweck, A. Brasch and J. Schiefler, Eur. Pat. 807,086 1996 to RWE-DEA
Aktiengesellschaft für Mineraloel und Chemie.
42. E.S. Martin, J.M. Stinson, V. Cedro III and W.E. Horn Jr., US Pat. 5,730,951 1998 to
Aluminum Co. of America.
43. A.A. Vierheilig, WO Pat. 9,920,389 1999 to Bulldog Tecnologies.
44. D. Stamires, M. Brady, W. Jones and F. Kooli, WO Pat 9,941,198 1999 to Akzo Nobel N.V.
45. H. Müller-Tamm, H. Frielingsdorf, G. Schweier and L. Reuter, German Pat. 2,163,851
1971 to BASF AG.
46. A.A. Bhattacharyya, G.M. Woltermann, J.S. Yoo, A. Karch and W.E. Cormier, Ind. Eng.
Chem. Res. 27 (1988) 1356.
47. J.S. Yoo, A.A. Bhattacharyya, C.A. Radlowski, Ind. Eng. Chem. Res. 30 (1991) 1444.
48. M. Gazzano, B. Montanari and A. Vaccari in Actas XV Simp. Iberoam. Catalisis, Herrero,
E., Annunziata, O, Perez, C., Eds., Univ. Nac. Cordoba, Cordoba (Arg), 1996, Vol. 3, 1967.
49. J. Pasel, P. Käβner, B. Montanari, M. Gazzano, A. Vaccari, W. Makowski, T. Lojewski, R.
Dziembaj and H. Papp, Appl. Catal. B18 (1998) 199.
50. T. Blasco, J.M. López Nieto, A. Dejoz and M.I. Váquez, J. Catal. 157 (1995) 271.
51. J.M. López Nieto, A. Dejoz and M.I. Váquez, Appl. Catal. A132 (1995) 41.
52. P. Dinka, K. Prandová and M. Hronec, Appl. Clay. Sci. 13 (1998) 467.
53. E.G. Derouane, R.J. Davis and N.J. Blom, Eur. Pat. Appl. 476,489 1992 to H. Topsoe A/S.
54. E.G. Derouane, V. Jullien-Lardot, R.J. Davis, N. Blom and P.E. Hoilund-Nielsen, in New
Frontieres in Catalysis, Guczi, L.Solymosi, F., Tètényi, P., Eds., Akadémiai Kiadó,
Budapest, 1993, Vol. B, 1031.
55. Z. Gandao, B. Coq, L.C. de Ménorval and D. Tichit, Appl. Catal. A147 (1996) 395.
56. Y.Z. Chen, C.M. Hwang and C.W. Liaw, Appl. Catal. A169 (1998) 207.
57. R. Unnikrishnan and S. Narayanan, J. Molec. Catal. A144 (1999) 173.
58. M. Rameswaran, E.G. Rightor, E.D. Dimotakis and T.J. Pinnavaia, in Proc. 9th Intern
Congress Catalysis, Phillips, M.J., Ternan, M., Eds., Chem. Inst. Canada, Ottawa, 1988,
Vol 2, 783.
59. T.J. Pinnavaia, M. Rameswaran, E.D. Dimotakis, E.P. Giannelis and E.G. Rightor, Faraday
Discuss. Chem. Soc. 87 (1989) 227.
60. H. Ukuhara, F. Matsunaga and Y. Nakashima, Eur. Pat. Appl. 0,323,192 1988 to Mitsui
Petrochemical Industries Ltd.
61. S. Narayanan and K. Krishna, Appl. Catal. A147 (1996) L253.
62. S. Narayanan and K. Krishna, Appl. Catal. A174 (1998) 221.
63. S. Narayanan and K. Krishna, Catal. Today 49 (1999) 57.
64. S. Miyata, T. Kumura, H. Hattori and K. Tanabe, Nippon Kagaku Zasshi 1971, 92, 514
(Chem. Abstr. 1971, 75, 70781c).
65. R. Teissier, D. Tichit, F. Figueras and J. Kervennal, French Pat. 00,094 1995 to ELF
Atochem.
66. D. Tichit, M.N. Benanni, F. Figueras, R. Tessier and J. Kervennal, Appl. Clay Sci. 13 (1998)
401.
67. F. Figueras, D. Tichit, M. Bennani Nacri and R. Ruiz, in Catalysis of Organic Reactions,
Herkes, F.E., Ed., Dekker, New York, 1998, 37.
68. F. Prinetto, G. Ghiotti and D. Tichit, in Proc. 12th Intern Congress Catalysis, A. Corma, F.V.
Melo, S. Mendioroz, J.L.G. Fierro, Eds., Studies in Surface Science and Catalysis, Elsevier,
Amsterdam, 2000, Vol. 130, 3243.
69. W.T. Reichle, J. Catal. 63 (1980) 295.
70. W.T. Reichle, Eur. Pat. Appl. 095,783 1983, to Union Crabide Co.
71. C.P. Kelkar and A.A. Schutz, Appl. Clay Sci. 13 (1998) 417.
72. J.L. Di Cosimo, V.K. Diez and C.R. Apesteguía, Appl. Clay Sci. 13 (1998) 433.
73. J. Lopez, R. Jacquot and F. Figueras, in Proc. 12th Intern Congress Catalysis, A. Corma,
F.V. Melo, S. Mendioroz, J.L.G. Fierro, Eds., Studies in Surface Science and Catalysis,
Elsevier, Amsterdam, 2000, Vol. 130, 491.
74. V.R.L. Constantino and T.J. Pinnavaia, Catal. Letters 23 (1994) 361.
75. A.L. McKenzie, C.T. Fishel and R.J. Davis, J. Catal. 138 (1992) 547.
76. A. Corma, V. Fornés and F. Rey, J. Catal. 148 (1994) 205.
77. J. Shen, J.M. Kobe, Y. Chen and J.A. Dumesic, Langmuir 10 (1994) 3902.
78. D. Tichit, M.A. Lhouty, A. Guida, B.H. Chiche, F. Figueras, A. Auroux, D. Bartalini and E.
Garrone, J. Catal. 151 (1995) 50.
79. K.K. Rao, M. Gravelle, J. Sanchez Valente and F. Figueras, J. Catal. 173 (1998) 115.
80. J. Sanchez Valente, F. Figueras, M. Gravelle, P. Kumbhar and J.-P. Besse, J. Catal. 189
(2000) 370.
81. E. Dumitriu, V. Hulea, C. Chelaru, C. Catrinescu, D. Tichit, and R. Durand, Appl. Catal.
A178 (1999) 145.
82. A. Corma, V. Fornés, R.M. Martin-Aranda and F. Rey, J. Catal. 134 (1992) 58.
83. W. Kagunya, Z. Hassan and W. Jones, Inorg. Chem. 35 (1996) 5970.
84. A. Bhattacharyya and M.P. Kaminsky, Eur. Pat. Appl. 0,536,879 (1992) to Amoco Co.
85. A. Bhattacharyya and D.B. Hall, Inorg. Chem. 31 (1992) 3869.
86. L. Li, S. Ma, X. Liu, Y. Yue, J. Hui, R. Xu, Y. Bao and J. Rocha, Chem. Mater. 8 (1996)
204.
87. S. Cheng and J.T. Lin, in Expanded Clays and Other Microporous Solids, Occelli, M. L.,
Robson, H. E., Eds., Synthesis of Macroporous Materials, Van Nostrand Reinhold, New
York, 1992, Vol. II, 170.
88. J.T. Lin and S. Cheng, in Abstracts of 11th Int. Congress on Catalysis, Baltimore, USA,
1996, Poster 012.
89. L. Forni, G. Fornasari, R. Trabace, F. Trifirò, A. Vaccari and L. Dalloro, in Proc. 12th Intern
Congress Catalysis, A. Corma, F.V. Melo, S. Mendioroz, J.L.G. Fierro, Eds., Studies in
Surface Science and Catalysis, Elsevier, Amsterdam, 2000, Vol. 130, 3513.
90. Y. Izumi, S. Sato and K. Urabe, Chem. Letters (1983) 1649.
91. S.Velu and C.S. Swamy, Appl. Catal. A119 (1994) 241.
92. S. Velu and C.S. Swamy, Appl. Catal. A162 (1997) 81.
93. S. Velu and S. Sivasanker, Res. Chem. Intermed. 24 (1998) 657.
94. H. Soo, B.C. Ream and H. Robson, US Pat. 5,064,804 1991 to Union Carbide Chemicals &
Plastics Technology Co.
95. M.P. Atkins and M. Chibwe, US Pat. 5,110,992 1992 to The British Petroleum Co.
96. M.W. Forkner, US Pat. 5,260,495 1993 to Union Carbide Chemicals & Plastics
Technology Co.
97. H.-C. Raths, W. Beuer, K. Friedrich and K. Hermann, US Pat. 5,292,910 1994 to Henkel
Kommanitgesellschaft auf Aktien.
98. M.P. Atkins, C.L. Depege and C.R.M. Forano, PCT WO 00,842 1997 to BP Chemicals Ltd.
99. J.A. Barhhorst, A.F. Elsasser Jr. And C.W. Blewett, US Pat. 5,907,067 1999 to Henkel Co.
100. A. Corma, S. Iborra, S. Miquel and J. Primo, J. Catal. 173 (1998) 315.
101. J.L. Di Cosimo, C.R. Apesteguía, M.J.L. Ginés and E. Iglesia, J. Catal. 190 (2000) 261.
102. A. Corma, S. Iborra, J. Primo and F. Rey, Appl. Catal. 114 (1994) 215.
103. M.J. Climent, A. Corma, S. Iborra and J. Primo, J. Catal. 151 (1995) 60.
104. A. Guida, M.H. Lhouty, D. Tichit, F. Figueras and P. Geneste, Appl. Catal. A164 (1997)
251.
105. M. Breuninger, US Pat. 5,932,748 1999 to Roche Vitamins Inc.
106. P.S. Kumbhar, J. Sanchez-Valente, J. Lopez and F. Figueras, J. Chem. Soc., Chem. Comm.
(1998) 535.
107. P.S. Kumbhar, J. Sanchez-Valente and F. Figueras, J. Chem. Soc., Chem. Comm. (1998)
1091.
108. J.C.A.A. Roelofs, A.J. van Dillen, M. Versluijs-Herder, J.T.B.T. Jastrzebski and K.P. de
Jong, in Abstracts of 4th Eur. Congress on Catalysis, Rimini, Italy, 1999, 217.
109. B.M. Choudary, M.L. Kantam, C.R.V. Reddy, K.K. Rao and F. Figueras, J. Molec. Catal.
A146 (1999) 279.
110. S. Ueno, K. Yamaguchi, K. Yoshida, K. Ebitani and K. Kaneda, J. Chem. Soc., Chem.
Comm. (1998) 295.
111. M.A. Aramendia, V. Borau, C. Jiménez, J.M. Luque, J.M. Marinas, F.J. Romero, J.R. Ruiz
and F.J. Urbano, in Proc. 12th Intern Congress Catalysis, A. Corma, F.V. Melo, S.
Mendioroz, J.L.G. Fierro, Eds., Studies in Surface Science and Catalysis, Elsevier,
Amsterdam, 2000, Vol. 130, 1667.
112. K Kaneda, S. Ueno and T. Imanaka, J. Molec. Catal. A102 (1995) 135.
113. K. Kaneda and S. Ueno, In Heterogeneous Hydrocarbon Oxidation, Warren, B.K., Oyama,
S.T., Eds., ACS Symp. Series, ACS, Washigton DC, 1996, Vol 638, 300.
114. K. Kaneda and T. Yamashita, Tetrahedron Lett. 37 (1996) 4555.
115. J.M. Fraile, J.L. García and J.A. Mayoral, Catal. Today 57 (2000) 3.
116. B.M. Choudary, M. Lakshmi Kantam and P. Lakshmi Santhi, Catal. Today 57 (2000) 17.
117. F. Medina Cabello, D. Tichit; B. Coq, A. Vaccari and N.T. Dung, J. Catal. 167 (1997) 142.
118. N.T. Dung, D. Tichit, B.H. Chiche and B. Coq, Appl. Catal. A169 (1998) 179.
119. D. Tichit, B. Coq, S. Ribet, R. Durand and F. Medina, in Proc. 12th Intern Congress
Catalysis, A. Corma, F.V. Melo, S. Mendioroz, J.L.G. Fierro, Eds., Studies in Surface
Science and Catalysis, Elsevier, Amsterdam, 2000, Vol. 130, 503.
120. P.S. Kumbhar, J. Sanchez-Valente and F. Figueras, Tetrahedron Lett. 39 (1998) 2573.
121. V.J. Bulbule, V.H. Deshpande, S. Velu, A. Sudalai, S. Sivasankur and V.T. Sathe,
Tetrahedron 55 (1999) 9325.
122. J.S. Yoo, A.A. Bhattacharyya, C.A. Rodlowski and J.A. Karch, Appl. Catal. B1 (1992)
169.
123. A. Corma, A.E. Palomares and F. Rey, Appl. Catal. B4 (1994) 29.
124. A. Corma, A.E. Palomares, F. Rey and F. Marquez, J. Catal. 170 (1997) 140.
125. A.E. Palomares, J.M. Lopez-Nieto; F.J. Lazaro, A. Lopez and A. Corma, Appl. Catal. B20
(1999) 257.
126. T. Lojewski, R. Dziembaj, R. Chyzy, A. Vaccari and B. Montanari, Polish J. Environm.
Studies 6 (1997) 71.
127. B. Montanari, A. Vaccari, M. Gazzano, P. Käβner, H. Papp, J. Pasel, R. Dziembaj, W.
Makowski and T. Lojewski, Appl. Catal. B13 (1997) 205.
128. M. Trombetta, G. Ramis, G. Busca, B. Montanari and A. Vaccari, Langmuir 13 (1997)
4628.
129. R.S. Mulukula and C. Detellier, J. Mater. Science Lett. 15 (1996) 797.
130. I.J. Shannon, F. Rey, G. Sankar, J.M. Thomas, T. Maschmeyer, A.M. Waller, A.E.
Palomares, A. Corma, A.J. Dent and G.N. Greaves, J. Chem. Soc., Faraday Trans. 92
(1996) 4331.
131. K. Bahranowski, E. Bielanska, J. Janas, T. Machej, L. Matachowski and E.M. Serwicka,
Polish J. Environm. Studies 6 (1997) 59.
132. K. Bahranowski, R. Dula, A. Gavel, J. Janas, T.L. Machej and E.M. Serwicka, Polish J.
Environm. Studies 6 (1997) 65.
133. J. Haber, K. Bahranowski, J. Janas, R. Janik, T. Machej, L. Matachowski, A. Michalik, H.
Sadowska and E.M. Serwicka, in Proc. 12th Intern Congress Catalysis, A. Corma, F.V.
Melo, S. Mendioroz, J.L.G. Fierro, Eds., Studies in Surface Science and Catalysis, Elsevier,
Amsterdam, 2000, Vol. 130, 599.
134. G. Centi, A. Galli, B. Montanari, S. Perathoner and A. Vaccari, Catal. Today 35 (1997) 113.
135. S. Kannan and C.S. Swamy, Appl. Catal. B3 (1994) 109.
136. S. Kannan and C.S. Swamy, Catal. Today 53 (1999) 725.
137. J.N. Armor, T.A. Braymer, T.S. Farris, Y. Li, F.P. Petrocelli, E.L. Weist, S. Kannan and C.S.
Swamy, Appl. Catal. B7 (1996) 397.
138. S. Kannan, Appl. Clay Sci. 13 (1998) 347.
139. H. Dandl and G. Emig, Appl. Catal. A168 (1998) 261.
140. J. Pérez-Ramirez, F. Kapteijn and J.A. Moulijn, Catal. Letters 60 (1999) 133.
141. R.D. Shannon, Acta Crystallogr. A32 (1976) 751.
142. X. Zhang, A.B. Walters and M.A. Vannice, Appl. Catal. B4 (1994) 237.
143. F. Kapteijn, J. Rodriguez-Mirasol and J.A. Moulijn, Appl. Catal. B9 (1996) 25.
144. J. Pérez-Ramirez, J. Overeijnder, F. Kapteijn and J.A. Moulijn, Appl. Catal. B23 (1999) 59.
145. J. Pérez-Ramírez, J.M. García-Cortés, F. Kapteijn, M.J. Illán-Gómez, A. Ribera, C.
Salinas-Martínez de Lecea and J.A. Moulijn, Appl. Catal. B25 (2000) 191.
146. D.L. King, J.A. Cusumano and R.L. Garten, Catal. Rev.-Sci. Eng. 23 (1981) 233.
147. M.J. Howard, M.D. Jones, M.S. Roberts and A.T. Taylor, Catal. Today 18 (1993) 325.
148. J.J. Spivey, S.K. Gangwal, J.R. Zoeller, J.C. Winslow and R.D. Srivastava, Eds., Catal.
Today 58 (2000) 231.
149. M.J. Brown, N.D. Parkins, Catal. Today 8 (1991) 305.
150. J.M. Fox, Catal. Rev.-Sci. Eng. 35 (1993) 169.
151. J.R. Rostrup-Nielsen, in Catalysis Science and Technology, Anderson, J.R.; Boudart, M.,
Eds., Springer-Verlag, 1984, Vol. 5, 1.
152. A. Solbakken, in Natural Gas Conversion, Holmen, A.; Jens, K.-J.; Klboe, S., Eds.,
Studies in Surface Science and Catalysis, 1991, Vol. 61, 447.
153. D.E. Ridler and M.W. Twigg, in Catalysis Handbook, 2nd ed., Twigg, M.W., Ed., Wolfe,
London, 1989, 225.
154. J.R. Rostrup-Nielsen, Catal. Today 18 (1993) 305.
155. J.N. Armor, Appl. Catal. A176 (1999) 159.
156. J.R.H. Ross, M.C.F. Stel and A. Zeini-Isfahani, J. Catal. 52 (1978) 280.
157. J.H. Edwards and A.M. Matra, in Natural Gas Conversion II, Curry-Hyde, H.E.; Howe,
R.F., Eds., Studies in Surface Science and Catalysis, 1994, Vol. 81, 291.
158. E. Ruckestein and Y.H. Hu, J. Catal. 162 (1996) 230.
159. A. Ashcroft, A.K. Cheetham, M.H.L. Green and P.D. Vernon, Nature 352 (1991) 225.
160. D. Dissanayake, M.P. Rosynek, K.C.C. Kharas and J.H. Lunsford, J. Catal. 132 (1991)
117.
161. V.R. Choudhary, A.S. Mamman and S.D. Sansare, Angew. Chem. Int. Ed. (English) 31
(1992) 1189.
162. V.R. Choudhary, A.M. Rajput and B. Prabhakar, J. Catal. 139 (1993) 326.
163. J.R. Rostrup-Nielsen and J.-H. Bak Hansen, J. Catal. 144 (1993) 38.
164. R. Blom, L.M. Dahl, A. Slagtern, B. Sortland, A. Spjelkavik and E. Tangstad, Catal. Today
21 (1994) 535.
165. Y.H. Hu and E. Ruckenstein, Catal. Letters 36 (1996) 145.
166. D.A. Hickman and L.D. Schmidt, J. Catal. 138 (1992) 267.
167. D.A. Hickman, E.A. Haupfear and L.D: Schmidt, Catal. Letters 17 (1993) 223.
168. G.A. Foulds and J.A. Lapszewicz, in Catalysis, Spivey, J.J., Agarwal, S.K., Eds., Royal
Society of Chemistry, London, 1994, Vol. 11, 413.
169. O. Clause, F. Trifirò, A. Vaccari and L. Zatorski, Appl. Catal. 73 (1991) 217.
170. A. Bhattacharyya and M.P. Kaminski, US Pat. 5,354,932 1994 to AMOCO Co.
171. A. Bhattacharyya, W.D. Chang, M.S. Kleefisch and C.A. Udovich, PCT WO 14,700 1994
to AMOCO Co.
172. A. Bhattacharyya, W.D. Chang, M.S. Kleefisch and C.A. Udovich, US Pat. 5,399,537 1995
to AMOCO Co.
to AMOCO Co.
to AMOCO Co.
175. S.B.J. Scott, PCT WO 37,390 1997 to BG PLC.
to AMOCO Co.
177. O. Clause, B. Rebours, E. Merlin, F. Trifirò and A. Vaccari, J. Catal. 133 (1992) 231.
178. A. Bhattacharyya, W.D. Chang, M.S. Kleefisch and C.A. Udovich, PCT WO 15,459 1999
to AMOCO Co.
179. F. Basile, L. Basini, G. Fornasari, D. Matteuzzi, F. Trifirò and A. Vaccari, in Actas XV Simp.
Iberoam. Catalisis, Herrero, E., Annunziata, O, Perez, C., Eds., Univ. Nac. Cordoba,
Cordoba (Arg), 1996, Vol. 3, 1843.
180. F. Basile, L. Basini, M. D’ Amore, G. Fornasari, A. Guarinoni, D. Matteuzzi, G. Del Piero,
F. Trifirò and A. Vaccari, J. Catal. 173 (1998) 247.
181. F. Basile, L. Basini, G. Fornasari, M. Gazzano, F. Trifirò and A. Vaccari, in Preparation of
Catalysts VII, Delmon, B; Jacobs, P.A.; Maggi, R.; Martens, J.A.; Grange, P.; Poncelet, G.,
Eds., Studies in Surface Science and Catalysis, Elsevier, Amsterdam, 1998, Vol. 118, 31.
182. F. Basile, G. Fornasari, M. Gazzano and A. Vaccari, Appl. Clay Sci. (2000), in press.
183. F. Basile, L. Basini, G. Fornasari, A. Guarinoni, F. Trifirò and A. Vaccari, in Natural Gas
Conversion V, Parmalina, A; Sanfilippo, D.; Frusteri, F.; Vaccari, A.; Arena, F., Eds.,
Studies in Surface Science and Catalysis, 1998, Vol. 119, 693.
184. F. Basile, G. Fornasari, F. Trifirò and A. Vaccari, in Proc. 12th Intern Congress Catalysis, A.
Corma, F.V. Melo, S. Mendioroz, J.L.G. Fierro, Eds., Studies in Surface Science and
Catalysis, Elsevier, Amsterdam, 2000, Vol. 130, 44.
185. F. Basile, G. Fornasari, F. Trifirò and A. Vaccari, Catal. Today (2000), in press.
186. A. Bhattacharyya, W.D. Chang and D.J. Schumacher, Appl. Clay Sci. 13 (1998) 317.
187. F. Basile, G. Fornasari, E. Poluzzi and A. Vaccari, Appl. Clay Sci. 13 (1998) 329.
188. BASF AG, UK Patent 1,462,059-60 1973.
189. J.R.H. Ross, in Catalysis, Specialist Periodical Reports, Bond, G.C., Webb, G. Eds., Royal
Society of Chemistry, London, 1987, Vol. 7, 1.
190. E. Errani, F. Trifirò, A. Vaccari, M. Richter and G. Del Piero, Catal. Letters 3 (1989) 65.
191. E.B.M. Doesburg, R.H. Höppener, B. de Koning, X. Xiading and J.J.F. Scholten, in
Preparation of Catalyst IV, Delmon, B.; Grange, P.; Jacobs, P.A.; Poncelet, G., Eds, Studies in
Surface Science and Catalysis, Elsevier, Amsterdam, 1987, Vol. 31, 767.
192. S. Gusi, F. Trifirò, A. Vaccari and G. Del Piero, J. Catal. 94 (1985) 120.
193. K. Richter, W. Kraus, G. Nolze and B. Peplinski, in New Frontiers in Catalysis, Guczi, L.,
Solymosi, F., Tétényi, P., Eds, Studies in Surface Science and Catalysis, , Elsevier, Amsterdam,
1993, Vol. 75, 2805.
194. R.G. Herman, C.E. Bogdan, P.L. Kumler and D.M. Nuszkoski, Mater. Chem. Phys. 35 (1993)
233.
195. J.L. Li and T. Inui, Appl. Catal. A139 (1996) 87.
196. S. Gusi, F. Pizzoli, F. Trifirò, A. Vaccari and G. Del Piero, in Preparation of Catalyst IV,
Delmon, B.; Grange, P.; Jacobs, P.A.; Poncelet, G., Eds, Studies in Surface Science and
Catalysis Elsevier, Amsterdam, 1987, Vol. 31, 753.
197. G. Fornasari, A. D’ Huysser, L. Mintchev, F. Trifirò and A. Vaccari, J. Catal. 135 (1992) 386.
198. G. Fornasari, S. Gusi, F. Trifirò and A. Vaccari, I.&E.C. Research 26 (1987) 1500.
199. G. Ravichandran and D.K. Chakrabarty, Catal. Letters 22 (1993) 179.
200. G. Fornasari, S. Gusi, T.M.G. La Toretta, F. Trifirò and A. Vaccari, in Catalysis and
Automotive Pollution Control, Crucq, A.; Frennet, A., Eds, Studies in Surface Science and
Catalysis, Elsevier, Amsterdam, 1987, Vol. 30, 469.
201. K.J. Smith and R.B. Anderson, J. Catal. 85 (1984) 428.
202. P. Courty, D. Durand, E. Freund and A. Sugier, J. Molec. Catal. 17 (1982) 241.
203. Y. Borodko and G.A. Somorjai, Appl. Catal. A186 (1999) 355.
204. M.A. Pena, J.P: Gomez and J.L.G. Fierro, Appl. Catal. A144 (1996) 7.
205. J.L.G. Fierro, in Proc. 12th Intern. Congress Catalysis, A. Corma, F.V. Melo, S. Mendioroz and
J.L.G. Fierro Eds., Studies in Surface Science and Catalysis, Elsevier, Amsterdam, 2000, Vol.
130, 177.
206. B.A. Peppley, J.C. Amphlett, L.M. Kearns and R.F. Mann, Appl. Catal. A179 (1999) 21.
207. K. Sekizawa, S. Yano, K: Eguchi and H. Arai, Appl. Catal. A167 (1998) 291.
208. R. Shiozaki, T. Hayakawa, Y.-Y Liu, M. Kumagai, S. Hamakawa, K. Suzuki, T. Itoh, T.
Shishido and K. Takehira, Catal. Letters 58 (1999) 131.
209. Y.-Y. Liu, K. Suzuki, S. Hamakawa, T. Hayakawa, K. Murata, T. Ishii and M. Kumagai, Chem.
Letters (2000) 486.
210. L.M. Kearns, J.C. Amphlett, E. Haliop, H.M. Jenkins, R.F: Mann and B.A. Peppley, Prepr.
Symp. Am. Chem. Soc., Div. Fuel Chem. 44 (1999) 905.
211. S. Velu, K. Suzuky and T. Osaky, Catal. Letters 62 (1999) 159.
212. S. Velu, K. Suzuky and T. Osaky, J. Chem. Soc., Chem. Comm. (1999) 2341.
213. A. Bhattacharyya and A. Basu, US Pat. 5,626,794 1997 to AMOCO Co.
214. H.J. Kohnke, German Pat. 19,534,434 1995 to Daimler-Benz AG.
215. A. Bhattacharyya, PCT WO 03,779 1999 to AMOCO Co.
216. K.D. Chung, M.S. Lee, O.S. Joo, S.H. Han and S.J. Uhm, in Hydrogen Power: Theor. Eng.
Solutions, Proc. Hyothesys Symp., Saetre, T.O. Ed., Kluwer, Netherland, 1998, 43.
217. H. Tagaya, S. Sato, T. Kuwahara, J. Kadokawa, K. Masa and K. Chiba, J. Mater. Chem. 4
(1994) 1907.
218. W.Y. Tseng, J.T. Lin, C.Y. Mou, S. Cheng, S.B. Liu, P.P. Chu and H.W. Liu, J. Am. Chem.
Soc. 118 (1996) 4411.
219. E.D. Dimotakis and T.J. Pinnavaia, Inorg. Chem. 29 (1990) 2393.
220. T. Kwon and T.J. Pinnavaia, Chem. Mater. 1 (1989) 381.
221. M. Doeuff, T. Kwon and T.J. Pinnavaia, Synth. Metals 34 (1989) 609.
222. G.M. Woltermann, US Pat. 4,454,244 1984, to Ashland Oil Inc.
223. S. Miyata and T. Hirose, Clays Clay Min. 26 (1978) 441.
224. F.A.P. Cavalcanti, A. Schutz and P. Biloen, in Preparation of Catalysts IV, Delmon, B.,
Grange, P., Jacobs, P.A., Poncelet, G., Eds., Studies in Surface Science and Catalysis,
Elsevier, Amsterdam, 1987, Vol. 31, 165.
225. M. Chibwe, L. Ukrainczyk, S.A. Boyd and T.J. Pinnavaia, J. Molec. Catal. A113 (1996)
249.
226. J. Twu and P.K. Dutta, J. Phys. Chem. 93 (1989) 7863.
227. J. Twu and P.K. Dutta, J. Catal. 124 (1990) 503.
228. A. Bhattacharyya, D.B. Hall and T.J. Barnes, Appl. Clay Sci. 10 (1995) 57.
229. A. Béres, I. Pálinkó, I. Kiricsi, J.B. Nagy, Y. Kiyozumi and F. Mizukami, Appl. Catal.
A182 (1999) 237.
230. T. Kwon and T.J. Pinnavaia, J. Molec. Catal. 74 (1992) 23.
231. J. Wang, Y. Tian, R.C: Wang and A. Clearfield, Chem. Mater. 4 (1992) 1276.
232. T.J. Pinnavaia, M. Chibwe, V.R.L. Constantino and S.K. Yun, Appl. Clay Sci. 10 (1995)
117.
233. E. Gardner and T.J. Pinnavaia, Appl. Catal. A167 (1998) 65.
234. M.A. Drezdon, US Pat. 4,774,212 1988 to Amoco Co.
235. M.A. Drezdon, in Novel Materials in Heterogeneous Catalysis, Baker, R.T.K., Murrell,
L.L., Eds., ACS Symp. Series, ACS, Washington DC, 1990, Vol. 437, 140.
236. K. Hashimoto, Y. Matsumura, M. Fukuchi and Y. Kera, Catal. Letters 19 (1993) 375.
237. J. Don Wang, G. Serrette, Y: Tian and A. Clearfield, Appl. Clay Sci. 10 (1995) 103.
238. F. Malherbe, C. Forano, B: Sharma, M.P: Atkins and J.-P. Besse, Appl. Clay Sci. 13 (1998)
381.
239. T. Kwon, G.A. Tsigdinos and T.J. Pinnavaia, J. Am. Chem. Soc. 110 (1988) 3653.
240. E.P. Giannelis, D.G: Nocera and T.J. Pinnavaia, Inorg. Chem. 26 (1987) 203.
241. T. Tatsumi, K: Yamamoto, H: Tajima and H. Tominaga, Chem. Letters (1992) 815.
242. C. Hu, X. Zhang, L: Xu, B. Mu, W. Zu and E. Wang, Appl. Clay Sci. 13 (1998) 495.
243. S. Bonnet, C. Forano, A. de Roy, J.-P. Besse, P. Maillard and M. Momenteau, Chem. Mater.
8 (1996) 1962.
244. L. Barloy, J.P. Laliter, P. Battioni, D. Mansuy, Y. Piffard, M. Tournoux, J.B. Valim and W.
Jones, New J. Chem. 16 (1992) 71.
245. M.E. Pérez-Bernal, R. Ruano-Casero and T.J. Pinnavaia, Catal. Letters 11 (1991) 55.
246. M. Chibwe and T.J. Pinnavaia, J. Chem. Soc., Chem. Comm. (1993) 278.
247. T.J. Pinnavaia, M.E. Pérez-Bernal, R. Ruano-Caserio and M. Chibwe, US Pat. 5,302,709
1994 to Michigan State University.
248. A. Cervilla, A. Corma, V. Fornés, E. Llopis, P. Palanca, F. Rey and A. Ribera, J. Am. Chem.
Soc. 116 (1994) 1595.
249. A. Cervilla, E. Llopis, A. Ribera, A. Corma, V. Fornés and F. Rey, J. Chem. Soc., Dalton
Trans. (1994) 2953.
250. B. Sels, D. De Vos, M. Buntinx, F. Pierard, A. Kirsch-De Mesmaeker and P.A Jacobs,
Nature 400 (1999) 855.
251. D.E. De Vos, B.F. Sels, W.H. Van Rhijn and P.A. Jacobs, in Proc. 12th Intern Congress
Catalysis, A. Corma, F.V. Melo, S. Mendioroz, J.L.G. Fierro, Eds., Studies in Surface
Science and Catalysis, Elsevier, Amsterdam, 2000, Vol. 130, 137.
252. B.F. Sels, D.E. De Vos and P.A. Jacobs, Tetrahedron Lett. 37 (1996) 8557.
253. D. Tichit and A. Vaccari, Appl. Clay Sci. 13 (1998) 311.
254. B. Ballarin, R. Seeber, D. Tonelli and A. Vaccari, J. Electroanal. Chem. 463 (1999) 123.
Chapter 11
HYDROGENATION CATALYSIS BY MIXED OXIDES

PREPARED FROM LDHS
A. Monzón1, E. Romeo1 and A. J. Marchi2
1
Departamento de Ingeniería Química y Tecnologías del Medio Ambiente, Universidad de
Zaragoza, 50009 Zaragoza. Spain. e-mail: amonzon@posta.unizar.es.
2
Instituto de Investigaciones en Catálisis y Petroquímica (INCAPE), FIQ, UNL,
CONICET, Santiago del Estero 2654, 3000 Santa Fe, Argentina.
INTRODUCTION: HYDROGENATION REACTIONS

One of the oldest and most diverse catalytic processes is the selective hydrogenation of
functional groups contained in organic molecules to produce fine chemicals, intermediates used
in the pharmaceutical industry, monomers for the production of various polymers, and fats and
oils for producing edible and inedible products. Indeed, there are more hydrogenation catalysts
available commercially than any other type, and for good reason, because hydrogenation is one
of the most useful, versatile, and environmentally acceptable reaction routes available for
organic synthesis.
There are two general families of materials used in functional group hydrogenations: noble
metals such as Pd, Pt, Rh and Ru; and transition base metals, such as Ni, Cu, Cr and Co and
their oxides. Often, metals from both families can perform similar hydrogenation functions, but
the decision as to which to use is based primarily on process economics. Base metals are far less
expensive and thus do not require tight metal control to avoid process losses. Additionally, they
do not require detailed contracts for metal recovery as does the use of precious metals. Their
major disadvantage is their lower activity, which requires larger reactors and almost always
more severe process conditions; the resulting higher temperatures and pressures translate into
higher capital and operating costs.
The Pd based catalysts usually employed in selective hydrogenation reactions present
deactivation problems such as poisoning, coking and sintering.1 The use of transition metals is
an interesting and cheaper alternative for selective hydrogenation catalyst. In addition, mixed
oxides as catalysts and catalytic precursors, seem to be the most promising option at present for
preparation of transition metal-based catalysts due to their ease preparation and handling.2,3
368 A. Monzón, E. Romeo and A. J. Marchi
One of the main aims when preparing mixed oxides is to attain a high dispersion of the
cations, avoiding any sort of segregation of the different phases which can be formed.2,4-7 It has
been recognised that coprecipitation is one of the most reliable and reproducible techniques for
the preparation of non-noble metal-based catalysts. This technique allows homogeneous
precursors to be used as starting materials, where two or more elements are closely mixed
together, and favours synergetic effects. One of the methods currently followed to achieve a
large dispersion is the use of hydrotalcites as precursors. These are layered double hydroxides
2+ 3+ x+ n-
(LDHs) with the general formula [M1-x Mx (OH)2] [A ]x/nymH2O. Their structure consists
of brucite-like, Mg(OH)2, layers where a partial M+2/M+3 substitution has taken place, leading
to a net positive charge, balanced by interlayer anions (generally carbonate), associated with a
varying amount of water. Hydrotalcites have attracted much attention in recent years as catalyst
precursors since, after calcination, they lead to mixed oxides, usually of small crystallite size,
high thermal stability and a large specific surface area.2 In addition, well dispersed metallic
particles are usually obtained after reduction treatment.2,8,9 For a given metal, support and
promoters can significantly influence activity and selectivity for certain hydrogenation
reactions.
The development of nickel catalysts resistant to deactivation (mainly by coke and sintering)
is one of the most interesting research challenges, due to the importance of these catalysts in
different reactions such as methane reforming with CO2,10-12 catalysed thermo-conversion of
biomass13 or catalytic cracking of methane to yield hydrogen.14 Nickel catalysts are also useful
in other reactions, namely, steam reforming of methane,6,15,16 production of synthesis gas,17,18
and selective hydrogenation of hydrocarbons.9,19,20 The high temperatures used in methane
reforming make necessary the use of high-temperature resistant catalysts (e.g., NiO-Al2O3).
These materials can be obtained through the thermal decomposition of hydrotalcites, leading to
solids with a spinel structure (e.g., NiAl2O4).14,19-21 The resistance to thermal ageing is mainly
related to the presence of the NiAl2O4 spinel.21-23 If calcination is carried out at intermediate
temperatures (ca. 500-700ºC), a meta-stable phase, usually known as inverse spinel, is obtained,
instead of the normal spinel phase.19,24 Materials with this structure exhibit outstanding
catalytic performances, because of the location of Ni+2 ions in sites of the crystal different to
those occupied in the normal spinel. Thus, the known ability of nickel to favour coke formation
is decreased if domains NiAl2O4 exist in the Ni-Al mixed oxides.18,20 The catalytic activity of
the partially inverse, spinel structure is related to the octahedral coordination of Ni+2 ions on the
external surface of the crystallites.2,19 However, the problem is that a high calcination
temperature (i.e., about 700ºC) is required to crystallise the spinel phase17,18 and therefore high
reduction temperatures are also needed to reduce Ni+2 to zero-valent nickel particles;17
moreover, the spinel phase usually becomes partially destroyed after the reduction treatment
and the final catalyst is constituted by large crystallites in an alumina matrix.17 With all these
problems, it is difficult to strike a balance in order to achieve a solid with the desired catalytic
properties.
Hopefully, the addition of other cations in order to stabilise the inverse spinel structures can
provide an alternative route to avoid some of these problems. Aluminates with an inverse
spinel-like structure containing metals such as Zn require lower decomposition temperatures
(even lower than 500ºC) than those required for the Ni-Al system to form well crystallised
structures,2,25,26 while the ZnAl2O4 phase is maintained after reduction with hydrogen.26,27 The
Hydrogenation Catalysis by Mixed Oxides Prepared from LDHs 369
final catalyst is then constituted by a well dispersed metallic phase on a substrate with an
inverse spinel structure.28
The selective hydrogenation of acetylene is an example of a reaction for which the use of
transition metals such as Ni is an interesting and cheaper alternative to the traditional Pd-based
catalysts usually used for this type of reactions.29 The hydrogenation of acetylene has as it most
important industrial application, the selective hydrogenation of an ethylene stream from
reactors where the steam reforming of naphtha takes place. Acetylene hydrogenation is
necessary in order to avoid the poisoning of the catalysts used during the subsequent
polymerisation of ethylene to obtain polyethylene.
Another example of the use of hydrotalcites as mixed oxide precursors in hydrogenation
reactions is the selective hydrogenation of nitriles over base/metal bifunctional catalysts. The
hydrogenation of nitriles is an important industrial reaction for the preparation of amines.
Conventional catalysts consist of heterogeneous transition metals such as Raney Ni and Co or
supported Ni. Due to the high reactivity of partially hydrogenated intermediates, the reaction
leads to a mixture of primary, secondary and tertiary amines. The operation process requires the
use of base promoters in the catalyst in order to poison the acid sites largely responsible for
coupling reactions between the strongly basic reaction products. The gas phase hydrogenation
of acetonitrile provides a typical example of the potential of LDH-like precursors for tuning the
selectivity in such a hydrogenation reaction.30,31 The main product is ethylamine, while the
by-products are formed by condensation between “imine-“ and “amine-like” adsorbed species
on metal and acid sites (bifunctional mechanism) as well as on the metal sites alone. The tuned
addition of Mg to Ni-Al catalyst decreases the surface acidity and consequently the
bifunctionalised formation of by-products.32 In addition, definite optimisation of the
hydrogenation Ni function, with respect to consecutive reactions, is achieved through the
addition of Co to the catalytic system and therefore to the formation of NiCo bimetallic
phases.32,33 Formation of by-products on the metal surface occurs through condensation at Ni0
sites between multibonded adsorbed species. The first role of Co is the dilution of the Ni
surface in small ensembles less prone to accommodating neighbouring multibonded species
and in this way the selectivity increases.
Normal and branched alcohols with carbon chains ranging from 4 to 18 atoms are
increasingly being required by the chemical industry for the production of solvents, plasticizers
and liquid detergents. These alcohols are mainly produced by hydrogenating aldehyde mixtures
obtained by hydroformilation of olefins over Co, Ni or Cu-chromite catalysts.34 The
hydrogenation of carbonyl compounds, such as ketones and aldehydes, into the corresponding
alcohol is an example of hydrogenation reactions for which transition metal oxide catalysts are
superior to noble metal catalysts for producing the most desirable product.35 For example,
Trifirò et al.34 show that Cu-M-Cr catalysts (M= Cu, Zn and Co), which are very active in the
hydrogenation of crude oxoaldehyde mixtures, may be obtained by the reduction of
non-stoichiometric spinel-type compounds (obtained from the calcination of hydroxycarbonate
coprecipitates). These catalysts do not require physical or chemical promoters, and at the same
time exhibit higher activity than that of commercial catalysts and, furthermore, a higher
stability towards by-products.
Nickel-based catalysts are used for the methanation of CO because they are less expensive,
very selective and no more sensitive to sulphur poisoning than other metals (except ruthenium).
Most of the work on the methanation reaction, with catalysts prepared from NiAlCO3-HTlcs,
has been done by the Ross and van Reijen groups36,37 The authors chose precursors based on
Ni,AlCO3-hydrotalcites. The catalysts obtained exhibited high hydrothermal stability under

steam reforming conditions. Three applications of methanation reactions are found in the
literature:36,38
1) purification of CO present in traces (0.3% vol.) in H2-rich syngas, used for NH3 synthesis.
Ni on a support with a high surface area is used; the temperature ranges from 250 to
350°C, at a pressure of 3.0 MPa;
2) production of SNG (synthetic natural gas) from syngas obtained from coal. In this case
the gas is richer in CO (3-20% vol.), and large amounts of water are present in the
product; the catalyst must work at higher temperature (250-450°C) and pressure;
3) synthesis of methane in the Adam and Eve project.38 In a first step the reforming of
methane is carried out using heated helium coming from nuclear plants as the heat source
for the endothermic reaction; afterwards the heat is recovered by the methanation of
syngas. In this case, too, the catalyst must operate in the presence of high concentrations
of water. It must be active at 250°C (inlet temperature of the reactor) and stable up to
750°C (exit temperature); moreover, the heat must be released at a high temperature as
possible.
Traditional commercial catalysts were unsuitable for the last two applications, requiring
the preparation of catalysts that were not only active and selective, but also stable at high
temperatures under hydrothermal conditions.
The first patent in which a NiAl-hydrotalcite was calcined to be used as an optimal
precursor for the synthesis of methane from syngas was published by BASF.39 It was claimed
that Ni6Al2(OH)16CO3.4H2O gave rise after calcination and reduction to catalysts which were
more active than those prepared by standard procedures, such as impregnation or precipitation.
A further peculiarity of the claimed catalyst was that the addition of alkali metals (usually
added to improve the catalytic activity) was not necessary.
Catalytic applications of hydrotalcites have been reported for other hydrogenation
reactions such as methanol synthesis at high temperatures and pressures (using Zn, Cr mixed
oxides as catalysts) and at lower temperatures and pressures (using Cu-containing mixed
oxides); or the synthesis of higher alcohols. Different classes of catalysts prepared by the
calcination of hydrotalcite precursors (Zn,Cr; Cu,Zn,Al(Cr); Cu,Co,(Zn),Al(Cr); all being
alkali-doped catalysts) have been claimed to be active and selective in the synthesis of mixtures
of methanol and higher molecular weight alcohols, the latter being used as high octane
blending stock for gasoline. Ni-based catalysts are also capable of hydrogenating the aromatic
ring of compounds like aniline, important for the production of cyclohexylamine,
N-phenylcyclohexylamine and dicyclohexylamine. In addition, cobalt-containing hydrotalcites
may be useful precursors of catalysts for the synthesis of hydrocarbons from CO/H2 mixtures
(Fischer-Tropsch synthesis). Catalysts containing both cobalt and copper were able to
homologate to a good extent, giving rise to the production of a wide range of hydrocarbons,
ranging in carbon number from C1 to C11. The existence of a synergetic effect between copper
and cobalt may be postulated as being responsible for the high catalytic activity observed. This
synergetic effect would seem to be correlated either with the presence of a non-stoichiometric
spinel-like phase, in which copper, cobalt as well as zinc are mainly located in octahedral
positions, or to an interaction between the well-dispersed metallic copper (formed under
reducing conditions) and the spinel-like phase.40
In summary, LDHs without any doubt constitute versatile precursors for catalysts with
tuneable properties. These materials are easy to prepare and, provided some minimal
precautions are taken, easy to activate and handle. Their calcination usually leads to spinel-like
structures which are almost “empty” and lead easily to non-stoichiometric structures
characterised by an excess of divalent cations, located in both tetrahedral and octahedral sites.24
These phases may be obtained by low-temperature methods and have different formation
mechanisms as a function of the nature of the elements present. Non-stoichiometric phases may
thus be useful precursors of hydrogenation catalysts with unusual physical and catalytic
properties.
This chapter comprises a review of the studies carried out in this field. First we present the
results obtained by our research group in connection with the acetylene hydrogenation reaction.
This reaction is taken as representative of hydrogenation reactions of unsaturated hydrocarbons,
mainly alkenes, alkynes and alkadyenes. In this section, special emphasis is put on the effect of
coke on the activity and selectivity of the reaction. The subsequent section is a review of the
main works relating to the hydrogenation of unsaturated heterohydrocarbons, particularly
nitro- and carbonyl compounds.
HYDROGENATION OF UNSATURATED HYDROCARBONS:

HYDROGENATION OF ACETYLENE
Although acetylene hydrogenation is a reaction non-sensitive to the structure, the
hydrogenolysis of the acetylene molecule is sensitive to the structure, and both reactions take
place simultaneously leading to the formation of undesired products such as coke and methane.
Coke and methane are formed from ethylidyne species and from dissociatively adsorbed
acetylene.41-43 The high dispersion of the metallic phase is a determining factor in the activity
and selectivity of the catalysts during the selective hydrogenation of acetylene. The formation
of these intermediate species requires a large density of clusters of three atoms on the catalyst
surface. Formation of coke and methane can thus be diminished by an ensemble effect through
the physical isolation of the Ni atoms.43 Therefore, the overall process can be considered as a
reaction “apparently sensitive” to the structure.
From the study carried out with NiO-Al2O3 catalysts modified with different catalytic
and/or structural promoters, it has been shown that the addition of certain metals to the catalyst
composition improves some aspects of its catalytic behaviour during acetylene hydrogenation.
Recent studies26,44,45 have shown that one way to diminish the concentration of clusters of three
atoms is by using a solid in which the Ni is well dispersed on a stable spinel such as the
structure of Zn aluminate. It has also been found that the addition of structural modifiers, such
as Cr2O3, to NiO-Al2O3 bulk catalysts diminishes coke formation.8,9,46 The addition of
promoters such as Co leads to an increase in the selectivity towards the desired product
(ethylene).47
One of the usual disadvantages when using Ni catalysts in hydrogenation reactions is the
formation of coke. The type and rate of coke deposition is a complex function of the operating
conditions, the metal loading, the composition of the support and the preparation method.48-51
Coke deposition on the catalyst modifies its activity and selectivity. In the case of acetylene
hydrogenation selectivity is affected more than activity.8,20,44,46,52
The interest in any study relating to the process of coke formation lies in being able to
predict its dependence on the operating conditions and on the type of feed, and to establish the
way in which the presence of coke on the catalyst surface affects its behaviour, i.e., activity,
selectivity and deactivation rate.
The mechanisms involved in the hydrogenation of acetylene and coke formation have been
widely studied.44,53,54
In this part of the present chapter we present all the characterisation results and the catalytic
results obtained from the kinetic tests carried out by using the acetylene hydrogenation reaction
with the following catalysts:
Base Catalyst
Ni-Al Ni substitution
Co-Zn-Al
Cu-Zn-Al
Addition of Zn
Additionof cations Ni-Zn-Al
to the support Addition of
elements to the
Ni-Zn-Fe-Al metallic phase
Ni-Co-Zn-Al
Ni-Zn-Cr-Al Ni-Cu-Zn-Al
The coprecipitation method at low relative supersaturation has been used to prepare these
catalysts, because it is considered that this method offers the best possibilities of obtaining
homogeneous materials of high specific surface area after calcination, a high dispersion level
among the different metals and singular catalytic properties attributed to the presence of
non-stoichometric inverse spinel-like phases.2,28,47,49 The interpretation of the catalytic results
are based on an analysis of the chemical mechanisms involved on the catalyst surface.44,53,54
Effect of Zn Addition on Ni-based Catalysts.
It has been found8,44 that the incorporation of ZnO as a structural modifier leads to
materials with an improved behaviour with respect to Ni-Al2O3 catalysts, commonly used in
selective hydrogenations.
The catalysts used for this study were prepared by the coprecipitation method and their
nominal compositions are shown in Table 1.
Physico-chemical Characterisation Results
The XRD patterns of the dried precipitates are shown in Figure 1 (left). Two poorly defined
phases were detected in the Ni/Al samples (Ni-Al and Ni-Ni-Al): aluminium hydroxide and
hydrotalcite-like. The degree of crystallinity of these samples is noticeably low, indicating that
the main component is an amorphous phase. This means that only heterogeneous precursors
can be obtained by coprecipitation of Ni+2 and Al+3 cations when K2CO3 is used as a precipitant
reagent and working at a pH close to 7.0. In contrast, only a well-crystallised hydrotalcite-like

phase was observed for the case of zinc-containing hydrated precursors. Furthermore, it is easy
to observe that their degree of crystallinity is higher than that obtained in the Ni/Al samples,
specially in the Ni-Zn-Zn-Al sample. These results indicate that it is possible to obtain
coprecipitates of high homogeneity at a pH equal to 7.0 when zinc is part of the solid structure.
According to these results, zinc addition to the coprecipitated solid seems to promote the
incorporation of Ni into the hydrotalcite-like structure.
Table 1.- Nominal composition for the study of the effect of Zn addition on Ni-based catalysts.
M2+:Ni and Zn; M3+:Al samples
Catalyst Nominal composition M2+/M3+ Ni/Al Zn/Al

Ni-Al NiAl2O4 0.5 0.5 0
Ni-Ni-Al (NiO)NiAl2O4 1.0 1.0 0
Ni-Zn-Al (NiO)ZnAl2O4 1.0 0.5 0.5
Ni-Zn-Zn-Al (NiO)0.5(ZnO)0.5ZnAl2O4 1.0 0.25 0.75
Zn-Al ZnAl2O4 0.5 0 0.5
M+2: Ni and Zn; M+3: Al
The XRD patterns of the corresponding mixed oxides are shown in Figure 1 (right). Two
phases were detected in the binary Ni/Al mixed oxides: a spinel-like phase, probably nickel
aluminate, and nickel oxide. The most intense signal for a nickel aluminate of spinel-like
structure is at 2θ=37.1º, while for nickel oxide it is at 2θ=43.4º. It is found that the I37/I43 ratio
grows as the nickel content decreases. This indicates that, in binary Ni/Al solids, the amount of
NiAl2O4 with respect to NiO becomes more important as the nickel load is reduced. The
addition of Zn leads to a further increase of the I37/I43 ratio. Thus, the peak at 2θ=43.4º almost
disappears in sample Ni-Zn-Zn-Al and its XRD pattern fully resembles that of the binary Zn-Al
sample. The XRD pattern of the binary Zn-Al oxide is in good agreement with that of a zinc
aluminate spinel. These results allow us to conclude that the content of spinel-like phase in the
series of mixed oxides increases in the following order: Ni-Ni-Al<Ni-Al<Ni-Zn-Al
<Ni-Zn-Zn-Al<Zn-Al. Zn addition seems to favour the formation of a non-stoichiometric
spinel structure, in which Ni+2 could be included, by thermal decomposition and sintering of a
solid with a hydrotalcite-like structure even at low temperatures. This evolution from a
hydrotalcite crystalline structure into a non-stoichiometric spinel would probably occur
through a topotactic transformation.55
The specific surface area of the different samples followed just the opposite order (Table 2).
Therefore, binary Zn-Al oxide has the lowest area (i.e., 120 m2/g). This is in agreement with the
fact that this solid has the highest crystallite size and degree of crystallinity. All samples
containing Ni exhibit areas between 200 and 250 m2/g.
According to the TPR profiles, Ni reducibility is almost the same in all mixed oxides used
in this work (see Figure 2). In addition, the reducibility of Ni spinel-like phases is considerably
lower than that found for pure NiO.56 In the case of pure NiO, the maximum H2 consumption is
reached at around 400 ºC. However, for samples prepared in this work the reduction starts
between 400 and 500 ºC, reaching a maximum H2 consumption at around 620 ºC.
Figure 1.- Powder X-ray diffraction diagram for the hydrated precursors (left) and for the calcined oxides
(right). Effect of Zn addition on Ni-based catalysts. Adapted from [44].
Table 2.- BET surface areas for the calcined oxides. Effect of Zn addition on Ni-based
catalysts
Catalyst SBET (m2/g)

Ni-Al 255
Ni-Ni-Al 235
Ni-Zn-Al 210
Ni-Zn-Zn-Al 205
Zn-Al 121
Taking into account that the amount of Ni in the Ni-Zn-Al catalyst is higher (ca. twice) than
that present in the Ni-Zn-Zn-Al catalyst and accepting that the area of the reduction peak is
proportional to the Ni content, it would be expected that the reduction peak of the Ni-Zn-Al
sample would be considerably larger than that of the Ni-Zn-Zn-Al sample. However, the areas
of these peaks are similar. It is possible that the differences between the anticipated areas and
those actually obtained are related to the Ni+2-spinel interaction. Thus, if the Zn content in the
Ni-Zn-Al sample is lower than in the Ni-Zn-Zn-Al sample, it is more likely in the former case
(Ni-Zn-Al) that the Ni+2 species will be located in the sites of the stoichiometric spinel usually
occupied by the Zn+2 species (tetrahedral sites). There would consequently be a higher
proportion of Ni+2 placed there, which could not be reduced at temperatures below 800ºC. The
excess Zn+2 in the Ni-Zn-Zn-Al sample would have a greater tendency than the Ni+2 to occupy
the more stable sites shifting, as a consequence, the Ni+2 towards the octahedral sites. The
reducibility of the Ni-Zn-Zn-Al sample would therefore be higher than that of the Ni-Zn-Al
sample, and this would account for the differences between the anticipated areas and those
experimentally obtained up to 800 ºC.
Figure 2.- Temperature-programmed reduction profiles of the calcined oxides. Effect of Zn addition on
Ni-based catalysts. Adapted from [44].
Both calcined and reduced samples were analysed by XPS. The reduction process was
carried out in situ, in H2 atmosphere at 500 ºC for 2.5 h. The results obtained by XPS are
summarised in Table 3. It can be observed that after reduction only between 40-50 % of nickel
on the surface was metallic, the rest remaining as Ni+2. It is also interesting to note that the
amount of metallic nickel is somewhat lower in the case of Zn-containing samples. No
significant differences in the binding energy of the different cations were observed upon
comparison of binary and ternary oxides. Furthermore, no evidence of Zn or Al reduction was
detected. Finally, the values of atomic ratios indicate that the surface is poorer in Ni and Zn than
the bulk, and the surface becomes poorer in Ni after the reduction treatment, which indicates
some degree of Ni sintering.
Table 3.- XPS results before and after reduction treatment. Effect of Zn addition on Ni-based
catalysts
Elements, Ni-Al Ni-Zn-Al

oxidation B.E. (eV) % Atomic ratio B.E. (eV) % Atomic ratio
states and
atomic ratios Calc. Red. Calc. Red. Calc. Red. Calc. Red. Calc. Red. Calc. Red.
+2
Ni 856.5 856.3 100 45 856.2 856.5 100 60
Ni0 - 852.8 - 55 - 853.0 - 40
Zn+2 - - - - 1022.5 1022.5 100 100
Al+3 74.4 74.4 100 100 74.4 74.4 100 100
Ni/Al 0.07 0.06 0.13 0.10
Zn/Al 0 0 0.13 0.17
Ni/Zn 0 0 1 0.58
Calc: calcined sample; Red: sample reduced at 500 ºC during 2.5 h.
Application to selective hydrogenation of acetylene.
Acetylene hydrogenation was performed in gas phase by using a thermogravimetric system

(CI Electronics Ltd., model MK2, U.K.) equipped with mass flow and temperature controllers.
This experimental system allows continuous recording of the sample weight changes and
temperature during reaction through a PC provided with a CI Electronics Multicard. Catalyst
activation (reduction) was carried out in-situ at 500ºC for 2.5 hours using a H2/N2 (1:1) mixture.
The operating conditions used for the kinetic tests were as follows: T= 175 ºC, H2/C2H2=4/1.
Wcat.=200 mg, QT=700 Ncm3/min and C2H2 concentration=15%.
The weight increase of the catalyst sample was continuously monitored during the reaction.
This increment was mainly due to adsorption of coke precursors and their further
transformation into coke. As shown in Figure 3, the amount of coke deposited on the binary
Ni/Al catalysts (Ni-Al and Ni-Ni-Al) increases dramatically with time. Thus, the amount of
coke deposited on these samples after only 15-20 min reaction was around 20 wt.%. In contrast,
coke deposition was much less important in ternary Ni/Zn/Al catalysts (Ni-Zn-Al and
Ni-Zn-Zn-Al). The quantity of coke formed over these samples was less than 7 wt.% after
almost 3h of reaction. The lowest amount of coke was observed for the ZnAl2O4 sample.
Figure 3.- Change in coke concentration with reaction time during acetylene hydrogenation. Effect of Zn
addition on Ni-based catalysts. Adapted from [44].
These results indicate that coke formation and the initial coking rate diminish as the Ni/Zn
ratio decreases, which means that nickel is also responsible for coke formation. Furthermore,
zinc inclusion into the matrix structure seems to reduce considerably coke deposition.
The catalysts were observed by SEM after reaction.44 From the analysis of the photographs
it can be concluded that at least two types of coke are formed on Ni-based catalysts during
acetylene hydrogenation, namely, whiskers and amorphous-like coke. In the case of binary
Ni/Al catalysts, whiskers are easily formed at the first stages of reaction. At the end of the run,
the large amount of amorphous-like coke deposited on these samples occluded the whiskers
formed in the first reaction stage. However, no whisker generation was observed in ternary
samples at the beginning of reaction, but whiskers were the main coke species detected on this
type of solid at the end of the run. The SEM photographs, obtained at different reaction times,
fully concur with the fact that the total coke deposition and the initial coking rate, determined
with the help of the thermogravimetric system, are lower in the case of ternary Ni/Zn/Al
catalysts.
The catalytic activity of clean Ni-based catalysts depends on the nickel content (Figure 4
left).
Figure 4.- Conversion vs coke concentration (left) and time (right). Effect of Zn addition on Ni-based catalysts.
Adapted from [44].
The binary Ni/Al samples undergo a faster deactivation than the ternary samples (Figure 4
right). In the case of ternary Ni/Zn/Al samples, the conversion level remains almost constant
after three hours of reaction. Furthermore, even when the nickel content is higher in the binary
solids, the intrinsic activity of ternary catalysts is somewhat higher than that corresponding to
binary catalysts. Thus, coke deposition has a stronger negative effect on the activity of the
binary solids, and it can be concluded that the presence of Zn+2 increases the stability of the
catalyst. This higher stability seems to be related to the important Ni-spinel interaction that
exists in the zinc-containing solids. Finally, it must be remarked that the ZnAl2O4 sample did
not show any activity for acetylene hydrogenation after the reduction treatment, but only a
small activity for coking.
Regarding the distribution of the reaction products in the outlet stream, the initial ethylene
yield is almost zero in all cases (Figure 5). Nevertheless, the ethylene yield increases as coke
deposition does. The effect of coke on the ethylene yield is more important by far in the ternary
Ni/Zn/Al catalysts than in binary samples (Figure 5 left). Furthermore, the influence of coke
appears to be more important as the Ni/Zn ratio decreases. Thus, the maximum ethylene yield
and selectivity are found in the Ni-Zn-Zn-Al catalyst. In contrast, with binary Ni/Al solids,
ethylene yields of 3-4% are only attained after a long period of contact (Figure 5 right),
corresponding to coke concentrations much higher than 60 %.
Figure 5.- Ethylene yield vs coke concentration (left) and time (right). Effect of Zn addition on Ni-based
catalysts. Adapted from [44].
In all cases, the initial methane yield was noticeable (Figure 6). Methane yields were much
higher in binary Ni/Al catalysts than in ternary Ni/Zn/Al. Besides, for a given series of catalyst
(i.e., binaries or ternaries), the initial methane yield diminishes as the nickel content in the solid
is lower. This is the opposite behaviour to that observed for the ethylene yield.
In addition, the methane yield decreases with coke deposition (Figure 6 left). In the case of
binary solids, methane is the main product in the gas phase during the first stage of reaction and
even during the last stage of reaction. Nevertheless, in the Ni/Zn/Al samples, the methane yield
dropped rather fast to zero.
Ni/Zn/Al catalysts gave an ethane yield at the first stages of the reaction higher than the
Ni/Al samples (Figure 7). The evolution of the ethane yield over time was different for samples
containing Zn with respect to those based only on Ni and Al. Thus, in the case of ternary
samples, the ethane yield reached a maximum for a coke concentration lower than 2% and then
decreased slowly with coke deposition. This evolution is just the opposite to that observed for
the ethylene yield (Figure 5), since both catalysts are almost inactive towards methane
formation. In the case of Ni/Al solids, the ethane yield increased quite fast to an almost constant
value (Figure 7 right). This evolution is therefore just the opposite to that observed for total and
methane yields (Figures 4 and 6). The evolution of ethane yield over time was almost the same
in both Ni/Al catalysts (Figure 7 right). However, in the case of ternary catalysts, ethane yield
was always lower for Ni-Zn-Zn-Al than for Ni-Zn-Al (Figure 7).
From these results, it can be concluded that the activity and selectivity of Ni-based
catalysts, used in the selective hydrogenation of acetylene, can be improved by incorporating
Zn+2 in the solid structure. The zinc-modified catalysts produce smaller amounts of coke and
methane in comparison with those without zinc. Furthermore, coke deposited on ternary
Ni/Zn/Al catalysts has a strong effect on ethylene production.
Figure 6.- Methane yield vs coke concentration (left) and time (right). Effect of Zn addition on Ni-based
catalysts. Adapted from [44].
Figure 7.- Ethane yield vs coke concentration (left) and time (right). Effect of Zn addition on Ni-based catalysts.
Adapted from [44].
The reason for the different catalytic behaviour could be the different crystalline structure
obtained when zinc is present in the catalyst matrix. Zinc addition favours the formation of
non-stoichiometric spinel-like phases, even at low calcination temperatures. The result is a
solid in which Ni+2 cations are highly interdispersed in the zinc aluminate phase (see XRD and
TPR results, Figures 1 and 2). The activation process by reduction with hydrogen leads to
solids in which the metallic nickel particles are strongly interacting with the zinc aluminate
matrix. Their high dispersion reduces the concentration of neighbour nickel atoms and,
according to the mechanism proposed,44,53,54 also the methane and coke yields.
However, the absence of Zn in the composition of the catalysts leads to the formation of
larger Ni crystallites; therefore, the probability of finding three-atom-arrangements increases,
favouring the formation of methane and hydrogenolytic coke. At the first stages of the reaction,
when the solid surface is “clean”, a large amount of coke and methane is produced on binary
Ni/Al catalysts because of the high number of hydrogenolytic sites present on their surfaces;
thus, the ethane yield for these catalysts is initially lower than for ternary Ni/Zn/Al catalysts.
The continuous decrease in methane formation originates the increase in ethane and ethylene
yields. Ethane yield increases with time because hydrogenolytic sites are left on the catalyst
surface which can be deactivated through coke deposition. Thus a decrease in activity is
observed for the binary catalysts while the ethane yield increases (Figures 4 and 7). When
ethane formation stops, drop in acetylene conversion also stops. The lower number of
hydrogenolytic sites on ternary Ni/Zn/Al catalysts leads to a very fast drop in the methane yield
because the hydrogenolytic sites are deactivated due to coke deposition. The ethane yield thus
continuously decreases over time while the ethylene yield simultaneously increases. Coke
formation continues, but this does not have a deactivating nature because it is formed on
hydrogenating sites.
Influence of the Substitution of Ni by Co or Cu on Ni-Zn-Al Catalysts.
Just as the addition of Zn, as a structural modifier, leads to an improved behaviour of the
catalyst during acetylene hydrogenation, Rodríguez8 has shown that the substitution of an
active metal by a different one, but of similar characteristics (e. g., Cu or Co), also leads to
relevant changes with respect to the amount of coke deposited, the activity level and the
selectivity, and the effect coke provokes on the last two. The experiments were carried out
under the same operating conditions as those used for the study of the effect of Zn addition. The
stoichiometric formula and the specific surface area of the solids obtained after decomposition
and calcination stages are shown in Table 4.
The catalysts containing Cu and Co show a specific surface area lower than the Ni-Zn-Al
catalyst. Considering that the degree of crystallisation is inversely proportional to the specific
area of the sample, the Cu and Co binary catalysts should be solids with a higher degree of
crystallisation.
Table 4.- Nominal composition and BET surface for the catalysts studied by Rodríguez.8
Influence of the substitution of Ni by Co or Cu on Ni-Zn-Al catalysts.
Catalyst Nominal composition SBET (m2/g)

mixed oxides
Ni-Zn-Al (NiO)ZnAl2O4 210
Cu-Zn-Al (CuO)0.25ZnAl2O4 166
Co-Zn-Al (CoO)ZnAl2O4 144
The XRD results (Figure 8) show diffraction peaks corresponding as much to a spinel-like
phase as to metallic oxides such as nickel oxide, which relative concentration depends to a large
extent on the catalyst composition. As these solids are poorly crystallised, it is not possible to
identify through this technique which divalent cation is present in the crystalline lattice, since
there is hardly any difference between the diffraction angles of the spinels corresponding to the
different metallic cations. The tendency of Co and Zn to form a spinel-like structure, in which
cobalt would occupy the octahedral sites, is very high.57 However, it has been previously
demonstrated that Cu does not form the hydrotalcite structure, unless another divalent cation is
present.2 Furthermore, the results obtained by Marchi,57 indicate that the tendency of Cu to
form the spinel-like structure is relatively low, although the presence of Zn favours the process.
Consequently, it is difficult to know if Zn is the cation which forms the spinel phase, or Zn and
Cu together. The model suggested by Marchi57 considers that the Cu-Zn-Al solid is mainly
formed by highly dispersed CuO in a non-stoichiometric zinc aluminate spinel. It is likely that
the presence of Cu favours the inclusion of Zn into the spinel-like crystalline structure.
Figure 8.- Powder X-ray diffraction diagram for the calcined oxides. Influence of the substitution of Ni by Co
or Cu on Ni-Zn-Al catalysts.
The activity results show that the nature of the active metal has a decisive effect as much on
the initial activity level as on its change over time (Figure 9). The Co-Zn-Al catalyst is the least
active for the main reaction, while the Ni-Zn-Al catalyst is the most active one. The activity of
the third binary catalyst (Cu-Zn-Al), in spite of being initially similar to that of the Ni-Zn-Al
sample, falls progressively as the reaction proceeds, so that after three hours the conversion
does not rise above 1%. Obviously, coke deposition on this catalyst has a drastic effect on its
activity, giving rise to its almost complete deactivation.
The selectivity towards the different gaseous reaction products (methane, ethane and
ethylene) has been plotted in Figure 10. It can be seen that the copper catalyst is more selective
to ethylene than the nickel one. The selectivity to methane is highest for the Co-Zn-Al catalyst,
and remains constant over the reaction time. On the other hand, the Cu-Zn-Al catalyst shows
the lowest selectivity to methane. The Ni-Zn-Al catalyst shows an initial selectivity to methane
similar to that observed for the Co-Zn-Al catalyst, but a steady decrease occurs until a value
close to zero is reached.
Figure 9.- Change in acetylene conversion with reaction time. Influence of the substitution of Ni by Co or Cu
on Ni-Zn-Al catalysts.
Figure 10.- Change in selectivity with reaction time. Influence of the substitution of Ni by Co or Cu on
Ni-Zn-Al catalysts.
The differences in activity and selectivity behaviour cannot be attributed to a lower

reducibility of Co with respect to Ni, since the TPR profiles (Figure 11) show that the
reducibility of the Co-Zn-Al catalyst is similar to that of the Ni-Zn-Al catalyst. Instead, Cu+2
has shown to be much more easily reducible than Ni+2 and Co+2 when it is interacting with a
non-stoichiometric zinc aluminate spinel,26 in agreement with the model suggested above for
the Cu-Zn-Al system.57
Figure 11.- Temperature-programmed reduction profiles of the calcined oxides. Influence of the substitution of
Ni by Co or Cu on Ni-Zn-Al catalysts.
As mentioned above, it is well known that hydrogenation reactions are non-sensitive to the
metal structure,58-60 that is, they progress with similar reaction rates independently of the active
metal used to carry them out. Thus, other reactions or secondary stages, such as coke deposition
or the adsorption of reactant molecules, which are reactions sensitive to the metal structure,60-62
determine the activity level of the catalysts.
The evolution of coke content with time for the three catalysts has been plotted in Figure 12.
It can be observed that the Co-Zn-Al and Cu-Zn-Al catalysts show similar initial rates of coke
formation and these are higher than that of the Ni-Zn-Al catalyst. Nevertheless, the change in
coke concentration over time is very different for each sample. While coke formation quickly
deactivates catalyst Co-Zn-Al, for the Cu-Zn-Al catalyst the rate of coke formation remains at
relatively high values all the time. This leads, after three hours of reaction, to the amount of
coke deposited on the Co-Zn-Al catalyst being no higher than that deposited on the Ni-Zn-Al
catalyst, while the amount of coke formed on the Cu-Zn-Al catalyst is much higher.
The fact that the coke formation is initially fast, while on the Co-Zn-Al catalyst at the same
time the methane selectivity is high, indicates that the break up of acetylene molecules is easier
on this metal (cobalt) than on nickel or copper. At the same time, the low activity for ethylene
and ethane formation, and the quick diminution in the rate of coke formation, can imply a
self-poisoning phenomenon of the metallic surface.60
Figure 12.- Coke concentration with reaction time during acetylene hydrogenation. Influence of the
substitution of Ni by Co or Cu on Ni-Zn-Al catalysts.
On the other hand, the low selectivity to methane of the Cu-Zn-Al catalyst, and the
pronounced deactivating effect originated by coke deposition on the activity of this catalyst for
ethane and ethylene formation, indicate that, on this metal, coke has a fundamentally polymeric
nature, and then on copper the break up of the acetylene molecules does not take place, or at
least occurs to a lesser extent than on cobalt.
Summarizing, the activity, selectivity and coking results obtained can be explained taking
into account that most of the metallic sites in the Cu-Zn-Al have a hydrogenating nature, being
able to produce ethylene and small (if any) amounts of methane. The coke formed on these sites
is a hydrogenated coke deriving from the polymerisation/condensation of the acetylene
molecules adsorbed on the catalyst surface. In this case, the large amount of coke deposited
deactivates the catalyst. For the Co-Zn-Al catalyst, most of the metallic sites have a
hydrogenolytic nature, and methane and graphitic coke formation on this type of site occur to a
large extent. These sites undergo a fast self-poisoning process. Finally, the Ni-Zn-Al catalyst is
an intermediate case in which both hydrogenolytic and hydrogenating sites are present. This
explains why on the Ni catalyst the formation of methane takes place but disappears very fast,
and why at the same time there is a certain degree of ethylene formation.
Influence of the Addition of Co or Cu as Catalytic Modifiers and Cr as

Structural Modifier to Ni-Zn-Al Catalysts
According to the results obtained in the two previous sections, it is clear that the addition of
Zn to Ni-based catalysts improves their performance during acetylene hydrogenation. The
substitution of Ni by Co in Ni-Zn-Al catalyst leads to a decrease in ethane selectivity and an
increase in the ethylene selectivity level; however, methane selectivity increases and the
activity of the catalysts is close to zero. The substitution of Ni by Cu leads to a decrease in
methane and ethane selectivity and an increase in ethylene selectivity. However this catalyst
(Cu-Zn-Al) undergoes a fast deactivation.
With the aim of combining the catalytic effects of Ni with those of Cu and Co, two new
catalysts were studied: Ni-Co-Zn-Al and Ni-Cu-Zn-Al. In addition, with the aim of studying
the influence of Cr, a Ni-Cr-Zn-Al catalyst was prepared and tested in acetylene hydrogenation.
The objective is to obtain a synergetic effect between the Ni and the modifier (Co, Cu and Cr)
leading to a catalyst with the positive properties of both. The stoichiometric formula and the
specific surface area of the solids obtained after the decomposition and calcination stages are
shown in Table 5.
Table 5.- Nominal composition and BET surface for the calcined oxides. Influence of the
addition of Co or Cu as catalytic modifiers and Cr as structural modifier to Ni-Zn-Al
catalysts.
Catalyst Nominal composition SBET (m2/g)

mixed oxides
Ni-Zn-Al (NiO)ZnAl2O4 210
Ni-Co-Zn-Al (NiO)0.5(CoO)0. 5ZnAl2O4 205
Ni-Cu-Zn-Al (NiO)0.5(CuO)0. 5ZnAl2O4 239
Ni-Cr-Zn-Al (NiO)ZnAl1.6Cr0.4O4 162
Although the Ni-Cr-Zn-Al cannot be rigorously defined as a bimetallic catalyst, since

chromium has been added as a structural modifier and therefore an important contribution to
the activity of the catalyst is not expected, a certain effect on the secondary reactions (i.e., coke
formation) can be expected, due to the different non-stoichiometry and acidic properties of the
aluminate-like and chromite-like structures. It is interesting to study the behaviour of other
trivalent metals (i.e. Cr+3) which can also form crystalline spinel-like structures. In this section
the results obtained with Ni-Zn-Al are shown again to provide a better perspective of the
differences (improvement or worsening) obtained by adding a second metal to this catalyst.
The Ni-Co-Zn-Al and Ni-Cu-Zn-Al catalysts show a similar value for the specific surface area
to that obtained for the Ni-Zn-Al catalyst, and these are better crystallized than those obtained
for the corresponding ternary catalysts (Co-Zn-Al and Cu-Zn-Al) (Figure 13). The
Ni-Cr-Zn-Al catalyst shows a lower BET surface in agreement with the results reported.2
Figure 13.- Powder X-ray diffraction diagram for the calcined oxides. Influence of the addition of Co or Cu as
catalytic modifiers and Cr as structural modifier to Ni-Zn-Al catalysts.
The activity tests were carried out under the same operating conditions as those described
in the previous two sections. The activity results (Figure 14) show an activity level similar
(13-15%) for all the catalysts and this level remains constant over the reaction time. The highest
activity is obtained for the Ni-Cr-Zn-Al catalyst.
Figure 14.- Change in acetylene conversion with reaction time. Influence of the addition of Co or Cu as
catalytic modifiers and Cr as structural modifier to Ni-Zn-Al catalysts.
Regarding the selectivity towards the different reaction products, the selectivity to methane
versus time has been plotted in Figure 15. It can be observed that for all the samples and
independently of the initial value, a fast diminution is obtained until a residual value close to
zero is reached. However, it is noticeable that the Ni-Cr-Zn-Al catalyst shows an initial
selectivity to methane higher than the other the samples and that for this catalyst the time
required to reach the residual value is longer.
Figure 15.- Change in methane selectivity with reaction time. Influence of the addition of Co or Cu as catalytic
modifiers and Cr as structural modifier to Ni-Zn-Al catalysts.
The partial replacement of Ni by Co or Cu gives rise to a marked increase in ethylene

selectivity (Figure 16). This increase is more obvious for Ni-Co-Zn-Al catalyst. The addition of
Cr to the Ni-Zn-Al catalyst does not modify the selectivity to ethylene.
The reverse sequence is obtained for the selectivity to ethane, since methane selectivity is
very low and the conversion is the combined sum of the ethane and ethylene yields, and since
for these catalysts the conversion is approximately equal, the selectivity to ethane and ethylene
are complementary. Thus, the Ni-Zn-Al catalyst is the most selective to ethane, while the
Ni-Co-Zn-Al catalyst is the least selective.
The coke concentration profiles have been plotted in Figure 17. The maximum amount of
coke after three hours of reaction corresponds to the Ni-Cu-Zn-Al catalyst, in agreement with
the results obtained with the Cu-Zn-Al sample. The Ni-Cr-Zn-Al is the least active catalyst for
coke formation.
Figure 16.- Change in ethylene selectivity with reaction time. Influence of the addition of Co or Cu as catalytic
modifiers and Cr as structural modifier to Ni-Zn-Al catalysts.
Figure 17.- Change in coke concentration with reaction time during acetylene hydrogenation. Influence of the
addition of Co or Cu as catalytic modifiers and Cr as structural modifier to Ni-Zn-Al catalysts.
The temperature-programmed reduction profiles (Figure 18) for these catalysts indicate
that Ni and Cu reduction takes place at different temperatures. However, the reduction of Ni in
the Ni-Cu-Zn-Al catalyst occurs at a lower temperature than in the rest of the solids, so that the
Cu reduction seems to catalyse the Ni reduction. These facts indicate that the results of catalytic
activity obtained in this work can not be due to the formation, at least to any great extent, of an
alloy between both metals (Ni and Cu). However, a clear interaction between both metals does
exist since the Ni reducibility is clearly modified. This is also evident from the band
superposition observed in the corresponding TPR profile. Thus, some small proportion of
Ni-Cu intermetallic compound may be formed. In other words, it is very likely that some kind
of interaction between Ni and Cu exists since the Ni-Zn-Al catalyst behaviour is modified with
the addition of Cu.
Figure 18.- Temperature-programmed reduction profiles of the calcined oxides. Influence of the addition of Co
or Cu as catalytic modifiers to Ni-Zn-Al catalysts.
The complete replacement of Ni by Cu in the Ni-Zn-Al catalyst leads to a high coke

deposition on the Cu-Zn-Al catalyst (see Figure 12) causing a drastic effect on the catalyst
activity, provoking its almost complete deactivation (see Figure 9). However, the partial
replacement of Ni by Cu to a certain extent avoids the catalyst deactivation (Ni-Cu-Zn-Al) and
increases the ethylene selectivity with respect to the Ni-Zn-Al catalyst. Therefore, a clear
synergetic effect of both metals (Ni and Cu) exists, giving as a result a catalytic material with an
improved behaviour.
The results obtained with the Ni-Co-Zn-Al catalysts show an activity and resistance to
deactivation similar to that shown by the Ni-Zn-Al catalyst, and a higher selectivity towards
ethylene without a significant increase in coke formation. The TPR profile for this catalyst
(Figure 18) shows only one peak at ca. 614 ºC. This reduction temperature is similar to that
obtained with the Ni-Zn-Al catalyst and lower than the temperature required to reduce Co+2
towards Co0 in a Co-Zn-Al catalyst (Figure 11). This fact indicates that the nickel reduction
promotes the cobalt reduction. In this case, a simultaneous reduction of both metallic cations is
obtained, thus accounting for the improved catalytic behaviour obtained with this catalyst with
respect to the Ni-Zn-Al sample, which could be due to a certain extent to the formation of a
nickel-cobalt alloy, or perhaps to a high level of dispersion of both metals.
Finally, the results obtained by Rodríguez8 with the Ni-Cr-Zn-Al, show a distribution of the
different reaction products (methane, ethane and ethylene) similar to that obtained with the
Ni-Zn-Al catalyst. However, it shows a higher activity and a lower trend towards coke
formation which makes the structural importance of chromium very clear.
Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe Catalysts
The previous section has shown the results obtained when the composition of a Ni-based
catalyst is modified through the addition of catalytic and/or structural (Co, Zn, Cr) promoters. It
has been seen that the nature of the support is one of the most important aspects which
determines the properties of a catalyst, besides providing an appropriate surface area which
guarantees a good dispersion of the active metal and prevents its sintering.
One of the most relevant results obtained is the possibility of improving the performance of
Ni-based catalysts by adding Zn+2 ions to the catalyst structure. The addition of Zn+2 ions must
be carried out from the very first stage of the catalyst preparation, i.e., during the
coprecipitation step. The decomposition and sintering of the Zn-containing hydrated precursor
obtained in this coprecipitation step, having a hydrotalcite-like crystalline structure, seems to
favour the formation of a non-stoichiometric spinel-like phase. The final catalyst, prepared by
activation of this oxide precursor in an H2 flow, leads to a diminution of coke formation and
turns out to be a more stable catalyst under the conditions of the acetylene hydrogenation
reaction.44 The addition of chromium to Ni-ZnAl2O4 catalysts as a support modifier leads to an
increase in the activity and the selectivity to ethylene and to a decrease in coke and methane
formation. The increase in the catalytic features of these materials shows a maximum for low
chromium contents.46 On the basis of these results, Ni-Zn-Al catalysts modified with small
quantities of chromium have been studied. In each case, the effect of the Ni/Zn ratio is analysed
in order to study the influence of the Zn content on the physico-chemical properties of this type
of solid. However, the M+2/M+3 ratio of the prepared catalysts was in this case equal to 2,
favouring the formation of the hydrotalcite-like structure. On the other hand, since this ratio is
higher than 1 (the limiting value established for superstoichiometric spinels), it is impossible to
avoid the segregation of the Ni and Zn oxides during the decomposition/calcination stage and
to obtain a pure spinel-like structure.
In addition, due to the important role that the support seems to play in this type of solids, a
new series of catalysts has been prepared with the aim of investigating the influence of the
Ni/Zn ratio on Ni-Zn-Al catalysts. These catalysts are the same as the previous ones, but are
now doped with small quantities of Fe, scarcely studied in the literature relating to this type of
catalyst, instead of Cr. These two series of solids allow us to make a comparison between two
different modifiers (Cr and Fe), and to check if the presence of one or the other modifies the
effect that the Ni/Zn ratio has on the catalyst behaviour.
Physico-Chemical Characterisation Results
All the catalysts were prepared by coprecipitation, by mixing an aqueous solution

containing the nitrates of the metal cations (Ni, Zn, Al, Cr, and Fe) in the desired amounts with
a 1 M aqueous solution of Na2CO3 at room temperature. The pH was maintained constant by
adding NaOH 2 M with a Dosimat 725 Methrohm and using a Methrohm pH-meter. The
following molar ratios were used: M+2/M+3=2/1; Al/Cr=Al/Fe=5/1, Ni/Zn=4/0, 3/1, 2/2, 1/3,
and 0/4. It is well known4 that hydrotalcite-type structures can easily be formed2 when a ratio
M+2/M+3=2 is used. A low Cr/(Cr+Al) ratio minimises coke formation in this reaction.45,46 In
order to compare the effect of the Fe addition, the same value of the Fe/Al ratios was selected.
The stoichiometric formulae and the ratio between the different cations of the solids studied in
this section are shown in Table 6.
Table 6.- Classification of the catalysts studied in this section. Study of Ni-Zn-Al-Cr and
Ni-Zn-Al-Fe catalysts.
M2+/M3+ Ni2+/M2+ Al Al
Catalyst Nominal Composition or
Cr Fe
NiZnCr-0 (ZnO)4(Al5/6Cr1/6)2O3 0
NiZnCr-1 (ZnO)3(NiO)(Al5/6Cr1/6)2O3 0.25
NiZnCr-2 (ZnO)2(NiO)2(Al5/6Cr1/6)2O3 2 0.5 5
NiZnCr-3 (ZnO)(NiO)3(Al5/6Cr1/6)2O3 0.75
NiZnCr-4 (NiO)4(Al5/6Cr1/6)2O3 1
NiZnFe-0 (ZnO)4(Al5/6Fe1/6)2O3 0
NiZnFe-1 (ZnO)3(NiO)(Al5/6Fe1/6)2O3 0.25
NiZnFe-2 (ZnO)2(NiO)2(Al5/6Fe1/6)2O3 2 0.5 5
NiZnFe-3 (ZnO)(NiO)3(Al5/6Fe1/6)2O3 0.75
NiZnFe-4 (NiO)4(Al5/6Fe1/6)2O3 1
As indicated in Table 7, the elemental chemical analysis data indicate that molar ratios for
metal cations in hydrotalcite-type precursors are very close to those in the initial nitrate
aqueous solutions, and that the Ni2+/M3+ ratio is maintained very close to the nominal ratio in
all cases. The Al/(Cr or Fe) ratio deviates from the theoretical value, this result being directly
related to the complexity of the aluminium analysis method used. Obviously, this ratio is also
maintained in the calcined oxides, as the treatment does not lead to the volatilisation of metal
compounds. The specific surface areas (calculated following the BET method) are summarised
in Table 8.
Table 7.- Real and nominal atomic ratios for the different metal cations. Study of Ni-Zn-Al-Cr
and Ni-Zn-Al-Fe catalysts.
Catalyst M2+/M3+ Ni2+/M2+ Al/(Cr or Fe)

exp. nom. exp. nom. exp. nom.
NiZnCr-0 1.8 0 0 5.9
NiZnCr-1 2.4 0.24 0.25 3.8
NiZnCr-2 2.1 2 0.51 0.5 4.8 5
NiZnCr-3 2.7 0.76 0.75 4.1
NiZnCr-4 2.4 1.01 1 4.5
NiZnFe-0 2.1 0 0 3.1
NiZnFe-1 1.9 0.23 0.25 2.9
NiZnFe-2 2.2 2 0.5 0.5 4.9 5
NiZnFe-3 2.3 0.72 0.75 5.3
NiZnFe-4 2.4 1.03 1 4.6
Table 8.- Composition and BET surface of the samples. Study of Ni-Zn-Al-Cr and
Ni-Zn-Al-Fe catalysts.
Catalyst Ni+2/ΣM+2 SBET (m2/g) SBET (m2/g)

precursors mixed oxides
NiZnCr-0 0 75 100
NiZnCr-1 0.25 104 98
NiZnCr-2 0.5 107 120
NiZnCr-3 0.75 58 144
NiZnCr-4 1 50 173
NiZnFe-0 0 59 90
NiZnFe-1 0.25 109 91
NiZnFe-2 0.5 158 110
NiZnFe-3 0.75 58 148
NiZnFe-4 1 169 149
The SBET values ranged from 50 to 169 m2/g for the HT samples, but from 90 to 173 m2/g
for the mixed oxides. The differences in these values do not follow a systematic trend, and
could be ascribed to different experimental conditions during the drying process. However, an
overall increase in the specific surface areas of the oxide samples is observed as the nickel
content is increased. This is due to the lower Zn content, since this cation favours the formation
of a well crystallised ZnO phase with a very low specific surface area.
Powder X-ray diffraction profiles for the hydrated precursors are included in Figure 19 for
the Cr- and Fe-doped samples.
Figure 19.- Powder X-ray diffraction diagrams for hydrated precursors. Cr-containing samples (left),
Fe-containing samples (right). Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts.
After precipitation, all the solids showed XRD diagrams corresponding to well crystallised
materials with a hydrotalcite-like structure. The differences between the Cr- and Fe-doped
samples are not significant due to the low content of these two metallic elements in the solids.
However, formation of the hydrotalcite phase is better observed for the Fe-containing samples,
above all for the samples with low nickel contents. This can be due to the different ionic radii of
these two metals, 0.69 and 0.64 Å, for Cr(III) and Fe(III), respectively. The latter is closer to the
ionic radius of Al(III), which is what determines the hydrotalcite structure in our case. An
increase in the Ni/Zn ratio leads to broader and distorted peaks as Zn has a greater tendency
than Ni to form the hydrotalcite structure, in agreement with the results found by Rodríguez,8
with Ni-containing precipitates in which M+2/M+3=1.
The UV-vis spectra (Figure 20) were recorded following the diffuse reflectance technique.
The spectra of the precursors containing Cr show bands at 575 and 410 nm due to octahedrally
coordinated Cr+3 ;63 their positions match quite well those reported in the literature for 4A2g(F)
→ 4T2g(F) and 4A2g(F) → 4T1g(P) spin-allowed, Laporte-forbidden transitions in [Cr(H2O)6]3+
species, in agreement with the similar environment expected around the Cr+3 ions in the
aqueous complex and in the brucite-like layers, [Cr(OH)6]. For those precursors containing Fe,
a broad band is recorded between 250 and 500 nm, associated with charge transfer processes
between oxide ions and Fe+3 (3d5 coordination in a weak field).
For samples NiZnCr-0 and NiZnFe-0, no other band is detected due to the absence of Ni in
these two solids. However, as the nickel content is increased, new bands develop at 375, 635
and 730 nm. Again, their positions are almost coincident with those reported for transitions
3
A2g(F) → 3T1g(P) and 3A2g(F) → 3T1g(F) in [Ni(H2O)6]2+, the band due to transition 3A2g(F)
→ 3T1g(F) being split by spin-orbit coupling.64 The other metal cations existing in the samples
have complete electronic configurations (d10 and d0, respectively, for Zn and Al), and thus do
not give rise to any absorption in this range.
Figure 20.- UV-vis spectra of the hydrotalcite precursors. Cr-containing samples (left), Fe-containing samples
(right). Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts.
Upon calcination in nitrogen at 500 ºC, the layered structure was destroyed, and the broad
maxima recorded (Figure 21) correspond to the presence of MO phases (M=Zn, Ni).
Decomposition of hydrotalcites usually leads to the formation of a mixture of oxides, AO and
AB2O4 (A=M+2, B=M+3). Since the samples studied in this part have a M+2/M+3 ratio equal to 2,
higher than the stoichiometric value (M+2/M+3=0.5) and even higher than the value limit
established for superstoichiometric spinels (M+2/M+3=1), then a pure spinel-like phase cannot
be obtained. In our case, the maxima recorded correspond exclusively to MO phases. The
maxima at 2θ = 42º and 2θ = 62º correspond to NiO, while the maximum at 2θ = 32º
corresponds to ZnO. The maximum at ca. 2θ = 36º corresponds to both phases. Changes in the
relative intensities of these maxima are in agreement with the relative contents of Ni and Zn,
and thus of their monoxides, in the solids.
Figure 21.- Powder X-ray diffraction diagrams for calcined samples. Cr-containing samples (left),
Fe-containing samples (right). Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts. Adapted from [52].
TPR profiles of the calcined samples are included in Figure 22. Among all the reducible
species in the samples, only Ni+2 is actually reduced under the experimental conditions used,65
together with Fe+3, although this gives rise to almost negligible curves because of its low
loading. Reducibility of Ni+2 species is similar in both series of samples. A shift of the main
reduction peak towards higher temperatures is observed when the Ni content is increased.
However, the peak reverts towards lower temperatures for those samples without Zn. This
result suggests that the interaction of the reducible Ni+2 with the support is different, depending
on the presence or absence of ZnO, and this difference will probably also affect the catalytic
performance of the solids. The reduction maximum between 200-380 ºC in the profiles of the
Cr-containing samples has been ascribed to reduction of Cr+6 (formed during calcination) to
Cr+3;66-68 the presence of Cr+6 species has been confirmed in this type of solid by XPS46,53 and
by EXAFS.53 Hydrogen consumption at ca. 350 ºC in the profiles of the Fe-containing samples
could be due to partial reduction of Fe+3 species.69-71
The reduction degree has been calculated from the weight loss during the activation stage
in the thermobalance. These calculations (shown in Table 9) are in good agreement with the
TPR results. The data in Table 9 show an increase in the surface concentration of the reduced Ni
as the Ni/Al ratio increases.
Comparing the Fe- with the Cr-doped samples, it is observed that the Fe presence favours
Ni reduction, mainly for samples with a high Ni content.
Figure 22.- Temperature-programmed reduction profiles of the calcined samples. Cr-containing samples (left),
Table 9.- Ni content and degree of Ni reduction. Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe
catalysts.
Sample Ni total Reduction (%) Ni0 g Ni0/m2 x 104

0
(g Ni/100 g (g Ni /100g cat.)
cat.)
NiCrZn-0 0 - - -
NiCrZn-1 12.3 90 11.1 11
NiCrZn-2 28.2 77 21.7 18
NiCrZn-3 48.0 66 31.7 22
NiCrZn-4 59.6 90 53.6 31
NiFeZn-0 0 - - -
NiFeZn-1 11.1 80 8.9 10
NiFeZn-2 29.8 76 22.6 21
NiFeZn-3 42.7 85 36.3 25
NiFeZn-4 60.3 95 57.3 38
Application to selective hydrogenation of acetylene
The prepared samples have been tested using the selective hydrogenation of acetylene
reaction. The effect of the Ni/Zn ratio on the activity, selectivity and coke formation on
Ni-Zn-Al catalysts modified with Cr or Fe has been studied. The kinetic experiments have been
carried out in a thermobalance at a temperature of 175 ºC and with a H2/C2H2 ratio of 3/1. For
all cases the catalyst mass used was 200 mg, the total flow 700 Ncm3/min and the C2H2
concentration 15%. The samples were reduced at 500 ºC for three hours in situ.
The change in coke formation over the reaction time during acetylene hydrogenation has
been plotted in Figure 23. As the Ni content is increased, the rate of coke formation increases.
In the samples without Zn (NiCrZn-4 and NiFeZn-4) the rate of coke formation is extremely
high, with concentrations larger than 50 % within a few minutes of reaction. The coke soon
falls from the thermobalance sample-basket making it impossible to continue the reaction
further, so that data are not provided for sample NiFeZn-4 in Figure 23 (right). Actually,
samples NiCrZn-4 and NiFeZn-4 are excellent catalysts for coke and methane formation.
A comparison shows that for high Ni contents the amount of coke formed is larger on the
Fe series than on the Cr series samples. However, for large Zn contents, no major differences
can be seen.
After catalytic reaction, the samples were characterised by XRD (Figure 24). Upon
reduction (prior to reaction), metallic Ni particles are formed, together with unreduced NiO
particles. Except for the NiCrZn-4 and NiFeZn-4 samples (without Zn), these metallic Ni
particles are not detected in the PXRD diagrams of the reduced samples (they would be
characterised by a peak at ca. 2θ=45º) because of their extremely small size or because of
oxidation. In the case of samples NiCrZn-4 and NiFeZn-4, the peak caused by metallic Ni is
stronger than that caused by NiO (ca. 2θ = 45º) in the XRD diagrams, indicating the presence of
large metallic crystallites. In addition, a diffraction maximum at ca. 2θ=26º for some Ni-rich
samples (NiCrZn-4, NiCrZn-3 and NiFeZn-4) is due to the presence of coke after reaction.
Finally, samples NiCrZn-0 and NiFeZn-0 show some activity for coke formation, although they
do not contain Ni. Obviously, the coke formed on these samples depends on the specific surface
area and the acidity of the support.44
Figure 23.- Change in coke concentration with reaction time during acetylene hydrogenation. Cr-containing
samples (left), Fe-containing samples (right). Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts. Adapted from
[52].
Data relating to change in activity with reaction time are given in Figure 25. As it can be
seen, only a minor deactivation is observed, despite coke formation on the catalyst surface. As
expected, the Ni-free samples (NiCrZn-0 and NiFeZn-0) are not active during hydrogenation,
while for both series of the other samples the conversion decreases as the Ni content increases.
A high Ni content does not improve the conversion of acetylene, but increases coke formation.
Figure 24.- Powder X-ray diffraction diagrams after catalytic reaction. Cr-containing samples (left),
Fe-containing samples (right). Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts.
Figure 25.- Change in acetylene conversion with reaction time. Cr-containing samples (left), Fe-containing
samples (right). Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts. Adapted from [52].
With respect to selectivities to gaseous products (ethylene, ethane and methane), it is

observed that, contrary to the conversion behaviour, changes in product distribution are
observed over the reaction time. It should be taken into account that selectivity values for
Ni-free samples (NiCrZn-0 and NiFeZn-0) cannot be compared with values for the other
catalysts, as the conversions were rather lower (see Figure 25).
As shown in Figure 26, catalysts NiCrZn-1 and NiFeZn-1 show the largest selectivities to
ethylene despite their high activities; this finding can be clearly seen in Figure 27, where
changes in selectivity to ethylene formation have been plotted vs. conversion.
Figure 26.- Change in selectivity to ethylene with reaction time. Cr-containing samples (left), Fe-containing
For the Cr series (Figure 27 (left)) the selectivity decreases with the Ni content, while for
the Fe series (Figure 27 (right)) a different behaviour is observed, although sample NiFeZn-1
(with the lowest Ni content) shows the highest selectivity. Changes in selectivity with reaction
time are quite significant (Figure 26) in Ni-containing catalysts. Such changes increase with the
reaction time reaching, for samples NiCrZn-1 and NiFeZn-1, values even greater than those for
Ni-free catalysts (NiCrZn-0 and NiFeZn-0).
As already mentioned, this increase in selectivity is ascribed to the beneficial role of coke
in this reaction.44,53 This conclusion is confirmed by data in Figure 28: a linear relationship
exists between the change in selectivity to ethylene formation and coke concentration. With
respect to the role of the added trivalent cation (Cr or Fe), it can be observed that for a given
coke concentration, Cr-containing catalysts (Figure 28 (left)) are always more selective than
those containing Fe (Figure 28 (right)), probably because of the different surface acidity arising
from these two cations. It can therefore be concluded that Cr has a larger beneficial role than Fe,
since similar activity and selectivity levels can be reached with a lower coke content.
Figure 27.- Change in selectivity to ethylene with conversion of acetylene. Cr-containing samples (left),
Figure 28.- Change in selectivity to ethylene with coke concentration. Cr-containing samples (left),
The change in selectivity to methane formation with the reaction time is given in Figures
29 and 30. Ni-containing catalysts show a large initial selectivity towards methane formation,
but this decreases sharply with the reaction time.
Figure 29.- Change in methane selectivity with reaction time. Cr-containing samples (left), Fe-containing
Figure 30.- Enlargement of Figure 29. Cr-containing samples (left), Fe-containing samples (right). Study of
Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts. Adapted from [52].
This selectivity to methane increases with the Ni content (Figure 30), more evidently in
samples containing Fe than in those containing Cr. Conversely, those catalysts without Ni
(NiCrZn-0 and NiFeZn-0) are weakly selective to methane. These selectivities slightly increase
with the reaction time, thus suggesting that methane formation follows different mechanisms in
the presence and in the absence of Ni.
Formation of methane and of coke in those catalysts containing Ni should be related to the
presence of hydrogenolysis-active sites, formed during the reduction of Ni+2 weakly interacting
with the support. These sites undergo a self-deactivation, leading to a decrease in coke and
methane formation.44,47,58 The relative concentration of these sites depends on the Ni/Zn ratio.
Thus, a maximum in methane and coke formation is observed for Zn-free samples (NiCrZn-4
and NiFeZn-4), as the absence of ZnO leads to the formation of “large” Ni crystallites, which
favour hydrogenolysis processes.44 Roughly speaking, the amount of reduced Ni increases as
the Ni/Zn ratio increases (see Table 9) in agreement with the XRD (Figure 24) and TPR (Figure
22) results. This fact leads to the development of larger Ni particles, thus favouring coke and
methane formation. The differences found for the Ni-free samples with respect to methane and
coke formation probably arise from the different acidities of the supports.
In the case of NiCrZn catalysts, for a given Ni/Zn ratio, the change in ethane selectivity
with the reaction time (Figure 31) initially grows, passes through a maximum and finally
diminishes. Both the value and the maximum position of the ethane selectivity increase with
the Ni/Zn ratio. It can be seen in figure 31 (left) that ethane selectivity reaches a maximum at
the beginning of the reaction for catalysts NiCrZn-2 and NiCrZn-3. This maximum is due to the
high level of methane formation at the first stages of the reaction. Ethane selectivity starts when
methane formation diminishes. When methane selectivity is almost negligible, ethane
selectivity also drops and then the catalyst activity is invested in the production of ethylene
(Figure 26). This result indicates that methane and ethane are formed on the same type of sites
(hydrogenolytic sites), while ethylene is formed on hydrogenating sites.
For Fe-containing samples (Figure 31 (right)), the selectivity diminishes with the reaction
time for all the samples except for catalyst NiFeZn-3. However, these samples are more
selective to ethane than the Cr-containing samples. These differences probably arise, as it has
already been mentioned, from the different acidities of the supports (modified with Cr or Fe).
Jebarathinam et al.,72 have reported a study on Zn(FexCr2-x)O4 catalysts with x ranging between
0 and 2, and they have found that the substitution of Cr+3 by Fe+3 leads to an increase in acidity,
which would explain that Fe-containing samples have a higher tendency to coke formation than
Cr-containing samples.
Sample NiFeZn-3 is the only one for which the selectivity to ethane increases rather than
decreases during the whole reaction time. It can be observed in Figures 29 and 30 that this
catalyst is the most active for methane production and its selectivity to methane can not be
underestimated at any time. Ethane selectivity is initially lower than for the rest of the series.
The continuous diminution in methane formation originates the increase in ethylene and ethane
selectivity (Figures 26 and 31).
All these results indicate that in both series of catalysts an optimum value of the Ni/Zn ratio
will lead to the best values for activity, selectivity and coke formation. The conversion values
and yield to ethylene have been plotted in Figure 32 (parts a and b, respectively) vs. the Ni/M+2
ratio.
Figure 31.- Change in ethane selectivity with reaction time. Cr-containing samples (left), Fe-containing
samples (right). Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts.
Figure 32.- a) Conversion of acetylene and b) yield to ethylene with the Ni/M+2 ratio at final reaction time.
Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe catalysts.
The maximum observed in both plots correspond to the optimum quantity of Ni in the
composition of the support (NiCrZn-1, NiFeZn-1 samples), which confirms the beneficial role
of added ZnO in modulating the catalytic properties of Ni. If the Ni concentration is increased,
conversion, selectivity and yield to ethylene decrease, while coke formation increases. This
increase in coke formation is even larger in Fe-containing catalysts than in those containing Cr.
The maximum obtained in these plots corresponds to the optimum quantity of

hydrogenolysis-active sites and, therefore, a maximum in the concentration of
hydrogenation-active sites (samples NiCrZn-1 and NiFeZn-1). As the Ni content increases, the
proportion of hydrogenolysis-active sites also increases, lowering the relative fraction of the
other metallic sites.
For given calcination and reduction conditions, the relative amounts of these two sorts of
surface sites depend on the Ni/Zn ratio. Consequently, the apparent structure sensitivity of the
overall acetylene hydrogenation reaction permits the introduction of changes in selectivity by
modifying the chemical composition of the catalyst. The presence of Zn drastically decreases
coke formation on the catalyst surface. Catalysts modified with Fe are more prone to coke
formation than those containing Cr.
Conclusions
The activity and selectivity of nickel-based catalysts on gas phase acetylene hydrogenation
is influenced by several factors which include: 1) coke deposition, 2) nature of the metal, 3)
metal-support interaction, and 4) catalyst composition. The hydrogenation of acetylene can be
considered an “apparently structure-sensitive” reaction. Coke makes the catalyst surface dirty
thereby diminishing methane and ethane formation (sensitive to the structure) and increasing
ethylene formation (insensitive to the structure). The proposed mechanism thus assumes the
existence of two types of metallic site on the catalyst surface (hydrogenolytic and
hydrogenating) related to different surface structures (crystallographic planes). The relative
proportion of each depends on the catalyst composition, the metal-support interaction and the
activation conditions. The nature of the coke deposited on each type of centre is different. As a
consequence of the different characteristics of each type of sites, the adsorption of the acetylene
molecule on each is also different, leading to the formation of the different reaction products
and of the two types of coke on each site. The effect of these two types of coke (associated with
the hydrogenolytic sites and associated with the hydrogenating sites) on the activity and
selectivity is different, and is closely related to the chemical reactions involved in their
formation. Coke deposited on the catalysts studied here has, in general, a positive effect, since it
hardly affects the activity, but leads to an increase in the selectivity to ethylene, the desired
product.
The characterisation and catalytic results indicate a clear influence of the nature of the
active metal on the coking process, the type of coke formed and the main reaction. A
comparison of the Ni-Zn-Al, Cu-Zn-Al and Co-Zn-Al catalysts shows that Ni, Cu and Co are
very different metals in respect to their hydrogenating and hydrogenolytic nature. Most of the
metallic sites in the Cu-Zn-Al catalyst have a hydrogenating nature, being able to produce
ethylene and very little (if any) methane. Coke formed on these sites is a hydrogenated coke.
However, the large amount of coke deposited deactivates the catalyst. For the Co-Zn-Al
catalyst, most of the metallic sites have a hydrogenolytic nature. Methane and graphitic coke
formation on this type of sites occurs to a large degree. These sites undergo a self-poisoning
process which leads to the deactivation of this catalyst and thus a diminution in the rate of coke
formation. Finally, the Ni-Zn-Al is an intermediate case in which both hydrogenolytic and
hydrogenating sites are present. This explains why on the Ni-Zn-Al catalyst the formation of
methane takes place, but disappears very fast, while at the same time the formation of ethylene
occurs to a certain extent. However, it is worth noting that the partial substitution of Ni by Co or
Cu in the Ni-Zn-Al catalyst leads to materials with an improved behaviour with respect to that
obtained with the ternary catalysts. This could be due to the formation, in varying degrees, of an
alloy between Ni and Co and between Ni and Cu. The proportion of the total metal which is
alloyed is higher in the former case. Formation of these types of intermetallic compound is
highly favoured by the close interaction existing between the metals constituting the solids
obtained from the LDH precursors.
The activity results indicate that the presence of Zn as a structural modifier of the
NiO-Al2O3 catalyst diminishes the selectivity to undesired reactions, such as coke and methane
formation, and leads to a more active and stable catalyst during acetylene hydrogenation. The
positive influence of Zn is favoured by the strong interaction existing between metal nickel
particles and the support matrix. This interaction is reached at the early stages of the catalyst
preparation, that is, from the LDH precursor, and is more or less maintained during the
decomposition, sintering and activation stages. Hydrated precursors with a hydrotalcite-like
structure (LDH) could be obtained when M+2/M+3=1 and when M+2/M+3=2. However, in the
first case, the main interaction in the active catalysts seems to be between the metal phase and a
non-stoichiometric zinc aluminate, while in the second case the interaction is between the metal
phase and ZnO. In any case, a significant improvement in the selectivity to ethylene was
obtained compared to Zn-free catalysts. These results indicate the importance of starting from
a solid in which Ni+2 and Zn+2 cations are in close interaction, as occurs in the case of solids
with a LDH structure. In this study, the catalytic results indicated the existence of an optimum
of the Ni/Zn ratio corresponding to 1/3. For this ratio, the highest activity and ethylene
selectivity levels are obtained, while maintaining a low rate of coke formation. The existence of
this optimum is a consequence of a minimum concentration of sites active for hydrogenolysis
(responsible for methane formation), most of the centres being active for hydrogenation
(responsible for ethylene formation). Thus, when the Ni/Zn ratio increases the metal-support
interaction tends to diminish, leading to the formation of larger nickel particles and therefore to
the formation of hydrogenolytic sites.
It can be concluded that the production, at the early preparation stage, of a hydrated
precursor with a LDH structure is a necessary condition for obtaining a mixed oxide with a high
degree of homogeneity. Thus, for the case of ΣM+2/ΣM+3=1, the decomposition and sintering of
a LDH precursor leads to a mixed oxide with a superstoichiometric spinel structure. No
segregation of any other oxide phase was detected in this case. Therefore, it can be said that the
high dispersion of metal cations existing in the LDH initial solid seems to be more or less well
preserved in the mixed oxide. However, in the case of a ΣM+2/ΣM+3=2 ratio, more than one
oxide phase was detected after decomposition and calcination. Here, the main crystalline
phases were NiO and ZnO. This means that LDH formation is a necessary but not sufficient
condition for obtaining a homogeneous mixed oxide. In any event, in both cases, ΣM+2/ΣM+3=1
and ΣM+2/ΣM+3=2, starting from a hydrotalcite phase seems to favour the formation of oxides
where NiO is highly dispersed on the support. This high interaction seems to play a decisive
role in the diminution of hydrogenolytic sites, favouring the generation of sites active for
hydrogenation.
HYDROGENATION OF UNSATURATED HETEROCOMPOUNDS

Hydrogenation of Acetonitriles and Nitro-Compounds
Hydrogenation of nitriles is a reaction of industrial interest for the production of amines,

which in turn are converted into polymer and agrochemical intermediates.35 An example is the
hydrogenation of adiponitrile to 1,6-hexanediamine to manufacture nylon-6,6: in a first stage,
adiponitrile is hydrogenated into 6-amino-hexanenitrile, and subsequently to
1,6-hexanediamine.73 Briefly, the hydrogenation of nitriles to the corresponding primary amine
can be written as follows:
R-CN + 2H2 → R-CH2NH2
The industrial production of these primary amines is usually accomplished in liquid phase
at elevated hydrogen pressures and temperatures, with heterogeneous transition metal catalysts.
The selectivity towards one type of amine is strongly determined by the catalyst. For instance,
Raney Co, Raney Ni and Ru are selective for primary amines, while Cu and Rh catalysts are
preferentially used in the preparation of secondary amines. Pt and Pd catalysts are highly
selective for the production of tertiary amines.35
Due to the high reactivity of imines, which are partially hydrogenated intermediates in the
hydrogenation of nitriles to amines, a conventional hydrogenation process gives a mixture of
primary, secondary and tertiary amines. Modification of the intrinsic acidity of catalysts by
alkaline additives leads to an important diminution of coupling reactions as, for instance, that
between a primary imine and a primary amine to give a secondary amine.74,75 These results are
consistent with the fact that primary, secondary and tertiary amines are basic species that can
strongly interact with the acid sites of a heterogeneous catalyst. On this basis, a mechanism
such as the one shown in Figure 33 was suggested by Verhaak et al.,74 for acetonitrile
hydrogenation. The mechanism considered two types of sites: one metallic and the other acidic.
The metallic site is where hydrogenation reactions occur and is involved in production of
amines. Imine and amine compounds interact on the acidic sites to give secondary and tertiary
imines, which in turn are hydrogenated on metallic sites to give the corresponding secondary
and tertiary amines. According to this mechanism, it can be expected that on changing the
character of the catalyst support from acidic to basic a diminution in the production of
secondary and tertiary amines will occur.
Figure 33.- Bifunctional mechanism proposed for the hydrogenation of acetonitrile.74

Consequently, acidic supports must be avoided if the desired products are primary amines.
Bond and Stone76 suggested that imines are less likely to remain adsorbed on a basic oxide
support and thus the amount of by-products will be reduced. With this in mind, they proposed
that magnesium oxide would be a logical choice for the support since this is a basic oxide and
can be readily prepared with a high surface area. They prepared Fe/MgO catalysts following
two basic preparation methods, impregnation (catalysts identified as IP) and coprecipitation. In
the latter case, the coprecipitation was carried out in three different ways: i) by adding a
(NH4)2CO3 solution to a mixture of Fe(NO3)3 and Mg(NO3)2 (identified as CCP); ii) adding a
mixture of Fe(NO3)3 and Mg(NO3)2 to a solution of (NH4)OH while maintaining the pH at 11
(identified as OH); iii) adding simultaneously a mixture of Fe(NO3)3 and Mg(NO3)2 to a
solution of (NH4)2CO3 while keeping the pH at 9.8 by the addition of (NH4)OH (identified as
HT). The XRD patterns show that two crystalline phases were formed in the case of the OH
precursors, one having a pyroaurite-like structure and the other with a brucite-like structure,
Mg(OH)2. This latter structure is, as we have seen above, closely related to the hydrotalcite
structure. In the case of CCP and HT, the only crystalline structure identifiable in the dried
precipitate was that of a magnesium hydroxycarbonate. After calcination, MgO and γ-Fe2O3
were detected for the OH and HT series, while α-Fe2O3 was observed in the CCP and IP series.
A magnesium aluminate spinel-like phase was also detectable in some cases. Furthermore, by
CO chemisorption and reactive N2O adsorption, Bond and Stone76 found that the Fe metal
surface area was the highest in the case of the OH series. In the hydrogenation of propanenitrile
in the liquid phase, at 200°C and pressures of ca. 30 bar, the selectivity to primary amine was
higher than 60% for all catalysts prepared by coprecipitation. The selectivity with the IP series
was, however, always lower than this value. The most active catalyst was an OH one having
10% of Fe. A similar trend was observed in acetonitrile hydrogenation in the gas phase at
235°C: the most active and selective catalysts were those prepared by coprecipitation, and
again the catalysts belonging to the OH series have the highest activity. The results obtained by
Bond and Stone76 show that: 1) it is possible to obtain high activity and selectivity in the
hydrogenation of nitriles to the corresponding primary amines; 2) the highest selectivity and
activity are reached for catalysts prepared by coprecipitation, particularly for catalysts obtained
from hydrated precursors having a brucite-like structure; 3) the latter type of catalyst has the
largest Fe metal surface area and metal dispersion on the basic oxide support. The authors
related these last physicochemical properties to the high activity found for the OH catalyst
series.
In some cases, high metal surface areas and metal dispersions have been reached when
non-stoichiometric magnesium aluminate, spinel-like, phases are used as supports. In a recent
review, Tichit and Fajula,32 show that, in hydrogenation of acetonitrile in the gas phase, the
selectivity to monoethylamine (MEA) reaches a maximum for a Ni(50)/Mg(15)/Al(35) ternary
catalyst. These authors suggest that such an optimum in Mg content is the result of a balance
between the reducibility of the metal and the acidic character of the support, both decreasing
with the incorporation of Mg. The lower reducibility is in agreement with a higher interaction
between the NiO particles and the magnesium aluminate spinel-like matrix. Tichit and Fajula32
suggest that the balance between the two functions, reducibility and acidity, can be altered by
three factors: 1) composition of ternary Ni/Mg/Al catalysts; 2) activation conditions; 3) the use
of bimetallic formulations of reducible cations, as for instance Ni-Co and Ni-Cu.
In order to consider the influence of the composition of Ni/Mg/Al catalysts on nitrile
hydrogenation, Medina et al.,77 Tichit et al.78 and Dung et al.,79 used Ni/Mg/Al catalysts of
different concentrations, prepared from hydrated precursors with a hydrotalcite-like crystalline

structure (LDH). As Bond and Stone previously did,76 they claimed that it is important to use a
basic oxide support in order to eliminate the undesirable coupling reactions. Hammet acidity
function H0 values of about 17 were obtained for some Mg/Al mixed oxides obtained by
calcination of hydrotalcites.80 This means that it is possible to obtain final catalysts with a
highly dispersed metal phase in a Mg/Al oxide matrix having strong basic properties.
Taking into account that the basicity of Ni/Mg/Al oxides depends on both composition and
calcination conditions,77 Medina et al.81 prepared by coprecipitation three samples of varying
composition and calcined each one of them at three different temperatures ranging from 350 to
700°C. The catalyst precursors were prepared by coprecipitation at room temperature and
pH=8.0 ±0.2, by adding simultaneously a solution containing the corresponding nitrates and
solutions of NH4OH and (NH4)2CO3 in different proportions. The calcination was carried out in
air flow at three different temperatures: 350, 500 and 700°C. The activation was performed in a
H2(10%)/N2 stream at 450 and 650°C. After precipitation all the samples showed the
characteristic XRD patterns of hydrotalcite-like phases. The main phase detected after
calcination had a NiO structure. At temperatures close to 500°C and above, a second phase with
a non-stoichiometric magnesium aluminate spinel-like phase was also observed. The TPR
results showed that Ni+2 reduction proceeds with greater difficulty when the amount of Mg
or/and Al increases and the calcination temperature is raised. These results are in agreement
with those found by Rodríguez et al.47 for the case of Ni/Zn/Al mixed oxides having a
non-stoichiometric zinc aluminate spinel-like structure. The decrease of Ni+2 reducibility has
been attributed to a strong interaction between the Ni metal phase and the non-stoichiometric
spinel-like phase. This interaction increases with the (Zn+Al)/Ni ratio and calcination
temperature. Furthermore, Medina et al.77 determined by TEM that the samples containing Mg
show a better dispersion of NiO and metal Ni than those free of Mg. The Ni/Mg/Al samples
were tested in the hydrogenation of acetonitrile in the gas phase, at atmospheric pressure, by
using a microflow reactor. For low Mg contents, Medina et al.77 observed that when replacing
part of the Ni by Mg there is an increase of both reactivity and selectivity to MEA. However, if
the amount of Mg is too high, the reducibility of the sample dramatically decreases and,
consequently, both reactivity and selectivity are also lowered. On the other hand, the sample
without Mg showed a very high activity, especially in relation to a high conversion to
secondary and tertiary amines due to the important acidity of this sample. Thus, Medina et al.77
claimed that there is an optimum load of Mg that favours both activity and selectivity to
primary amine. An explanation for this may be the lower acidic behaviour of the samples with
low Mg content compared to those without Mg. It is worth noting that these catalysts, having
such a peculiar basic behaviour, were obtained by decomposition of ternary Ni/Mg/Al hydrated
precursors with a hydrotalcite-like crystalline structure. This is particularly different from the
work of Bond and Stone,76 from the point of view that they did not incorporate Al in their
samples, perhaps to be sure of obtaining an oxide support with strong basic properties.
However, the work of Medina et al.77 shows that it is possible to obtain catalyst with these
strong basic properties even when Al is incorporated into the formulation.
In another work, Medina et al.30 prepared a series of Ni/Mg/Al precursors with a
hydrotalcite-like phase having different amounts of each cation. The preparation method was
the same as that used in the previous work,77 the only difference being that the precipitation
temperature was 80°C. Heats of adsorption of hydrogen, carbon monoxide, acetonitrile and
monoethylamine were determined by microcalorimetry. TPD (temperature-programmed
desorption) profiles of the adsorbates were then performed. The catalytic tests were carried out
in the gas phase using a microflow reactor at atmospheric pressure, feeding acetonitrile diluted
with hydrogen. The authors found that there are no great differences in the adsorption heats of
H2, CO and acetonitrile. However, they claim that some trends are apparent. The adsorption
heats of H2 and CO are somewhat higher in the Mg containing samples than in the Mg-free
samples. The opposite is true for the case of acetonitrile and MEA. For ternary Ni/Mg/Al
samples, the hydrogen TPDs show that at least two bound states of hydrogen exist which
desorb at around 260 and 330°C. For hydrogen adsorbed on Ni/Al2O3, two bound states were
also detected, but with maxima at 330 and 430°C. Thus, the behaviour of hydrogen desorption
is similar in both cases, but with an important shift to lower desorption temperatures for
Mg-containing samples. Adsorbed acetonitrile TPD experiments show that peaks at low
temperatures, between 70 and 170°C, disappear and other peaks move to higher temperatures
as the Mg content increases. The TPD of MEA on the Mg-free sample shows peaks at low
temperatures, between 120 and 220°C, and two other peaks at higher temperatures with
maxima at 280 and 510°C. The only Mg-containing sample studied by TPD of MEA gives only
one peak at ca. 160°C. In the catalytic tests, MEA was the main organic compound with
selectivity normally higher than 70%. Diethylamine (DEA), N-ethylethylimine (EEI) and
triethylamine (TEA) were the usual by-products. Trace amounts of ethane, methane and
oligomeric products were sometimes detected at high reaction temperatures. In general, the
authors found that: 1) EEI is the main by-product at low temperature and conversion, while at
high temperature and conversion the main by-products are DEA and TEA; 2) the samples
containing only Ni as divalent cations exhibit similar selectivity to MEA even though the
activity is different; 3) the activity and the selectivity to MEA increase with the Mg content
until a maximum is reached; 4) the selectivity to DEA and TEA diminish with the Mg content.
These results were associated with a lower acidic nature of the support or a Ni d-band
modification. Measurements of acetonitrile and MEA adsorption supported the former
explanation. The electron enrichment of the Ni d-band, after Mg addition, would account for
the 20 kJ/mol increase in the heat of CO adsorption compared to the Mg free sample.
Tichit et al.78 reached similar conclusions when studying the hydrogenation of acetonitrile
and valeronitrile (pentylnitrile) with Ni/Mg/Al catalysts. These catalysts were prepared by the
same method as described in the work of Medina et al.77 Tichit et al.78 found that the
Mg-containing catalysts were more active and selective to the primary amine than the Mg-free
samples, both in the gas-phase hydrogenation of acetonitrile and the liquid-phase
hydrogenation of valeronitrile. However, the main difference with the work of Medina et al.77
was that during the liquid-phase hydrogenation of valeronitrile, the selectivity to penthylamine
(MPA) did not reach a maximum value as did occur with MEA selectivity in the gas-phase
acetonitrile hydrogenation. Selectivities to MPA as high as 95% were found for the Ni/Mg/Al
sample with the highest Mg content. Measurements of differential adsorption heats of MEA
and NH3 TPDs showed that Mg containing samples are less acidic than those without Mg.
These results indicate a decrease in the number and strength of the acid sites necessary to
favour coupling reactions. In any case, Tichit et al.78 claimed that the influence of Mg is not
limited to the inhibition of acid sites on the support, but that it also has an important influence
on the metal Ni particles. This can operate in two ways: 1) a modification of the electronic Ni
d-band; 2) the possible appearance of patches of MgOx species on the surface of the Ni
particles which will interact with the C≡N bond.82 The first explanation is very likely, due to the
following two facts: 1) a very high dispersion of metal Ni and NiO was found to exist in the
non-stoichiometric magnesium aluminate spinel-like matrix, as determined by TEM;77 2) the

support has a strong basic character, so that a negative charge transfer from the support to the
metal Ni particles is very likely to take place. Thus, an electron “enrichment” of the Ni d-band
is expected to be favoured by these two phenomena. If we accept that the production of
secondary and tertiary amines can also take place on the metal Ni surface,82 then it is likely that
the proposed electron “enrichment” of the Ni d-band leads to a decrease of the electron
donation from the unsaturated –CH=NH system and, possibly, the nucleophilic attack at the C
atom by the amine does not take place. Thus, Tichit et al.78 suggested that the basicity of the
support will play a part, decreasing the formation of secondary and tertiary amines on both
metal Ni and support surfaces.
Dung et al.79 studied the influence of activation conditions on nitrile hydrogenation. This is
another parameter that can influence the activity and selectivity to MEA of Ni/Mg/Al catalysts.
The preparation of the catalysts was the same as that used in previous works.78 The test reaction
was the hydrogenation of acetonitrile in gas phase. The results obtained in this reaction were
complemented with FTIR studies of CO and CD3CN adsorption on Ni/Mg/Al catalysts. Two
types of catalyst were studied in this work: 1) a Ni/Mg/Al catalyst with an approximate
composition of Mg0.42Ni1.43AlOx; 2) a Ni/ γ-Al2O3 catalyst prepared by dry impregnation. The
catalysts were calcined at temperatures ranging from 120-500°C and reduced between 400 and
550°C. Dung et al.79 claim that the highest selectivity to MEA with the Ni/Mg/Al catalyst was
reached after calcination at 350°C and reduction at 500°C. At this point, it has to be considered
that transamination reactions, which negatively affect selectivity to MEA, can take place on
both the metal and the acid sites. Thermal treatments can influence both the acid-base character
of the support surface and the electron density at the Ni sites. In the work of Dung et al.,79 IR
spectroscopy of adsorbed CD3CN provided evidence that the ratio between weak Brönsted acid
sites and basic sites was the lowest after calcination at 350°C and reduction at 450°C. Thus, the
adsorption of CD3CN showed that the acidity of this type of catalyst was the lowest for the
above activation conditions. On the other hand, IR spectroscopy of CO provided evidence that
the Ni d-band suffered some modifications by interaction with the Mg(Al)O matrix: the
stretching frequency of CO adsorbed on Ni, at low coverage, took on different values when the
activation conditions were changed. This reflects some modifications of the Ni d-band with the
activation conditions. However, no correlation was found between these changes in the Ni
d-band and the catalytic activity of Ni/Mg/Al. On the contrary, as it has been said above, the
increase in selectivity to MEA showed a good correlation with the decrease of acidity of the
sample. Again, the decrease of the support acidity has been held responsible for lowering the
acid-catalysed transamination reaction, which produces the undesirable secondary and tertiary
amines. Thus, it was concluded that with Ni/Mg/Al catalysts the selectivity to MEA in the gas
phase hydrogenation of acetonitrile is mainly determined by the acidity of the support and not
by the electron density at Ni sites. In addition, it was found that catalyst activity diminished as
the calcination temperature was raised: this behaviour can be ascribed to the decrease of Ni
reducibility due to an increase of interaction between nickel and the Mg(Al)O matrix.22,44
Coq et al.33 carried out an interesting study of acetonitrile hydrogenation in the gas phase
using Ni/Co/Mg/Al catalysts. The hydrated precursors were prepared by coprecipitation, at
20°C and pH=9 ±0.2, of an aqueous solution of the corresponding nitrates with a 1M NaOH
solution. It was determined by XRD that all the solids exhibited the layered structure of LDHs.
The reducibility of Ni and Co species was determined by TPR and the accessibility to metallic
Ni and Co phases by H2 chemisorption using a static apparatus. The acid-base properties of the
support and metal function were characterised by adsorption of CD3CN and CO, followed by
FTIR spectroscopy. In general, two regions of hydrogen consumption were detected in the TPR
experiments: a low temperature region which was ascribed to reduction of Co3O4 and
NixCo3-xO4 species, and a high temperature zone attributed to reduction of NiMg(Al)O mixed
oxides as well as CoxMg1-xAl2O4 and NixMg1-xAl2O4 spinel-like phases. At quasi-constant Mg
loadings but varying the Ni/(Co+Ni) ratio, it was observed that the high temperature reduction
peak was narrower as the Co content increased. Also, this peak shifted to lower temperatures as
the Ni content was increased. It is worth noting that this high temperature reduction band
appears in the Ni-Co containing samples as a single peak, unlike the convolution of the
reduction profiles of the Co/Mg/Al and Ni/Mg/Al samples. The Co/Mg/Al sample was
quasi-inactive during the hydrogenation of acetonitrile. For quaternary Ni/Co/Mg/Al samples,
on the other hand, the TOF (Turn Over Frequency), defined as the number of CH3CN
molecules converted per unit of time and per (Ni+Co) surface atom, goes through a maximum
for Ni/(Ni+Co)=0.5. This seems to indicate that there is a synergistic effect between Ni and Co.
Furthermore, the selectivity to the by-products, EEI, DEA and TEA, varies from 4.5% to 6.4%
with the Ni content, reaching a minimum value of 2% for the same ratio Ni/(Ni+Co)=0.5. The
synergistic effect between Ni and Co, which decreases the formation of by-products, can be
accounted for by a modification of the Ni-Co metallic phase and/or the acid-base properties of
the Mg(Al)O support. Dung et al.79 found a good correlation between the selectivity to
EEI+DEA+TEA and the intensity ratio of the bands at 2295 and 2170 cm-1, I2295/I2170, observed
after CD3CN adsorption on Ni/Mg(Al)O catalysts. The band at 2295 cm-1 was associated with
CD3CN interacting with acid sites and the band at 2170 cm-1 with CD3CN interacting with
basic sites. For the case of quaternary Ni/Co/Mg/Al catalysts, Coq et al.33 did not find such a
good correlation between the I2295/I2170 ratio and selectivity to EEI+DEA+TEA, which means
that there is no clear relationship between acidity-basicity and selectivity to by-products.
Moreover, it seems that selectivity to by-products depends on the composition of the bimetallic
NiCo phase. Upon adsorption of CO on NiCo/Mg(Al)O catalysts, three bands were detected
during FTIR measurements: one at 2035 cm-1, assigned to CO linearly chemisorbed on Ni,
another at 1935 cm-1, assigned to bridged CO on Ni, and a third at 1900 cm-1, assigned to
NixCO species. A small contribution at ca. 1980 cm-1 was detected in some cases, which can be
attributed to CO interacting with Co. The ratio between the integrated optical density of bands
due to linear (L band) and bridged or multicentered (M band) CO species, defined as
AL/(AL+AM), shows that there is a decrease of bridged and multicentered CO species with the
addition of Co. This is consistent with a lower probability of encountering the required Nix
arrangements to form NixCO complexes (x ≥ 2). Besides, CO becomes less strongly bonded
upon Co addition, this being consistent with the fact that a bimetallic NiCo compound is being
formed. Thus, Coq et al.33 attributed the increase in selectivity to MEA to the formation of a
NiCo bimetallic phase, which leads to the reduction of Nix atom arrangements responsible for
the production of the undesirable transamination reaction. It is worth noting that Rodríguez et
al.47 gave a similar explanation to interpret the higher selectivity to ethene and the lower
production of coke during the hydrogenation of ethine when Co was added to Ni/Zn(Al)O
catalysts. In this last case, the increase in selectivity to ethene and the lower coke deposition
were attributed to a decrease in the number of three Ni-atom arrangements necessary to favour
the mechanism responsible for methane, ethane and coke formation.
According to the results discussed above, it can be concluded that the undesired
consecutive transamination reaction, which can occur between “imine” and “amine-like”
species, takes place in two different ways: 1) through a bifunctional mechanism on both metal
and acid sites; 2) on the metal sites only. The Mg addition decreases the surface acidity, causing
a decrease in the transamination reaction through the bifunctional mechanism. On the other
hand, the Co addition decreases the number of Nix atom arrangements necessary to favour the
second mechanism which involves metal Ni sites only. These two factors strongly depend on
the catalyst composition and activation conditions. Catalysts having a spinel-like structure,
obtained by decomposition and calcination of LDH precursors, are a very good option for
performing the selective hydrogenation of nitriles to MEA for two reasons: 1) it is relatively
easy to optimise the basicity of the oxide support by incorporating the appropriate amount of
Mg; 2) it is possible to form bimetallic compounds having a very low concentration of metal
sites responsible for the undesirable side reactions. In both cases, these changes can be
performed while keeping a high dispersion of the metal phase, which is important in order to
maintain a high activity of the catalysts.
Another reaction of interest involving organic nitrogen compounds is the hydrogenation of
nitroaromatics. This is an excellent example of the wide variety of products that it is possible to
obtain with different catalysts and reaction conditions.35 For instance, aniline, hydroxylamine,
p-hydroxyaniline or biphenyldiamine can be produced during the hydrogenation of
nitrobenzene, depending on the types of catalyst, solvent and reaction conditions used. The
hydrogenation of nitroaromatic compounds is usually carried out by using Pt/C, Pd/ C,
sulphided Ni and copper chromites supported on kieselghur. In all cases, the aromatic nature of
the ring is maintained. However, depending on the catalyst and the reaction conditions used,
important amounts of hydroxylamines, which are intermediates often formed in the production
of anilines,83 may be produced. This type of compound is undesirable since it is toxic and
metastable, and can yield azo and azoxy products. Selective reduction of organic nitro
compounds to anilines can be obtained by hydrogen transfer, an easy and safe method.84 Indeed,
aromatic amines, widely used as intermediates for dyes and photographic, pharmaceutical and
agricultural chemicals and antioxidants, are prepared by this method with Pt/C, Pd/C or Raney
Ni catalysts. An alternative is the use of hydrazine as a hydrogen donor. Specifically, it was
reported by Hirashima and Manabe85 that aminoarenes can be produced with high yields and
purity using hydrazine hydrate in the presence of FeCl3/C. These authors proposed that highly
dispersed Fe hydroxide is the catalytic species. On this basis, Auer et al.71 suggested using
LDHs as catalytic materials taking into account that this type of solid contains highly dispersed
metal cations. They prepared Fe-Mg-Al LDHs by precipitating the corresponding sulphates
with Na2CO3 at 60°C. The aim was to study the activity of Fe-Mg-Al LDH catalysts, not
subjected to previous thermal treatments, for the reduction of nitroarenes with phenylhydrazine
and hydrazine hydrate. The reduction of 4-nitrotoluene was the reaction selected. This reaction
was carried out in a batch reactor at 70°C. These authors found71 that Fe-Mg-Al LDHs were
very good catalysts for the reduction of 4-nitrotoluene to 4-aminotoluene with phenylhydrazine
or hydrazine hydrate as a reducing agent. The selectivity to 4-aminotouluene was 100% for all
the catalysts investigated. The activity increased with: 1) the Mg(II)/Al(III) ratio; 2) the Fe
surface area; 3) the Fe(III)/Fe(II) ratio.
Kumbhar et al.84 used Mg-Fe hydrotalcite as a catalyst for the reduction of several nitro
compounds using hydrazine hydrate as a reducing agent. Mg-Fe hydrotalcite-like solids were
obtained by precipitation of the corresponding nitrates with NaOH+Na2CO3 at 20°C and pH=9.
The hydrated precursors obtained by coprecipitation were then submitted to thermal treatment
in a N2 flow at 450°C. The catalytic measurements were performed in a batch reactor a 60°C. It
was determined that the catalyst was deactivated after each run. However, the original activity
could be restored by thermal treatment in nitrogen at 450°C. This is because the main origin of
deactivation is hydration of the catalyst by water coming from the reaction product and
hydrazine hydrate. This water induces the partial regeneration of the hydrotalcite-like phase
which causes a decrease of surface area.55 The nitro compounds used by Kumbhar et al.84 were
p-nitrotoluene, 4-cloronitrobenzene, 4-bromonitrotoluene, 4-nitrotoluene, 2-nitrotoluene,
4-methoxy-nitrotoluene, nitrobenzene and 1,3-dinitrobenzene. The authors claim that good
results were obtained even with electron-attracting substitutes. The less reactive compounds
were nitrobenzene, 4- and 2-nitrotoluene and 4-methoxy-nitrotoluene. It was determined by
Mössbauer spectroscopy that the reaction follows a redox mechanism in which Fe3+ is reduced
to Fe2+ by hydrazine and oxidised to Fe3+ by the nitroaromatic. This mechanism seems to be
favoured by the high dispersion of iron on the Mg-Fe catalyst obtained from the
hydrotalcite-like material. On the other hand, a low selectivity to hydroxylamine was observed
with this type of catalyst. Since the hydrogenation of hydroxylamine involves a surface
carbanion, it can be speculated that the higher activity may be related to the high basicity of the
surface. Thus, Kumbhar et al.84 claimed that the reduction of nitro compounds to the
corresponding amines, using hydrazine hydrate as a reducing agent, can be efficiently catalysed
with activated FeMg hydrotalcites. The main remarks on this process are: 1) the Mg-Fe catalyst
showed a very low selectivity to undesired intermediate products such as hydroxylamines; 2)
this catalyst can be regenerated and recycled very easily; 3) the process is safe, clean and
operates at atmospheric pressure with cheap catalysts.
In conclusion, the above examples show that Ni and Fe based catalysts, obtained from
Ni(Fe)/Mg/Al LDHs, are very active and selective in hydrogenation and reduction reactions
involving organic nitrogen compounds such as nitriles and nitroarenes. The high dispersion of
the metal phase and the interaction with the basic support play a very important role in these
types of reaction. However, as far as we know, no applications of activated LDHs in the direct
hydrogenation of nitroarenes with molecular hydrogen have been reported. It would be
interesting to see what happens if H2 is used instead of hydrazine with the aim of obtaining the
corresponding anilines from nitroarenes.
Hydrogenation of Carbonyl Compounds
There are several hydrogenation reactions for which transition metal oxide catalysts are
better than noble metal catalysts for producing the most desirable product.35 This is the case
with the hydrogenation of carbonyl compounds, such as ketones and aldehydes, into the
corresponding alcohol. For example, CuO/Cr2O3 is more effective in the complete
hydrogenation of 2-ethylhexanal to 2-ethylhexanol than Pt based catalysts. CuO/Cr2O3
catalysts are also widely employed in the hydrogenation of furfural to furfuryl alcohol, the
hydrogenation of fatty esters to fatty alcohols and the hydrogenation of maleic anhydride (MA)
to γ-butyrolactone (GBL). These Cu/Cr-based catalysts are normally prepared by
coprecipitation of Cu(NO3)2 and CrO3 or Cr(NO3)3 with a base such as Na2CO3 or NaHCO3.
Since the precipitation pH is different for each ion, this, together with the order of addition of
the reactants, influences the morphology and activity of the final catalyst. If the appropriate
coprecipitation conditions are used, hydrated precursors with a hydrotalcite-like structure can
be preferentially obtained.86 Depending on the calcination conditions and solid composition,
the main phases formed by calcination of these hydrated precursors are usually CuO and a
non-stoichiometric spinel-like phase.
Castiglioni et al.,87,88 showed a very interesting application of this type of Cu-Cr catalyst in
the hydrogenation of maleic anhydride (MA), an α, β unsaturated carbonyl compound, to
obtain γ-butyrolactone (GBL). GBL is of industrial importance since it is used as a solvent and
as an intermediate for the production of other compounds of higher aggregate value. GBL can
be obtained by various processes, but hydrogenation of MA is the most direct method and does
not require the use of hazardous materials. It is worth noting that with Cu/Cr catalysts this
hydrogenation reaction proceeds consecutively (Figure 34). In a first step, the conjugated C=C
bond of MA is hydrogenated to give succinic anhydride (SA). Then, by a
hydrogenation-dehydration reaction, SA is converted to GBL, which in turn is transformed into
tetrahydrofuran (THF) through a similar reaction. If GBL is the desired product, the following
facts must be taken into account: 1) GBL can be easily hydrogenated to THF; 2) by-products
such as alcohols, acids, esters and others, can be obtained from THF and GBL. Therefore, it is
important to take into account the factors that favour these last two reactions. A knowledge of
these factors will help to develop the appropriate catalyst having the necessary requirements of
activity, selectivity and lifetime.
Figure 34.- Scheme of reaction for the hydrogenation of maleic anhydride.
With this idea in mind, Castiglioni et al.,88 prepared a series of Cu-Cr catalysts by
coprecipitation of the corresponding nitrates with NaHCO3 at pH=8.0 ±0.1. After calcination,
the main phases detected by XRD were CuO and non-stoichiometric cubic spinel-type phases.
The formation of non-stoichiometric spinel-like phase, containing an excess of bivalent cations,
was confirmed by combining the results obtained by quantitative XRD and chemical analysis
and on the basis of the cubic lattice parameter. It was found that these Cu/Cr catalysts were very
active in the hydrogenation of MA and GBL in gas phase between 180-300°C, at atmospheric
pressure. For MA hydrogenation at low temperatures, THF and n-butanol were the main
products, while at temperatures higher than 275°C ethanol was detected, indicating
considerable hydrogenolysis activity. The results obtained by Castiglioni et al.88 strongly
suggested that the determining step with Cu/Cr catalysts is the hydrogenation of SA to GBL.
Subsequently, these authors87 substituted copper ions, located in the non-stoichiometric
spinel-like phase, with other divalent cations, such as Cd2+, Zn2+ and Mg2+. They found
evidence of the formation of a mixed spinel-like phase, containing Cu2+ together with one of
the divalent cations mentioned above. The partial substitution of the copper ions gave rise to a
decrease in MA and GBL conversion. In particular, substitution of Cu2+ ions with Cd2+ ions led
to a considerable deactivation. The samples containing Cd2+ were the only ones that did not
give complete conversion of MA. Addition of Zn2+ ions led to an increase in GBL yield, even
though hydrogenation to THF remained significant at the highest temperature. The increase in
GBL yield was thus attributed to a higher activity in the hydrogenation of SA to GBL. On the
other hand, Mg2+ addition significantly decreased the activity in the over-hydrogenation and,
principally, hydrogenolysis reactions. With the aim of combining the effect of the Zn2+ and
Mg2+ ions on the MA hydrogenation reaction, a Cu/Zn/Mg/Cr catalyst was prepared and tested.
The partial substitution of Cu2+ ions with both Zn2+ and Mg2+ ions gave rise to an increase in
GBL production, with a maximum yield of 74.6% at 245°C, and the almost complete absence
of hydrogenolysis reactions. In the light of various results discussed in relation to the
hydrogenation of nitriles, it is likely that the addition of Zn2+ and Mg2+ ions to Cu/Cr catalysts
leads to one or more of the following consequences in the hydrogenation of MA: 1) a
modification of the electronic density and/or surface structure of the metal phase; 2) a decrease
in the concentration of acidic sites; 3) the formation of new types of site capable of activating
the C=O groups of SA to be hydrogenated to GBL; 4) a reduction of the number of active sites
responsible for over-hydrogenation and hydrogenolysis reactions. The close interaction
between Cu2+ and the other divalent cations, favoured by the particular structure of these
catalysts, leads to an increase in these effects on the hydrogenation of MA in the gas phase.
Nevertheless, in spite of their high activity in the hydrogenation of carbonyl compounds,
Cu-Cr based catalysts are becoming increasingly difficult to use. This is because of the
increasing legal restrictions on the use of chromium-containing catalysts, due to the toxic
nature of the Cr6+ ions present in the spent catalyst. Aluminium-containing catalysts seem to be
a very interesting alternative to replace chromium.86,89
Castiglioni et al.89 found that aluminium-containing samples favour the formation of a well
crystallised hydrotalcite-like (HT) phase, in agreement with the results obtained by Marchi57
and Rodríguez,8 while chromium leads to quasi-amorphous hydroxycarbonates. They prepared
Cu/Zn/Al catalysts by coprecipitation of the corresponding nitrates with NaHCO3 at
pH=8.0 ±0.1. The hydrated precursors were calcined at 380°C for 24 hours and then activated
in situ in a flowing H2(5%)/N2 stream at 330°C. It was found by XRD that, after calcination,
samples with low copper contents gave only poorly crystallised cubic spinel-type phases. At
higher copper contents, CuO was also detected. The Al-containing samples had higher surface
areas and smaller pores and pore volumes than those containing chromium. Again, evidence
was obtained by XRD and TPR of bivalent cupric ions inside the cubic spinel-like phase, giving
rise to a non-stoichiometric spinel phase or strongly interacting with it. Furthermore, it was
determined by TPR that the relative quantity of Cu2+ ions strongly interacting with the
non-stoichiometric spinel phase with respect to non-interacting Cu2+ decreased with the copper
content. The catalytic tests showed that the best catalytic performances were obtained with the
aluminium-containing samples with the lowest copper content. However, it was also found that
with catalysts of low copper content, the maximum GBL yield shifted towards higher
temperatures, at which the formation of unwanted by-products increased. In addition,
Al-containing samples showed higher adsorption phenomena and lower mechanical strength
than Cr-containing catalysts. Taking this into account, Castiglioni et al.89 prepared a
Cu/Zn/Al=25:25:50 (atomic ratio %) sample in order to improve the crystallinity of the
precursor, taking advantage of the best packing of the elements in the brucite-like sheets of the
ternary HT phases. With this catalyst, the maximum GBL yield was achieved at 245°C with the
production of small amounts of unwanted products. These catalysts showed a partial
diminution of adsorption phenomena and better mechanical properties. However, the catalytic
performances were not fully satisfactory and, in order to reduce the influence of these two
deficiencies, the catalyst was pelletised. The catalytic tests with GBL showed an important
decrease in the hydrogenation capacity of the pressed sample. However, a surprisingly higher
yield in THF was also determined, probably due to lower production of unwanted low-cost
by-products, mainly n-butanol and butyric acid. A similar behaviour was observed in the
catalytic tests with a MA/GBL solution, but now the maximum GBL yield shifted to 275°C.
These changes in the hydrogenation capacity of pressed samples was attributed to variations in
surface area and pore size distribution due to pressure treatments. The positive effect of
pressure treatments is that activation in GBL ring opening and overhydrogenation reactions are
reduced considerably. These results indicate that micropores hardly participate in the reaction.
Instead, the decrease in larger macropores modifies the GBL/THF ratio, reducing the
production of unwanted by-products. This decrease also reduces the irreversible adsorption
phenomena, responsible for tar formation. Thus, Castiglioni et al.89 claim that a pelletisation
treatment may improve not only the physical properties of the catalysts, but also have a positive
effect on the selectivity by reducing the overhydrogenation and hydrogenolysis reactions.
In a later work, Castiglioni et al.86 found that Cu/Zn/Al catalysts, when used in gas-phase
MA hydrogenation, showed complete MA conversion and high GBL yields when the
Al-content was about 17% (atomic ratio) and the Cu/Zn ratio was between 0.5 and 1.0. In
agreement with their earlier works, they reported that Al-containing catalysts exhibited better
performances than Cr-containing catalysts. Chromium-containing catalysts are very active in
overhydrogenation and hydrogenation reactions and only poorly active in the hydrogenation of
SA. Both factors reduce the GBL yield considerably. The presence of aluminium favoured the
GBL yield. It is worth noting that a high aluminium content favoured the formation of THF and
irreversible surface adsorption (with tar formation), while a low aluminium content favoured
overhydrogenation and hydrogenolysis reactions. For catalysts with 24% aluminium, GBL
yields as high as 96% were reached for high zinc contents. In contrast, when the aluminium
concentration was about 17%, the GBL yield became poorer as the Cu/Zn ratio was decreased.
The authors also tested Ga-containing catalysts, but found that they did not show sufficiently
significant differences with Al-containing samples to justify their use, given the significantly
higher cost.
According to the results obtained by Castiglioni et al.,86 it can be stated that Al-containing
catalysts can replace Cr-containing catalysts in the vapour phase hydrogenation of MA to GBL.
Cu/Zn/Al catalysts of appropriate composition lead to complete conversion of MA and high
GBL yields, with low hydrocarbon production and tar formation. With this type of catalyst, a
high interaction between metal and a non-stoichiometric spinel phase can be obtained. Thus,
the preparation of a catalyst in which a very finely dispersed copper metal phase is in intimate
contact with other surface sites present on the non-stoichiometric spinel-type phase would
allow the generation of new types of active sites that are more active and selective for the
desired reaction. Furthermore, it can also lead to an almost complete elimination of undesirable
active sites, responsible for the production of unwanted by-products. This is what seems to be
happening when Al replaces Cr in the copper-based catalysts used for hydrogenation of MA to
GBL.
Cu (Zn, Co)/Cr catalysts, prepared by the reduction of non-stoichiometric spinel-type
compounds, were also tested in the hydrogenation of oxoaldehyde mixtures.34 The aim was to
obtain normal and branched alcohols with carbon chains ranging from 4 to 18 atoms, required
for the production of solvents, plasticizers and detergents. The hydrogenation of crude
oxoaldehyde mixtures is a difficult operation since a large variety of by-products can be
obtained. Trifirò et al.34 prepared a series of Cu (Zn, Co)/Cr catalysts by the coprecipitation
method, in conditions similar to those used by Castiglioni et al.,88 and tested them in the
hydrogenation of oxoaldehydes mixtures. They found that the catalysts were more active and
selective than commercial catalysts and were less sensitive to poisoning when Cu was partially
substituted with Zn. Furthermore, Trifirò et al.34 suggested that the high activity of these solids
could be related to the formation of mixed spinel-type phases.
By means of a comparison of the results obtained by Castiglioni et al.,88 working with
Cu/Zn/Cr and Cu/Zn/Al catalysts in the hydrogenation of MA, and those obtained by Trifirò et
al.,34 working with Cu/Zn/Cr catalysts in the hydrogenation of oxoaldhehyde mixtures, it would
be of great interest to see what would happen if Cu/Zn/Al catalysts were used in the latter
reaction. At the light of the results described above, Cu/Zn/Al catalysts could be expected to
show a similar or better performance than Cu/Zn/Cr catalysts in the hydrogenation of
oxoaldehyde mixtures. According to the results obtained by both Trifirò et al.34 and Castiglioni
et al.,88 the formation of non-stoichiometric spinel-type phases plays a very important role in
the hydrogenation reactions of carbonyl compounds. This type of phase can easily be formed
in a ternary Cu/Zn/Al system depending, of course, on the solid composition. Furthermore, in
some cases, Cu/Zn/Al can be shown to be a better catalyst than Cu/Zn/Cr for MA
hydrogenation in the gas phase, with the additional advantage that Cu/Zn/Al catalysts are
chromium-free. Thus, it could be expected that Cu/Zn/Al ternary systems could satisfactorily
replace Cu/Zn/Cr catalysts in the hydrogenation of oxoaldehyde mixtures in the gas phase.
Another interesting case of hydrogenation of α, β unsaturated carbonyl compounds is
found in acetophenones and indanones. The desired products from the hydrogenation of
indanones are indenes, while for acetophenone hydrogenation they are styrenes. Indenes are
important intermediates in metallocene synthesis. The conventional processes for the
preparation of indenes are, in general, two-step syntheses. As an example, in the first step
indanone can be converted to the corresponding alcohol by using a reductive agent (NaBH4,
LiAlH4 or KBH4). In a second step, the alcohol is transformed to indene by dehydration using
an acid catalyst. A scheme of this two-step process is represented in Figure 35.
Figure 35.- Reaction mechanism for indene synthesis from indanones.
Roesky et al.90 suggested a new method to synthesize indenes or styrenes from indanones
or acetophenones, using an oxide catalyst and hydrogen as a reductive agent, with a one-step
heterogeneous gas phase process. They prepared a Zn/Al binary catalyst by coprecipitation
with ammonia solution at pH≈9. The main crystalline phase detected by XRD, after calcination
at 600°C and treatment in H2 flow at 450°C, was a ZnAl2O4 spinel. The catalytic tests were
carried out in the gas phase, at atmospheric pressure and in the temperature range of 300-350°C,
using several indene and acetophenone compounds. The best catalyst for the conversion of
2-methylindanone to 2-methylindene was that with an Al/Zn ratio of 2. Roesky et al.90 found
that, in general, this type of Zn/Al catalyst works satisfactorily in the one-step synthesis of
styrenes and indenes from acetophenones and indanones. They attributed the catalytic
behaviour to the acid/base properties of this Zn/Al binary solid. However, the selectivity to the
desired product strongly depends on the substitute group in the acetophenone or the indanone
compounds. Thus, in the case of the alkyl or aryl substitute group, both the conversion and
selectivity to the desired product are high. However, when the substitute groups are alkoxy,
acetoxy or hydroxyl, the main product is phenol, while the desired product is not detected. In
addition, the rate determining step of the reaction seems to be hydrogenation, since the
intermediate alcohol was never found in the product analysis.
At the light of the results obtained by Roesky et al.,90 it would be interesting to see what
happens when a system such as a metal/non-stoichiometric spinel-type phase is used as a
catalyst in the hydrogenation-dehydration reaction of indanones and acetophenones. It would
be expected that the hydrogenation step, assumed to be the determining step, could be favoured
when a metal phase is present. The main role of this metal phase would be to provide the
activated hydrogen required to accelerate the hydrogenation of indanones and acetophenones to
the corresponding alcohols. Furthermore, it is likely that a metal phase would allow a decrease
in the reaction temperature for this reaction. In other words, a metal/Zn/Al system, similar to
that used for MA hydrogenation, could be an interesting alternative as a catalyst for this
reaction.
Among the hydrogenation reactions of organic compounds with more than one functional
group, the selective hydrogenation of α, β unsaturated aldehydes is a reaction of particular
interest due to its important application in pharmaceuticals, the food industry and fragances. In
general, the desired product is the corresponding unsaturated alcohol, which means that the
C=O group, rather than the C=C bond, must be hydrogenated. This is an interesting problem of
regioselectivity since it is easier to hydrogenate the ethylenic group due to both thermodynamic
and kinetic factors.
The corresponding unsaturated alcohol (UOL) can be obtained by selective hydrogenation
of the functional C=O group (step 1, Figure 36), while the saturated aldehyde (SAL) can be
produced by selective hydrogenation of the C=C bond (step 2, Figure 36) of the unsaturated
aldehyde (UAL). Both the saturated aldehyde and the unsaturated alcohol can then be further
hydrogenated to give the saturated alcohol (SOL) (steps 3 and 4, Figure 36). Other possible
reactions are the isomerization of UOL into SAL and the direct hydrogenation of UAL to SOL.
Undesirable side reactions are hydrogenolysis and decarbonylation of reactants and products,
not shown in Figure 36.
Figure 36.- General reaction scheme for hydrogenation of  -unsaturated aldehydes.
To summarise, the hydrogenation of α, β unsaturated aldehydes is, in general, a complex

reaction in which several products can be obtained, but only one is usually desired: the
corresponding unsaturated alcohol (UOL).
Taking into account that UOL is the desired product, the metal base catalysts used in this
reaction can be classified in three different categories: 1) slightly selective (Pd, Rh, Ni); 2) very
selective (Ir, Os); 3) moderately selective (Pt, Ru, Co). Very high selectivities to UOL can be
found with Ir and Os based catalysts. However, these metals are very expensive, making their
use unattractive from an industrial point of view. In the case of Pt and Ru, it is possible to reach
high selectivities to UOL by the use of special supports (C, zeolites), the formation of
bimetallic compounds (Pt-Co, Pt-Fe) and the addition of metallic ions (FeCl3, SnCl4). Gallezot
and Richard91 wrote an extensive and detailed review on the use of these modified catalysts in
the selective hydrogenation of α, β unsaturated aldehydes. Several arguments are used to
explain the influence of these modifications on the selectivity of noble metal based catalysts. In
particular, metal-support interactions and the addition of metallic ions seem to be very
important in order to modify the catalytic behaviour of the metal phase.
With this idea in mind, Marchi et al.92 proposed to modify the catalytic behaviour of
metallic copper in the hydrogenation of cinnamaldehyde by interaction with a
non-stoichiometric spinel-like phase. In the reaction scheme shown in Figure 36,
cinnamaldehyde (CAL) is the unsaturated aldehyde (UAL) and can be converted by
hydrogenation to cinnamyl alcohol (COL), the corresponding unsaturated alcohol (UOL), and
to hydrocinnamaldehyde, the saturated aldehyde (SAL). As mentioned above, the desired
product is UOL. In order to verify the influence of the spinel phase on the catalytic behaviour of
copper, Marchi et al.92 prepared two different types of catalyst: 1) Cu(12%)/SiO2, by the
incipient wetness impregnation method; 2) Cu(12%)/Zn/Al by the coprecipitation method at
pH≈ 7.2 ±0.2, with the simultaneous addition of the corresponding nitrates and Na2CO3. In the
Cu/SiO2 sample, only a CuO phase with a tenorite structure was detected on the silica surface
after calcination at 400°C. In the case of Cu/Zn/Al sample, however, after thermal treatment in
flowing N2 at 500°C of a well crystallised HT-like hydrated precursor, the only crystalline
phase detected was a non-stoichiometric spinel-type phase; no evidence of phase segregation or
CuO formation was detected. The combined TPR and XRD results indicated that copper is
highly dispersed and strongly interacts with a zinc aluminate, non-stoichiometric spinel-type
phase.22 The hydrogenation of cinnamaldehyde in liquid phase showed that Cu/Zn/Al was
much more active than the Cu/SiO2 catalyst (Figure 3792). In the case of Cu/SiO2, there is a
clear linear relationship between conversion and time. This was confirmed by fitting the
conversion data in function of the time and assuming different reaction orders for the reactive.
The best fitting was obtained with a reaction order equal to zero for cinnamaldehyde. The best
fitting for the Cu/Zn/Al, however, was obtained when two different reaction orders were
assumed for cinnamaldehyde: order two for step 1 and order one for step 2.93 These differences
in the reaction orders suggest that it is very likely that the reaction mechanism is different for
both types of copper based catalyst. Moreover, the two different orders found for step 1 and step
2 with the Cu/Zn/Al catalyst could indicate that COL and SAL are produced in different ways
and/or different types of active site.
Figure 37.- Conversion of cinnamaldehyde with time with copper based catalysts.
The Cu/Zn/Al is not only more active in the hydrogenation of cynnamaldehyde in liquid
phase, but also more selective (Figure 38). The COL yield (open symbols) with the Cu/SiO2
catalyst is significantly lower than the corresponding values for SAL (solid symbols), whereas
in the case of the Cu/Zn/Al catalyst both yields are comparable. Cu/Zn/Al is also considerably
more selective to COL than the Cu/SiO2 catalyst. Both the initial activity and the selectivity to
COL were about one order of magnitude higher with Cu/Zn/Al than with Cu/SiO2.93 The higher
catalytic activity and selectivity of Cu/Zn/Al to COL in the hydrogenation of CAL in the liquid
phase was related to the strong interaction between the small metal copper crystallites and the
zinc aluminate spinel-type phase. Marchi et al.93 suggested that on the surface of the
non-stoichiometric spinel-type phase there are cationic sites able of interacting with the
functional C=O group of CAL. The CAL molecule is adsorbed on-top on these cationic sites
and activated by them. Metal copper crystallites can adsorb and activate hydrogen, which in
turn can migrate to the vicinity of the CAL adsorbed on the cationic sites and hydrogenate the
functional C=O group to give COL. This interaction between CAL, adsorbed on-top on
cationic sites, and activated hydrogen, adsorbed on the surface of the small metal copper
crystallites, is favoured by the close interaction between the metal copper particles and the
cationic sites present on the surface of the non-stoichiometric spinel-type phase. This physical
model of very small metal copper particles highly dispersed in a non-stoichiometric zinc
aluminate spinel-type phase, which can originate new types of active sites that can strongly
interact with the functional C=O group, seems to be a good explanation for the results obtained
by Marchi et al.,93 in the hydrogenation of CAL in liquid phase.
Figure 38.- Intermediate products yield in the hydrogenation of cinnamaldehyde.
Another example of increased activity in the hydrogenation of α, β unsaturated aldehydes

is the case of nickel-based catalysts employed in the hydrogenation of citral.94 The nickel-based
catalysts were tested in both cinnamaldehyde and citral hydrogenation in the liquid phase. The
results obtained in the hydrogenation of cinnamaldehyde show that Ni/Zn/Al catalysts are
somewhat more selective to COL than Ni/SiO2 catalysts. The hydrogenation of citral is a more
complex reaction than the hydrogenation of CAL due to the fact that it has three potential
hydrogenable bonds: 1) the functional C=O group; 2) the conjugated C=C bond; 3) the isolated
C=C bond. The hydrogenation of citral, according to the reaction scheme shown in Figure 39,
can thus give a series of additional products compared to the hydrogenation of CAL.
Some of these products are of great interest for flavourings and fragrances, as well as
intermediates for the production of other compounds of higher value. For instance, geraniol and
nerol are used in perfumery, while citronelol is used by the soap and detergent industries due to
its rosy scent. Citronelal has limited use in fragrances and flavourings since it is easily oxidised
and unstable in an alkaline medium. Instead, it is used in the production of hydroxycitronellal,
methoxycitronellal and menthol. Geraniol and nerol are also used as starting materials for the
synthesis of hydroxycitronellal, ionones, vitamins A and E and carotenoids. The unwanted
products are usually 3,7-dymethyloctanal (3,7-DMAL) and 3,7-dymethyloctanol (3.7-DMOL).
Hydrogenation of citral is therefore a reaction of great interest since useful products such as
citronellal, citronellol, geraniol and nerol can be obtained by different routes.
Figure 39.- General reaction scheme for citral hydrogenation.
However, when nickel-based catalysts are used, the route is that shown in Figure 40. Thus,
among the products of major interest, citronellal and citronellol are normally obtained; neither
geraniol nor nerol are produced.
Figure 40.- Reaction scheme of citral hydrogenation on nickel-based catalysts.
In order to study the influence of the metal nickel/spinel-type matrix interaction in the
hydrogenation of citral in the liquid phase, Marchi et al.94 compared the performance of a
Ni/SiO2 catalyst with that of Ni/Al and Ni/Zn/Al catalysts, prepared by the coprecipitation
method. It was found that the global activity followed the order Ni/Zn/Al >Ni/Al > Ni/SiO2.
This was the same order as the activity in the conversion of citronellal into citronellol (Figure
41). The citronellol yield (open symbols, Figure 41) was about 95% after 6 h reaction with
Ni/Zn/Al, but less than 30% for Ni/SiO2 (solid symbols, Figure 41). Furthermore, the
maximum yield in citronellal, about 80%, was reached after 2 h reaction with Ni/Zn/Al, while a
reaction time close to 5 h was necessary when Ni/SiO2 was used as a catalyst. No 3,7-DMAL
was detected in any case, while the 3,7 DMOL yield was lower than 5% in all cases. Ni/Al
catalysts showed an intermediate behaviour between Ni/SiO2 and Ni/Zn/Al. Characterisation
by XRD and TPR shows that, after calcination, Ni/SiO2 is mainly composed of large NiO
crystallites on the surface of the silica support. By reduction in H2 flow at 400-500°C, large
metal Ni crystallites are also formed. Ni/Zn/Al oxide, obtained by decomposition of LDH
hydrated precursors, has a spinel-type structure where NiO and/or Ni2+ ions are highly
dispersed and interact with a non-stoichiometric zinc (nickel) aluminate-like phase. After
reduction in similar conditions to those mentioned for the Ni/SiO2 sample, a more or less well
dispersed metal nickel phase in the spinel-type matrix can be obtained. Volumetric
measurements of chemisorbed H2 and CO reveal that there are also important surface structural
differences between the Ni/SiO2 sample and those prepared by coprecipitation. Studies of
chemisorbed CO by FTIR confirm the observations made by the volumetric method. Thus, the
higher activity of the Ni/Zn/Al catalyst in the hydrogenation of the C=O group, observed in
both cinnamaldehyde and citral hydrogenation, is again attributed to the strong metal-spinel
interaction. In this case, the bulk and surface structure of Ni crystallites is significantly
modified by this interaction, which strongly affects the catalytic behaviour of metal nickel in
the hydrogenation of cinnamaldehyde and citral in liquid phase.
Figure 41.- Citral hydrogenation in liquid phase with nickel-based catalysts.
The results obtained by Marchi et al.94 show that the activity of metal copper and nickel in
the hydrogenation of α, β-unsaturated aldehydes in the liquid phase can also be improved by
strong interaction with a non-stoichiometric spinel-type phase prepared by thermal
decomposition of LDHs.
Another hydrogenation reaction in which carbonyl groups are involved is the conversion of
acetone into 2-propanol and methyl isobutyl ketone (MIBK). Acetone hydrogenation is an
important reaction due to its application in chemical heat pumps for waste heat recovery, for
which a high selectivity to 2-propanol is required. Another interesting product of this reaction is
MIBK, which is mainly used as a solvent for cellulose and resin based coating systems and for
vinyl, epoxy and acrylic processes.95 In this reaction, three routes seem to be possible: 1) the
hydrogenation of acetone to give 2-propanol on metallic sites; 2) the conversion of acetone into
MIBK, involving both metallic and acid sites; 3) a condensation reaction of three molecules of
acetone to give isophorone, involving only the acidic function of the catalyst.96 Thus if
2-propanol is the desired product, a metal catalyst, such as Ni-Raney, could be suitable for this
reaction. If, however, high selectivity to MIBK is required, then a bifunctional catalyst having
both metallic and acid-base sites would be better. Narayanan and Unnikrishnan95 prepared a
series of Ni/Al catalysts by the coprecipitation method at constant and varying pH. The
hydrated precursors were calcined in air at 450°C and then activated in an H2 flow at 450°C.
The reaction was carried out in gas phase, at 100-200°C, feeding a mixture of
acetone-hydrogen. Narayanan and Unnikrishnan95 found that the catalyst prepared by varying
the pH was more selective to MIBK, while that prepared by the constant pH method was more
selective to 2-propanol. The only important difference they found between both catalysts was
the specific surface area. The catalyst prepared by constant pH gave a the higher surface area,
290 m2/g, as against 197 m2/g for the sample prepared by the varying pH method. Modification
of the catalysts by addition of Mg, Fe and Co led to a decrease in surface area and to an increase
in MIBK selectivity, in agreement with the above results. In this last case, acetyl acetone was
also detected in the product stream. On the other hand, when the nickel loading was raised, the
selectivity to 2-propanol increased at the expense of MIBK. This is not unexpected, taking into
account the type of active sites involved in the production of each compound. An increase in
the temperature produces an augmentation of acetyl acetone selectivity to the detriment of
MIBK selectivity. These results confirm the initial assumption on the types of active site
involved in each reaction; only metal sites seem to be responsible for 2-propanol production
while MIBK formation also needs sites of an acid-base nature. In a more recent work,
Narayanan and Unnikrishnan96 studied the behaviour of Ni/Al, Co/Al and Fe/Al catalysts
prepared by the coprecipitation method. Their results provide further evidence that a dual
function mechanism, involving both metal and acidic sites, decides the selectivity to the
products. Furthermore, the authors found that nickel-based catalysts were the most active,
followed by cobalt and iron. They characterised the metal and acidic functions of the catalysts
and found that: 1) the hydrogen uptake was very low for Co/Al and Fe/Al when compared to
the Ni/Al catalyst; 2) the acidity of Ni/Al, Co/Al and Fe/Al are very similar; 3) the acidity
decreases with metal loading. The catalytic results showed that for Co(10%)/Al and
Fe(10%)/Al, which have very little metallic content, the main product is isophorone. As the
metal loading was raised, the yields of 2-propanol and MIBK increased. The Ni/Al catalyst was
found to be more selective to MIBK, while Co/Al showed higher selectivity to 2-propanol.
Thus, Narayanan and Unnikrishnan96 concluded that the product selectivity depends on: 1)
metal nature and metal loading, since hydrogenation activity is in accordance with their
hydrogen adsorption capacity; 2) reaction conditions. However, they did not study the
influence of the type of support in this reaction. It could be expected that, by changing the
nature of the support, the acid-base character of the catalyst would change and the selectivity to
MIBK could therefore be manipulated, avoiding the conversion of acetone into isophorone and
other undesirable products. A Ni/Zn/Al catalyst with a non-stoichiometric spinel-like structure
would be an interesting choice for this type of study because of the amphoteric character of the
zinc aluminate support that can be obtained.
The results shown in this section clearly indicate that base metal/non-stoichiometric
systems, obtained by decomposition and/or calcination of LDH solids, are very good catalysts
in the hydrogenation of carbonyl compounds. This type of catalyst has, in many cases, a better
global activity and selectivity to the desired product than some conventional catalysts prepared
by impregnation, for example. This improvement in the catalytic performance can be attributed
to a high dispersion and strong interaction of the metal phase with the non-stoichiometric
spinel-type matrix. The result of this strong interaction could be both changes in the catalytic
behaviour of the metal and in the generation of new active sites, which in some cases produce a
significant improvement in catalytic performance.
Other Reactions
There are several other reactions in which catalysts with a non-stoichiometric spinel-type
structure, obtained by thermal decomposition and/or calcination of LDHs, have been applied.
The synthesis of methanol, higher alcohols and hydrocarbons from syngas are examples. In this
respect, Trifirò and Vaccari,24 pointed out that Cu(Co,Zn)/Cr non-stoichiometric phases may be
useful precursors for catalysts with unusual properties in alcohol or hydrocarbon synthesis
from syngas. In both cases, they observed a strong increase in activity, attributed to specific
synergetic effects between two elements that constitute the catalyst, for example Cu and Co.
These synergetic effects are strongly favoured by the close contact and strong interaction
existing between the cations present in the non-stoichiometric spinel-like phase. Gonçalves
Coelho et al.97 used Cu/Zn/Al(Cr) catalysts with a non-stoichiometric spinel-type structure in
methanol synthesis and arrived to similar conclusions. Gusi et al.98 reported that the catalytic
activity of Cu/Cr systems could be modified by the presence of another element; zinc promoted
methanol synthesis and cobalt produced different effects depending on its quantity. Fornasari et
al.,99 in agreement with Gusi et al.,98 found that small amounts of Co led to a noticeable
modification in the surface reactivity of the catalysts: a dramatic deactivation, without any
change in selectivity, was observed for a cobalt content up to 2%, while an increase in activity
with a high selectivity to hydrocarbons was detected for higher cobalt contents. Both the
poisoning effect of low cobalt loadings and the activity increase with higher cobalt loads were
attributed to a synergetic effect between a well-dispersed metal copper phase and the
cobalt-containing spinel-type matrix. Grandvallet et al.100 studied the behaviour of
Cu/Co/Zn/Al in contact with a syngas feed under similar reaction conditions to those used in
the low pressure process for methanol synthesis. They found that both higher alcohols and
hydrocarbons, having a Schulz-Flory distribution, can be obtained with this type of catalyst.
Again the catalytic behaviour of the quaternary system was attributed to a synergetic effect
between copper and cobalt favoured by the particular structure of the non-stoichiometric
spinel-type phase. Dalmon et al.101 have reviewed higher alcohol synthesis on cobalt-based
catalysts and concluded that the cobalt-copper association appears to be at the heart of the
Cu/Co/Zn/Al formulation. Taking into account that cobalt and copper are well dispersed in the
oxide matrix, which is favoured by the particular structure of a non-stoichiometric spinel-like
phase, they can form an alloy after reduction. Dalmon et al.101 proposed that this is the site that
activates CO both dissociatively and non-dissociatively; a dual function required for the
formation of alcohols. Fornasari et al.40 found that hydrocarbon mixtures with a Schulz-Flory
distribution were the main products when Cu/Co/Zn/Cr catalysts were employed. A maximum
in activity was reached for catalysts containing comparable amounts of copper and cobalt. The
catalytic activity was again attributed to a synergetic effect between copper and cobalt,
favoured by the interaction existing between a well-dispersed metal copper and a
non-stoichiometric spinel-like phase. The synthesis of alcohols and hydrocarbons represents
another very important field of application for spinel-like catalysts obtained by thermal
decomposition of LDH precursors. The results mentioned above clearly demonstrate the
potential of this type of catalyst in the synthesis of methanol, higher alcohols and hydrocarbons.
The selectivity to any of these compounds depends on the catalyst composition and the relative
amounts of the elements involved in their formulation. Thus, Cu/Co/Zn/Al catalysts can be
selective to higher alcohols while Cu/Co/Zn/Cr catalysts are usually selective to hydrocarbons,
especially when the Cu/Co ratio is around one. Furthermore, Cu/Zn/Cr catalysts are selective to
methanol under high pressure process conditions. In all cases, both the high activity and
selectivities observed were attributed to synergetic effects favoured by the strong interaction
between the metal particles and the matrix of a non-stoichiometric spinel-type phase.
Other reactions of interest in which catalysts of spinel-like structure have been used are the
methanation of CO and of CO2. Tsuji et al.102 prepared a Ni(II) ferrite sample by two different
methods, coprecipitation and oxidation, in order to study its catalytic behaviour in CO2
methanation. The precursors obtained by both methods were thermally treated in a nitrogen gas
flow at 300°C for 1-2 h and tested in the methanation of CO2 using a continuous-flow fixed bed.
The reaction was carried out at 300°C in a gas stream feed with a molar ratio of H2/CO2=4.
Before reaction, the only crystalline phase detected by XRD in both types of calcined samples
was of a spinel-like structure. The crystallite size, determined by XRD and TEM, was smaller
for the samples prepared by coprecipitation than for those obtained by oxidation. Mössbauer
and IR spectroscopies gave further evidence that only ferrite compounds, in which iron ions are
in both tetrahedral and octahedral coordination, constitute the solid structure of the samples
prepared by the two methods. Tsuji et al.102 found that the catalysts prepared by the
coprecipitation method, having the smaller crystallite size and the higher specific surface area,
were more active and selective in the CO2 methanation reaction than those prepared by
oxidation. They assumed that the selectivity to CH4 depended on the ferrite particle size.
However, the specific activity (mmol.m-2.s-1) of samples prepared by coprecipitation was about
one-half of that of samples prepared by oxidation. Tsiju et al.102 considered that only oxygen
sublattice points, whose density is lower in coprecipitated samples, are the active sites in CO2
methanation on Ni(II) ferrites, while metal sites seem not to be involved. However, after a 10 h
run, the XRD pattern of catalysts prepared by coprecipitation showed low, broad peaks
assigned to metallic nickel or iron along with strong spinel peaks, while only spinel peaks were
detected for the catalyst obtained by the oxidation method. It is worth noting that the CH4 yield
increased to the detriment of the CO yield when coprecipitated catalysts were used instead of
those obtained by oxidation. Tsiju et al.102 attributed the lower selectivity to CO to the smaller
crystallite size of the oxides obtained by the coprecipitation method. However, it is important to
consider the possibility that this type of catalyst could have a higher reduction potential than
those prepared by oxidation. The metal phase could then be more easily formed in reaction
conditions and play some role in the reduction of CO. On this point, Alzamora et al.6 published
an extended paper with detailed information about the best conditions for obtaining a very
active and stable metallic nickel phase in nickel-alumina catalysts, prepared by the
coprecipitation method, to be used in Adam´s methanation. They concluded that the samples
prepared by the coprecipitation method, when calcined at low calcination temperatures, appear
to be very active and stable under relatively extreme reaction conditions. If a small particle size
is achieved for the nickel oxide rich phase prior to reduction, the resultant material will have a
high stability as well as activity in the methanation reaction. Thus, the metallic phase dispersed
in the spinel-type phase seems to play an important role in this reaction.
Nickel-based catalysts are also capable of hydrogenating the aromatic ring of compounds
such as, for instance, aniline. Aniline hydrogenation is important for the production of
cyclohexylamine, N-phenylcyclohexylamine and dicyclohexyalmine, which are useful
intermediates. Narayanan et al.103 tested nickel-alumina catalysts prepared by constant and
varying pHs in aniline hydrogenation in gas phase at 200-250°C. The catalysts prepared by the
constant pH method had higher pore volumes and surface areas at all metal levels. The metal
dispersion was very poor for both methods of preparation, but it must be taken into account that
a large number of metal ions are inside the oxide matrix. It is worth noting that no evidence of
bulk nickel aluminate was found. Hydrogenation of aniline with this type of catalyst produced
mainly N-phenylcyclohexylamine, while other products were cyclohexylamine,
dicyclohexylamine and cyclohexane. In another work, Narayanan et al.104 compared the
activity and selectivity of Co/Al2O3 and Ni/Al2O3 catalysts in the hydrogenation of aniline. In
this case the samples were prepared by the constant pH method. Co/Al2O3 catalysts,
considerably less active than Ni/Al2O3, selectively produced cyclohexylamine. Ni/Al2O3
catalysts can also produce N-phenylcyclohexylamine and dicyclohexylamine, the first being
the main product. All of these products are important chemical intermediates and can be
selectively synthesized by choosing the appropriate catalyst and reaction conditions. These
results suggest that it could be very interesting to modify the selectivity of nickel-based
catalysts, while keeping high levels of conversion, by using Ni(Co)/Zn/Al catalysts with a
spinel-type structure. These catalysts can be prepared by thermal decomposition of LDHs
obtained by coprecipitation at constant pH. According to the mechanism proposed by
Narayanan et al.104 and to results previously described in this chapter,33,47 it is likely that the
addition of Zn and/or Co to Ni/Al catalysts can modify the selectivity of metal nickel in favour
of cyclohexylamine.
In some cases, mixed oxides obtained by calcination of LDHs are used as supports for
noble metal catalysts. As an example, Chen et al.,105 tested Pd supported on Mg/Al mixed
oxides in the hydrogenation of phenol to produce cyclohexanone. Cyclohexanone is a very
important intermediate in the production of carprolactam, which is itself used in the
manufacture of Nylon 6 and polyamide resins. Cyclohexanone can be obtained by a two-step
process: in the first step phenol is hydrogenated to cyclohexanol over a nickel catalyst and in
the second step cyclohexanol is dehydrogenated into cyclohexanone. There is also the
possibility of obtaining cyclohexanone by a one-step process avoiding the endothermic step of
dehydrogenation, which is advantageous for investment and energy savings. The industrial
catalyst used for the one-step process is normally Pd/Al2O3, which shows a 50-60% selectivity
to cyclohexanone at approximately 20% conversion. Chen et al.105 prepared several Mg/Al
LDHs by coprecipitation maintaining a constant pH of about 10 at 40°C. The LDHs were
calcined in air at 550°C and afterwards the Pd was added by incipient impregnation. The
Pd-based catalysts supported on ex-LDHs turned out to be more active and selective than
Pd/Al2O3 catalysts at 180°C. The low activity and selectivity of the latter was attributed to the
acidity of the alumina. Both activity and selectivity can be improved when alumina is modified
with CaO. Chen et al.105 concluded that basic and neutral supports favour the formation of
cyclohexanone. This seems to be related to the adsorption mode of the phenol molecule: the
basic sites of the calcined hydrotalcite seem to favour the adsorption mode of phenol that can be
preferentially hydrogenated into cyclohexanone. Another parameter that would play an
important role is the specific surface area of the support. Calcined hydrotalcites with a ratio of
Mg/Al ≤ 4, having a surface area in the range of 200-250 m2/g, showed better catalytic
performance than samples with a ratio of Mg/Al > 4 whose surface area was in the range of
20-50 m2/g. Thus, Mg/Al ex-LDHs of high specific surface area seem to be suitable supports
for the one-step process of phenol hydrogenation.
There are several other reduction and hydrogenation reactions in which catalysts obtained
by thermal treatment of LDHs can be used. However, we believe that the examples discussed in
this chapter are more than sufficient to demonstrate the importance that this type of catalyst can
attain in this field. They are very versatile and can be prepared using different bivalent and
trivalent cations in a wide range of compositions while maintaining a high degree of

homogeneity. This particular characteristic allows us to obtain catalysts of a wide range of
surface areas, varying acid-base character and different types of active sites enabling the
regulation of the catalytic behaviour of these special types of solid.
CONCLUDING REMARKS
Base metal catalysts are widely used in hydrogenation reactions both in liquid and gas
phase. These catalysts can be prepared in different ways, including the coprecipitation method
which leads to hydrated precursors with a high degree of homogeneity. A solid with a LDH
crystalline structure in which the metal cations are randomly distributed can be obtained if
suitable precipitation conditions are chosen. The close contact of the cations in this structure
can be preserved in the subsequent preparation steps, depending on the preparation conditions
and the LDH composition. In some cases, where M+2/M+3 ≤ 1, the thermal decomposition of a
LDH precursor gives an oxide with a non-stoichiometric spinel-like structure. In this structure
the cations retain the high interaction originally existing in the hydrated precursor before
calcination. If M+2/M+3 > 1, the decomposition process results in a mixture of crystalline oxides
with a general formula MO or M3O4 (M = Ni, Co, Cu, Fe, Zn, Mg, etc.). In the first case,
activation in H2 leads to a final catalyst in which the metal phase is highly dispersed in a
non-stoichiometric spinel-like phase. This means that the crystalline spinel phase can be
preserved even after the reduction step. The probability of preserving this crystalline phase
increases if Zn+2 and/or Mg+2 are present in the solid matrix. In the second case, after activation
in H2, there is a metal phase interdispersed in the matrix of a MO crystalline phase, where MO
corresponds to one or more of the non-reducible cations (Zn+2 and/or Mg+2, for instance). In
any case, the final catalyst is a solid where small metal particles are strongly interacting with
the support matrix. In this type of solid, physicochemical properties such as acidity, basicity,
pore size distribution, specific surface area and exposed metal surface can be conveniently
tailored by choosing the appropriate composition and preparation conditions. Hence, there is a
large number of potential catalysts with special characteristics which can be used in different
hydrogenation reactions.
Among the hydrogenation reactions in which this type of catalyst has been used, we can
single out hydrogenation of alkynes, dienes, nitriles, nitro-compounds, carbonyl compounds
and aromatic compounds, as well as the synthesis of higher hydrocarbons and alcohols from
mixtures of CO, CO2 and H2. In all of these reactions a very important role is played by the
strong interaction existing between the metal phase and supports reached in the final catalyst
obtained using a LDH precursor as starting material.
For example, a strong interaction between metal nickel particles and Zn-containing
supports results in a diminution of hydrogenolytic sites in favour of hydrogenating sites. As a
consequence, the production of coke and methane diminishes and the selectivity to the partially
hydrogenated compounds in the hydrogenation of alkynes and dienes increases. The number of
hydrogenolytic sites can be reduced even further by the formation of bimetallic compounds
such as Ni-Co and Ni-Cu. The close contact between these elements, found from the very
beginning in the starting LDH precursor, plays a fundamental role in the production of these
bimetallic compounds at relatively low temperatures. The formation of these types of
bimetallic compound is desirable not only for the hydrogenation of alkynes and dienes, but also
for the production of primary amines from nitriles. In the latter case, the formation of a Ni-Co
bimetallic phase was found to be responsible for the diminution of the Nix atom arrangements,
responsible for the undesirable transamination reactions.
The acid-base nature of the support is also very important in the production of primary
amines by the hydrogenation of nitriles. Acidic supports must be avoided if the desired
products are primary amines. The appropriate selection of elements and preparation conditions
during the precipitation step makes it possible to obtain a final solid having important basic
properties, favouring the production of primary amines as against secondary and tertiary ones.
Thus, a Ni/Mg/Al system is preferred for this reaction instead of a system not containing
magnesium. Coprecipitation in appropriate conditions allows the preparation of a hydrated
precursor with a LDH type structure. This hydrated precursor can be converted, by calcination
and subsequent activation at the appropriate temperatures, into a catalyst where the metal phase
is highly dispersed in a Mg/Al oxide matrix with strong basic properties and high specific
surface area.
A very interesting example of a synergetic effect has been proposed in order to explain the
catalytic behaviour of Cu-Co-Zn-Al catalysts employed in the synthesis of higher alcohols. In
this case, the strong interaction between Cu and Co favours the generation of two types of
active site in intimate contact, one able of chemisorbing CO in a non-dissociative way and the
other of leading to a chain growth. The final result is obtaining alcohols with more than two
carbon atoms in the chain.
This type of catalyst can also be used in liquid phase hydrogenations, as in the case of the
synthesis of unsaturated alcohols from the corresponding α, β unsaturated aldehydes.
Cu-Zn-Al and Ni-Zn-Al catalysts, obtained by decomposition and activation of LDH
precursors, have shown very interesting properties in the hydrogenation of cynnamaldehyde
and citral in the liquid phase. An increase in activity and/or selectivity was observed compared
to Cu/SiO2 and Ni/SiO2 catalysts with the same metal loading. This behaviour was again
attributed to a strong interaction between the metal phase and the support matrix having a
superstoichiometric spinel-like crystalline structure. This strong interaction could have two
effects: 1) the generation of a more active metal surface by modification of the electron density
of the metal phase; 2) the generation of new types of site selective in the hydrogenation of the
functional carbonyl group.
In summary, there are numerous possibilities for the use of LDH solids as catalytic
precursors for hydrogenation reactions, both in liquid and gas phase. The main advantages of
using these types of precursor as starting materials are: 1) a high degree of homogeneity and
interaction between metal and support can be achieved in the final catalyst; 2) the formation of
intermetallic compounds at relatively low activation temperatures is possible; 3)
physicochemical properties, such as acid-base nature, pore size distribution and specific
surface area can be more or less easily tailored by an appropriate selection of the components,
their relative ratios and the preparation conditions. Each of these factors appears to play a very
important role in a great number of hydrogenation reactions, some of which have been
discussed in this chapter.
However, there remain a large number of other possibilities for which this type of solid
may be used as a catalyst for hydrogenation or dehydrogenation reactions, especially in those
cases where Cr-containing catalysts have to be replaced due to legal restrictions. On the other
hand, new formulations could also provide interesting alternatives to be tested in this type of
reaction. Some examples of these have been mentioned in this chapter. Finally, in spite of the
great advances made in this field, we still lack a complete understanding of these complex
catalytic systems. Such an understanding will require the use of a great number of
characterisation techniques, precisely because of the great complexity of the system. In some
cases it has been possible through the use of combined characterisation techniques to find good
relationships between bulk and surface properties and the catalytic behaviour of the system. In
other cases, greater efforts are required in order fully to understand how the particular structure
of these catalysts acts in the reaction in question.
ACKNOWLEDGEMENTS
The authors acknowledge financial support from DGES-MEC (Madrid, Spain, Grant
PB97-1020) and from Departamento de Educación y Cultura-DGA (Zaragoza, Spain, P07/98).
REFERENCES
1. L. Guczi, R.B. LaPierre, A.H. Weiss and E. Biron, J. Catal. 60 (1979) 83.
3. D. Tichit and A. Vaccari (Eds.), Appl. Clay Sci. 13 (1998).
4. F. Schüth and K. Unger in: G. Ertl, H. Knözinger, J. Weitkamp (Eds.), Handbook of
Heterogeneous Catalysis, Wiley-VCH, Weinheim, 1 (1997) 72.
5. C.J. Wright, C.G. Windsor and D.C. Puxley, J. Catal. 78 (1982) 257.
6. L.E. Alzamora, J.R.H. Ross, E.C.K. Kruissink and L.L. van Reijen, J. Chem. Soc.
Faraday Trans. 1 77 (1981) 665.
7. E.I. Ko in: G. Ertl, H. Knözinger, J. Weitkamp (Eds.), Handbook of Heterogeneous Catalysis,
Wiley-VCH, Weinheim, 1 (1997) 86.
8. J.C. Rodríguez, Ph.D Dissertation, Faculty of Science, University of Zaragoza, Spain,
June (1996).
9. J.C. Rodríguez, E. Romeo, A. Monzón, A. Borgna and A.J. Marchi in “Proc. XV
Iberoamer. Symp. Catal.”, Córdoba, Argentina, (1996) 909.
10. J.H. Edwards and A.M. Maitra, Fuel. Proc. Technology 42 (1995) 269.
11. M.C.J. Bradford and M.A. Vannice, Appl. Catal. A: General 142 (1996) 73.
12. M.C.J. Bradford and M.A. Vannice, Appl. Catal. A: General 142 (1996) 97.
13. J. Arauzo, D. Radlein, J. Piskorz and D.S. Scott, Energy and Fuels 8 (1994) 1192.
14. T. Zhang and M.D. Amiridis, Appl. Catal. A: General 167 (1998) 161.
15. A. Al-Ubaid and E.E. Wolf, Appl. Catal. 40 (1988) 73.
16. J.R.H. Ross, M.C.F. Steel and A. Zeine-Isfahani, J. Catal. 52 (1978) 280.
17. A. Bhattacharyya and V.W. Chang, Stud. Surf. Sci. and Catal. 88 (1994) 207.
18. Y.G. Chen and J. Ren, Catal. Lett. 29 (1994) 39.
19. J.P. Jacobs, A. Maltha, J.G.H. Reintjes, J. Drimal, V. Ponec and H.H. Brongersma, J. Catal.
147 (1994) 294.
20. J.A. Peña, J. Herguido, C. Guimon, A. Monzón and J. Santamaría, J. Catal. 159 (1996)
313.
21. O. Clause, B. Rebours, E. Merlen, F. Trifirò and A. Vaccari, J. Catal. 133 (1992) 231.
22. A.J. Marchi, J.I. Di Cosimo and C.R. Apesteguía, Stud. Surf. Sci. Catal. 75 (1993) 1771.
23. F. Trifirò, A. Vaccari and O. Clause, Catal. Today 21 (1994) 185.
24. F. Trifirò and A. Vaccari, Stud. Surf. Sci. and Catal. 67 (1991) 157.
25. Ph. Courty, D. Durand, E. Freund and A. Sugier, J. Molec. Catal. 17 (1982) 241.
26. A.J. Marchi, J.I. Di Cosimo and C.R. Apesteguía, Catal. Today 15 (1992) 383.
27. Ph. Courty and C. Marcilly, Stud. Surf. Sci. Catal. 16 (1983) 485.
28. A.J. Marchi, J.I. Di Cosimo and C.R. Apesteguía in “Proc. 9th Int. Cong. on Catal.”, M.J.
Phillips, M. Ternan (Eds.), Calgary, Canadá, 2 (1988) 529.
29. R.G. Oliver and P.B. Wells, J. Catal. 47 (1977) 364.
30. F. Medina, D. Tichit, B. Coq, A. Vaccari and N.T. Dung, J. Catal. 167 (1997) 142.
31. D. Tichit, F. Medina, B. Coq and R. Dutartre, Appl. Catal. A: General 159 (1997) 241.
32. D. Tichit and F. Fajula, Stud. Surf. Sci. Catal. 125 (1999) 329.
33. B. Coq, D. Tichit and S. Ribet, J. Catal. 189 (2000) 117.
34. F. Trifirò, A. Vaccari, G. Braca and A.M. Raspolli Galletti in “Catalysis of Organic
Reactions”, M.G. Scaros and M.L. Prunier (Eds), (1995) 475.
35. R.J. Farrauto and C.H. Bartholomew, “Hydrogenation and dehydrogenation of organic
compounds” in Fundamentals of Industrial Catalytic Processes, Blackie Academic &
Professional, London, (1997) 411.
36. J.R.H. Ross in G.C. Bond and G. Webb (Eds.), “Catalysis, Specialist Periodical Reports”,
Royal Society of Chemistry, London, 7 (1985) 1.
37. E.C. Kruissink, L.E. Alzamora, S. Orr, E.B.M. Doesburg, L.L. van Reijen, J.R.H. Ross
and G. van Veen in B. Delmon, P. Grange, P. Jacobs and G. Poncelet (Eds.), “Preparation
of Catalysts II”, Elsevier, Amsterdam, (1979) 143.
38. B. Höhlein, R. Menzer and J. Range, Appl. Catal. 1 (1981) 125.
39. UK Patent 1,462,059-60 (1973), to BASF AG
40. G. Fornasari, S. Gusi, F. Trifirò and A. Vaccari, Ind. Eng. Chem. Research 26 (1987) 1500.
41. L.S. Lobo, D.L. Trimm and J.L. Figuereido in “Proc. 5th Int. Cong. on Catal.”, Palm Beach,
1972, J.W. Hightower (Ed.), North-Holland, Amsterdam, 2 (1973) 1125.
42. G.A. Somorjai, L.L. Kesmodel and L.H. Dubois, J. Chem. Phys. 20 (1979) 2180.
43. J.H. Moses, A.H. Weiss, K. Matusek and L. Guczi, J. Catal. 86 (1984) 417.
44. J.C. Rodríguez, A.J. Marchi, A. Borgna and A. Monzón, J. Catal. 171 (1997) 268.
45. V. Rives, F.M. Labajos, R. Trujillano, E. Romeo, C. Royo and A. Monzón, Appl. Clay Sci.
13 (1998) 363.
46. E. Romeo, M.J. Sádaba, J.C. Rodríguez, C. Guimon, A. Borgna, A.J. Marchi and A.
Monzón in “Proc. XVI Iberoamer. Symp. Catal.”, Cartagena de Indias, Colombia, (1998)
313.
47. J.C. Rodríguez, C. Guimon, A. Marchi, A. Borgna and A. Monzón, Stud. Surf. Sci. Catal.
111 (1997) 183.
48. M.S. Kim, N.M. Rodríguez and R.T.K. Baker, J. Catal. 131 (1991) 60.
49. M.S. Kim, N.M. Rodríguez and R.T.K. Baker, J. Catal. 134 (1992) 253.
50. R.T.K. Baker, Carbon 27 (1989) 315.
51. R.T.K. Baker and J.J.Jr. Chludzinski, J. Phys. Chem. 90 (1986) 4734.
52. Monzón, E. Romeo, C. Royo, R. Trujillano, F.M. Labajos and V. Rives, Appl. Catal. A:
General 185 (1999) 53.
53. E. Romeo, Ph.D Dissertation, Faculty of Science, University of Zaragoza, Spain,

December (1999).
54. E. Romeo and A. Monzón, submitted for publication (2000).
55. A.J. Marchi and C.R. Apesteguía, Appl. Clay Sci. 13 (1998) 35.
56. P.H. Bolt, F.H.P.M. Habraken and J.W. Geus, J. Catal. 151 (1995) 300.
57. A.J. Marchi, Ph. D Dissertation, Faculty of Chemical Engineering, Universidad Nacional
del Litoral, Argentina, August (1988).
58. G.A. Somorjai in “Catalysis Design. Progress and Perspectives: The Building of Catalysts,
A Molecular Surface Science Approach”, L.L. Hegedus (Ed.), John Wiley and Sons. Inc.,
New York, (1987) 11.
59. G.A. Somorjai and J. Carrazza, Ind. Eng. Chem. Fundam. 25 (1986) 63.
60. J.P. Boitiaux, J. Cosyns and E. Robert, Appl. Catal. 49 (1989) 235.
61. S.M. Davis, F. Zaera and G.A. Somorjai, J. Catal. 85 (1984) 206.
62. P.P. Lankhorst, H.C. Jongste and V. Ponec in “Catalysts Deactivation. Studies in Surface
Science and Catalysts” (B. Delmon and G.F. Froment Eds.) Elsevier, Amsterdam, 6
(1980) 43.
63. F.M. Labajos and V. Rives, Inorg. Chem. 35 (1996) 5313.
64. F.M. Labajos, V. Rives and M.A. Ulibarri, Spectroscopy Lett. 24 (1991) 499.
65. V. Rives, M.A. Ulibarri and A. Montero, Appl. Clay. Sci. 10 (1995) 83.
66. K. Fuda, K. Suda and Matsunaga, Chem. Lett. (1993) 1479.
67. M. Del Arco, M.V.G. Galiano, V. Rives, R. Trujillano and P. Malet, Inorg. Chem. 35 (1996)
6362.
68. M. Del Arco, V. Rives, R. Trujillano and P. Malet, J. Mater. Chem. 6 (1996) 1419.
69. D. Jones and B.D. McNicol, “Temperature-Programmed Reduction for Solid Materials
Characterization”, Marcel Dekker, New York, (1986) 95.
70. M. Del Arco, P. Malet, R. Trujillano and V. Rives, Chem. Mater. 11 (1999) 624.
71. S.M. Auer, J.-D. Grunwaldt, R.A. Köppel and A. Baiker, J. Molec. Catal. 139 (1999) 305.
72. N. Jebarathinam, M. Eswaramoorthy and V. Krishnasamy, Appl. Catal. A: General 145
(1996) 57.
73. F. Medina, P. Salagre, J.E. Sueiras and J.L.G. Fierro, J. Molec. Catal. 68 (1991) L17.
74. M.J.F.M. Verhaak, A.J. van Dillen and J.W. Geus, Catal. Lett. 26 (1994) 37.
75. F. Medina, P. Salagre, J.E. Sueiras and J.L.G. Fierro, Appl. Catal. A: General 92 (1992)
131.
76. G. C. Bond and F. S. Stone, Stud. Surf. Sci. Catal. 101 (1996) 257.
77. F. Medina, R. Dutartre, D. Tichit, B. Coq, N.T. Dung, P. Salagre and J.E. Sueiras, J. Molec.
Catal. A: Chemical 119 (1997) 210.
78. D. Tichit, F. Medina, R. Durand, C. Mateo, B. Coq, J.E. Sueiras and P. Salagre,
“Heterogeneous Catalysis and Fine Chemicals IV”, H.U Blaser, A. Baiker and R. Princs
(Eds.), Elsevier Science B. V., Amsterdam (1997) 297.
79. N.T. Dung, D. Tichit, B.H. Chiche and B. Coq, Appl. Catal. A: General 169 (1998) 179.
80. Corma, V. Fornés and F. Rey, J. Catal. 148 (1994) 205.
81. T. Reichle, S.Y. Kangand and D.S. Everhardt, J. Catal. 101 (1986) 352.
82. J.L. Dallons, A. Van Gysel and G. Jannes in “Catalysis of Organic Reactions”, W.E. Pascoe
(Ed.), Marcel Dekker, New York (1992) 93.
83. P. Baumeister, H.-U. Blaser and M. Studer, Catal. Lett. 49 (1997) 219.
84. P.S. Kumbhar, J. Sanchez-Valente, J.M.M. Millet and F. Figueras, J. Catal. 191 (2000) 467.
85. T. Hirashima and O. Manabe, Chem. Lett. (1975) 259.

86. C.L. Castiglioni, M. Ferrari, A. Guercio, A. Vaccari, R. Lancia and C. Fumagalli, Catal.
Today 27 (1996) 181.
87. G.L. Castiglioni, C. Fumagalli, R. Lancia, M. Messori and A. Vaccari, Chemistry &
Industry (1993) 510.
88. G.L. Castiglioni, M. Gazzano, G. Stefani and A. Vaccari, “Heterogeneous Catalysis and
Fine Chemicals” in 3rd Int. Symposium, Poitiers, (1993) 143.
89. G.L. Castiglioni, A. Guercio, A. Vaccari and R. Lancia, J. Porous Mater. 2 (1995) 79.
90. R. Roesky, J. Weiguny, H. Bestgen and U. Dingerdissen, Appl. Catal. A: General 176
(1999) 213.
91. P. Gallezot and D. Richard, Catal. Rev.-Sci. Eng. 40 (1998) 81.
92. A.J. Marchi, F.S. Lauxmann, E.R. Benvenuto and C.R. Apesteguía in “XV. Simposio
Iberoamericano de Catálisis”, Córdoba, Argentina, 2 (1996) 1135.
93. A.J. Marchi, D. Gordo and C.R. Apesteguía, unpublished results.
94. A.J. Marchi, E.A. Maglione, E.R. Benvenuto and C.R. Apesteguía, in “10° Congresso
Brasileiro de Catalisis”, Salvador, Brasil, 1 (1999) 161.
95. S. Narayanan and R. Unnikrishnan, Appl. Catal. A: General 145 (1996) 213.
96. S. Narayanan and R. Unnikrishnan, J. Chem. Soc., Faraday Trans. 94 (1998) 1123.
97. M. Goncalves Coelho, A. Vaccari, M. Gazzano and J.M. Correa Bueno in “Natural Gas
Conversion II”, H.E. Curry-Hyde y R.F. Howe (Eds.), Elsevier Science B.V., (1994) 343.
98. S. Gusi, F. Pizzoli, F. Trifirò, A. Vaccari and G. Del Piero, Stud. Surf. Sci. Catal. 31 (1987)
753.
99. G. Fornasari, A.D. Huysser, L. Mintchev, F. Trifirò and A. Vaccari, A., J. Catal. 135 (1992)
386.
100. P. Grandvallet, Ph. Courty and E. Freud in “Proc. 8th Int. Congress on Catalysis”, Berlin, II
(1984) 81.
101. J.A. Dalmon, P. Chaumette and C. Mirodatos, Catal. Today 15 (1992) 101.
102. M. Tsuji, T. Kodama, T. Yoshida, Y. Kitayama and Y. Tamaura, J. Catal. 164 (1996) 315.
103. S. Narayanan, R. Unnikrishnan and V. Vishwanathan, Appl. Catal. A: General 129 (1995)
9.
104. S. Narayanan and R. Unnikrishnan, J. Chem. Soc., Faraday Trans. 93 (1997) 2009.
105. Y.Z. Chen, C.W. Liaw and L.I. Lee, Appl. Catal. A: General 177 (1999) 1.
Chapter 12
LAYERED DOUBLE HYDROXIDES AND THEIR

INTERCALATION COMPOUNDS IN PHOTO-CHEMISTRY
AND IN MEDICINAL CHEMISTRY
Umberto Costantino and Morena Nocchetti

Dipartimento di Chimica, Università degli Studi di Perugia, Via Elce di Sotto, 8, I-06123
Perugia, Italy.
Tel.**39.075.585.5565; Fax **39.075.585.5566; E-mail: ucost@unipg.it
INTRODUCTION
Many efforts have been made in the past few years to build up, into the interlayer region of
layered solids, supramolecular assemblies with special functionalities in the field of
photochemistry, electrochemistry, molecular recognition, chiral recognition and catalysis.1-5
Furthermore, the interlayer region of layered solids is starting to be used as a privileged
reaction vessel to perform chemical reactions between the guest themselves (polymerisation
reactions) or between the guests and the host (topotactic and grafting reactions).6 In addition,
the interlayer region of a layered solid may be considered a micro-container where guest
species are stored, protected from oxidation or photolysis, and withdrawn for use by a chemical
signal, i. e., by a deintercalation process.4 Other interesting reactions performed with layered
solids are "exfoliation reactions", that consist of separating the sheets of a layered compound
into individual lamellae. This goal is reached with the aid of specific intercalation or
de-intercalation reactions and leads to colloidal dispersion of lamellae. These dispersions can
be used to obtain materials with a very high specific surface area useful in catalysis or films and
thin layers with applications ranging from optical coating to microelectronics.7
As a consequence of these findings, research in intercalation chemistry has shifted from
fundamental aspects related to the determination of insertion mechanisms and of the
disposition of guest species in the interlayer region, to the preparation of new materials, not
obtainable through other synthetic procedures. Relatively “poor” materials such as natural
clays, synthetic layered phosphates and oxychlorides of transition metal ions, acquire a great
added value after intercalation of substrates with special functionalities. For example, insertion
436 Umberto Costantino and Morena Nocchetti
of dyes and chromophores into lamellar hosts has produced materials for use as tunable lasers,
fluorescent, and non linear optics devices.8
Layered Double Hydroxides (hereafter LDHs) compare favourably with other lamellar
hosts in the production of High-Tech materials for several reasons. First of all, they are
practically the only class of lamellar hosts consisting of positively charged layers balanced by
exchangeable anions (other are hydroxyacetates). Thus, functional organic or organo-metallic
species with anionic groups (carboxylic, phosphonic, sulphonic) which, in general, are much
more numerous than those with cationic groups, can be intercalated, via anion exchange
processes, only in this class of layered hosts. Furthermore, LDHs are a versatile class of
compounds in so far as it is possible to modulate their properties by changing the nature of the
divalent(s) and/ or trivalent cations in the brucite-like sheet and it is possible to alter the charge
density of the layers by altering the molar ratio of divalent to trivalent cation.9-13 These
considerations have induced many research groups to use LDHs as hosts for the intercalation of
species with magnetic, photochemical, and optical proprerties with the aim of immobilizing
these species on a solid support and/or of modulating their properties by confining them in a
constrained medium. It is also relevant to recall that hydrotalcites Mg-Al or Mg-Fe are used in
medicine as antiacids and against sideremia,9 respectively, and that they can be used as
drug-carriers, once the drug contains an anionic function and it has been inserted into the
interlayer region. In this chapter we shall try to rationalize the work done for the application of
LDHs in the field of photophysics and photochemistry and in medicinal chemistry, taking into
account important reviews published recently.8,12,13 For sake of clarity, we will initially recall
some fundamental concepts of photochemistry.
PHOTOPHYSICAL AND PHOTOCHEMICAL PROCESSES IN A

CONSTRAINED MEDIA
A full understanding of photo-processes requires the knowledge of the nature and
properties of electronic excited states. A molecule with all electrons spin-paired possesses a
total spin quantum number equal to zero and a spin multiplicity equal to one. Such an electronic
ground state is denoted by the symbol S0. When this molecule is suitably irradiated, electrons
are promoted to the LUMO frontier orbitals. The excitation does not involve a change in the
electron spin, the total spin quantum number is still zero and the excited state is a singlet state
denoted S1 , S2 and so on. If there exists some means of changing the spin of the excited
electron, an excited state is generated with a spin multiplicity of three, denoted as a triplet state
and abbreviated by the symbol T1, T2, etc. For the most part, photochemistry of chomophores
deals with the first excited singlet and triplet states.
A species that does not react with another substrate after excitation cannot persist in the
excited state over time and de-excitation processes occur, the excess of energy being released as
thermal (non radiative transitions) or radiation (radiative transitions) energy. Radiative
transition is called fluorescence if it involves a de-excitation process S1→ S0 and
phosphorescence if it originates in the de-excitation of an excited state of spin multiplicity
different from that of the ground state (i.e., T1→S0). Radiationless transitions involve processes
that are called Internal Conversion (IC), if they occur between states of the same spin
multiplicity, and Intersystem Crossing (ISC), if they occur between states of different spin
Layered Double Hydroxides and their Intercalation Compounds… 437
multiplicity. Figure 1 reports a Jablonsky diagram that is a useful schematic portrayal of the
possible transitions that may occur between the different energy levels of an excited species.14
The processes above described are essentially photophysical processes. In many instances
the light excitation of a species involves a chemical transformation with structural changes and
even with formation of new products. Light excitation may induce cis-trans isomerisation,
cycloaddition, electrocyclization, dissociation or formation of a tautomeric equilibrium. The
species that, as a consequence of these structural rearrangements, change colour (or in general
absorb light in a different spectral region) are called photochromic. Thus, photochromism may
be represented by the simple schemes A + hν1→ B; B +∆(hν2)→ A. The A species absorbs light
of suitable frequency, undergoes a structural change and is converted into the B species.
Photochromism is generally reversible in so far as the B species transforms into the A species
because of light (hν2) or heat (∆) absorption.15
Figure 1. Jablonsky diagram showing the relative positions of the electronic energy levels of a molecole. (IC,
internal conversion; ISC, intersystem crossing).
Another de-excitation path of a light-excited species is energy transfer to a reactive

molecule, usually denoted as a quencher, that extinguishes the luminescence emission. In the
condensed state, intermolecular energy transfer, at a relatively long range (up to 10 nm), can
take place between a species, called sensitiser, that is able to absorb the excitation light, reach a
singlet or triplet status and transfer part of the excitation energy to another species that emits
light. Energy transfer occurs because of the overlapping between the emission spectra of the the
sensitiser (the donor) and the absorption spectra of the acceptor. Energy transfer mechanisms
involve dipole-dipole interactions between the excited donor and the non excited acceptor. In
some cases the interaction between the donor and the acceptor allows an electron transfer with
the formation of an ionic couple. Many attempts have been made to stabilise the charge
separation, since the system obtained could be used for the storage and conversion of sunlight.
Finally, mention should be made of non linear optic effects shown by non centrosymmetric
species when interacting with light. These materials produce a new light field that is different in
wavelength or phase. For example, it has been found that many chromophores with a large
molecular hyperpolarisability present the phenomenon of second harmonic generation (SHG),
that is, they are able to convert a light signal into a ligth emission with frequency twice that of
the absorbed light. This effect is of great importance in the development of optical systems for
transmission and recording of data.16
All the above mentioned photophysical and photochemical effects of interaction of light
with matter are highly sensitive to the microenvironment of the excited chromophore, so that
the emission maximum of an excited species depends on its aggregation state. The fluorescence
maximum of a dye in the microcrystalline state is red-shifted in comparison to that of the same
dye in diluted solution. The energy difference between the fluorescence maxima has been
attributed to the change of the emitting state energy in the crystal (compared to the single
molecule) caused by coulombic or electron exchange type interactions of the excited species
with the neighboring unexcited molecules. Hence, one can control fluorescence,
photochromism, quenching, SHG and other properties of photoreactive species by organising
them into matrices with appropriate geometry and chemical environment. With the
development of inclusion chemistry and of supramolecular chemistry much research has been
done on the preparation of inclusion compounds or composites in which the chromophores are
immobilised in organic 17 (urea and thiourea, deoxycholic acid, cyclodextrins, micelles,
Langmuir-Blodgett films and liquid crystals) and inorganic 1 (zeolites and related materials,
lamellar solids and glasses) systems, in order to organise them into ordered structures, with a
given orientation and chemical environment. Among the various systems, lamellar solids have
a special role. At least two levels of organisation of guest species in lamellar solids may be
envisaged: the first refers to the organisation on the surface of the microcrystals, the second to
the arrangement in the interlayer region. Both depend on the nature and density of the active
sites and on the shape and size of the guest. Figure 2 reports a pictorial representation of the
possible arrangement of given species on the surface (see Fig. 2a and 2b) and in the interlayer
region of LDHs with different charge densities. Fluorescence emission of a chromophore
depends on its orientation and on the packing density in the interlayer region. These systems are
candidates for solid state tunable lasers. It is possible to impose a given orientation on the
molecular anions if the intercalation process is performed under an electric field and obtain
materials with SHG proprerties are obtained (Fig.2g). It is also possible to cointercalate two
different species, a donor and an acceptor, to obtain energy (or charge) transfer in the interlayer
to produce systems for energy storage and conversion (Fig.2h).
Finally, it is evident that these systems offer guest sites of relatively restricted dimensions
and therefore the photophysical and photochemical properties of the chromophore can be
modified for a variety of reasons including restricted molecular motion, limited access of
potential reactants or hydrophilic and hydrophobic effects. In turn, changes in the
photophysical properties may provide important information on the microenvironment of the
intercalated chromophore and thus on the microstructure of the host-guest system. Taking into
account the above mentioned concepts, a review of the synthetic procedures and the
characterisation of LDH-chromophore complexes recently published together with their
potential applications will be made.
SYNTHETIC STRATEGIES TO OBTAIN INTERCALATION COMPOUND

AND COMPOSITE LDH-CHROMOPHORES
The insertion of a guest species into the interlayer region of a layered host is a fascinating
phenomenon. The layers maintain their integrity but move apart in a direction perpendicular to
the layer plane to give room to the incoming guests. It is not conceivable that the layered
crystals open at once to accomodate the guest species. It is very likely that the layers bend and
curl at the edge of the micro-crystals and the process goes on towards the core of the
microcrystals with an advanced phase boundary mechanism. The rigidity of the layers will thus
play an important role in the intercalation mechanism and in the energetics of the process.
Layered crystals with charged layers contain exchangeable counterions in the interlayer region
and the intercalation of a given guest will require an ion exchange reaction between the two
species. Layered double hydroxides possess relatively rigid layers (the rigidity parameters has
been evaluated to be 4.8 18), positively charged as a consequence of the isomorphous
substitution of a divalent cation by a trivalent cation, and contain exchangeable anions.
The first way to obtain LDH-chromofore intercalated compounds is therefore to perform
an anion exchange reaction. In designing the reaction, attention should be given to the nature of
the counterion originally present in the LDH. Since chromophores are much bulkier anions
than common counterions, it is important to choose a counterion that is weakly held and that
determines a large gallery height to facilitate the diffusional processes. For the most common
counterions, the selectivity scale 19 follows the order CO32- > SO42- >>OH- >F->
Cl->Br->NO3->ClO4-. LDHs containing nitrate or perchlorate anions are, therefore, the most
suitable precursors for the uptake of anionic dyes. They have also a relatively higher interlayer
distance. LDHs containing chloride anions are also frequently used. LDHs in the carbonate
form are excellent precursors for investigating the surface uptake of the chromophores, since
the interlayer carbonates are not involved in the exchange process, whereas the surface
carbonates or hydrogencarbonates are easily replaced by the dye.
To study the intercalation mechanism it is worth constructing the anion exchange
isotherm,20 in order to obtain the relative selectivity coefficient and to follow the structural
changes occurring at different degrees of exchange, by recording the X-ray diffraction powder
patterns of samples with different loadings. As an example, Figures 3a and 3b show the uptake
curve of methylorange anions in Zn-Al-Cl LDH and the PXRD patterns of samples at different
exchange percentages. It may be seen that the dye is exchanged with high selectivity and that
the ion exchange process occurs with a first order phase transition from the Cl-phase (interlayer
distance 7.74 Å) to the methylorange-phase (interlayer distance 24.2 Å).21
Figure 2. Possible arrangement of given species on the surface (a)and (b) and in the interlayer region of LDHs.
Case (g) refers to an oriented disposition of guests; case (h) to the cointercalation of two different guests (e.g.
donor-accepter).
If high steric hindrance prevents direct exchange, two other procedures may be used to
obtain the intercalation compound. The first procedure involves direct synthesis by
coprecipitation, the second procedure is concerned with the so called “memory effect” of
hydrotalcites.
The direct synthesis procedure requires the precipitation of the LDHs in the presence of the
anionic form of the chromophore. To succeed in this, M(II) and M(III) cations must be
introduced as salts of anions with low affinity for the host (nitrate, chloride, acetate) and the
presence of strongly held anions such as carbonates or sulphates must be carefully avoided.
Coprecipitation is performed at controlled pH (between 9 and 10) with the addition of NaOH
solution to the solution containing the metal cations and the chromophores. The M(III)/M(II)
molar ratio and hence the charge density of the obtained LDH must be chosen according to the
size and charge of the chromophore. The cross section of the guest should not exceed the free
area around each charge on the layer plane in order to avoid the “covering effect” and to obtain
the fully converted LDH. Well crystallised samples are formed when the guests have a high
self-assembly tendency. In other cases a hydrothermal treatment of the intercalates formed may
improve the crystallinity of the products.22
The second procedure, typical of Mg-Al-CO3 LDH, concerns the possibility of
reconstructing the layered structure when conctacting the material previously calcinated at
300-500°C in water or in a solution of given anions.23 Recent results indicate that at these
temperatures the original hydrotalcite is converted into a mixture of magnesium and aluminum
oxides and the oxides have ”memory” of the original structure.24 In fact, in the presence of
water they regenerate the double hydroxides in the form of brucite-like sheets and the positive
charges are balanced by OH- ions. If the reconstruction is obtained in a solution containing
anions, these could be incorporated to produce intercalation compound of LDH with this anion.
An advantage of this method in comparison with the direct synthesis procedure is that the
incorporation of competing inorganic counterions is avoided and that the chromophore may be
present in solution as a free acid. Possible contamination by carbonates is still a problem and
the whole procedure must be carried out in N2 atmosphere. The procedure is not general.
Among LDHs only Mg-Al and in some instances Zn-Al show the “memory effect” in a manner
so clean as to obtain the intercalation compound as a single phase.
Figure 3. (a) Methylorange uptake of [Zn0.67Al0.33(OH)2]Cl0.33·0.6H2O as a function of the amount of

methylorange offered in solution. (b) X-ray powder diffraction patterns of Zn-Al-LDH samples having
increasing methylorange exchange percentage: (a) 4%, (b) 9%, (c) 46%, (d) 70%, (e) 84%. Reprinted from U.
Costantino, N. Coletti, M. Nocchetti, G. G. Aloisi, F. Elisei, Anion exchange of methyl orange into Zn-Al
synthetic hydrotalcite and photophysical characterization of the intercalates obtained, Langmuir 15 (1999)
4454, © 1999, with permission from The American Chemical Society.
Table 1 summarises the literature data on the immobilation of different chromophores in

LDHs. The table shows the type of host, the type of guest, the synthetic procedure used and,
where available, the composition and the main photophysical and photochemical behaviour. It
can be seen that the above mentioned synthetic strategies have been employed to obtain the
incorporation into LDH of different types of chromophores. It is also interesting to note that, in
spite of the large variety of LDHs presently available, the choice is limited to Mg-Al and Zn-Al.
Both these LDHs are easily obtained with a good crystallinity degree, show the “memory
effect” and are white. Some attention has also been paid to [LiAl2(OH)6]- which consists of
sheets of aluminium octahedra with vacancies filled by lithium ions.9
In the following part, with reference to Table 1, the properties of the intercalation
compounds or of the composites prepared will be discussed in relationship to the nature of the
guest and hence of the photoprocesses investigated.
LDH - ANIONIC DYE INTERCALATION COMPOUNDS AND THEIR

FLUORESCENCE PROPERTIES
Relatively few papers deal with the preparation of composites containing anionic dyes. For
the reader convenience, figure 4 shows the structural formula of the dyes considered. Miyata
determined the anion exchange isotherm Cl-/Naphthol YellowS2- in a Mg-Al LDH. He found
that the dye is exchanged with high selectivity and that it is accommodated in the interlayer
region as a divalent anion with the main axis almost perpendicular to the layer plane. He
suggested the use of LDH for the removal of this acid dye from waste solutions.19
Figure 4. Structural formula of indicated dyes.

Table 1. Layered Double Hydroxides-chromophores intercalation compounds and composites. The synthetic procedure, composition and
photofunctions of the obtained systems are also reported. References in round brackets.
LDH HOST GUEST(S) SYNTHETIC PROCEDURES COMPOSITION PHOTOFUNCTIONS (REFS)

Mg/Al Naphthol Yellow S Anion exchange 100% of AEC (19)
Mg/Al Indigo carmine, New coccine Direct Synthesis and Anion exchange 75% of AEC (25)
Zn/Al Methyl Orange Anion exchange 94% of AEC Fluorescence (21)
Zn/Al Fluorescein Anion exchange 67% of AEC Fluorescence (26)
Zn/Al Phenolptalein Anion exchange 54% of AEC Fluorescence
Mg/Al and Zn/Al Substituted Rhodanine and Xanthene dyes Reconstruction 48-100% of AEC Fluorescent Probe (27)
Mg/Al Ruthenium polypyridine complex Direct Synthesis 27% of AEC Luminescent Probe (28)
Mg/Al Dioxorhenium (V) ions Direct Synthesis 15% of AEC Excited-state properties (29)
Mg/Al Derivative Porphyrin Anion exchange 81% of AEC (30)
Mg/Al Derivative Porphyrin Anion exchange ≈ 100% of AEC Hole burning technology (31)
Mg/Al Co(II) phtolocyanine Reconstruction Photocatalysis (33,34)
Mg/Al Co(II), Cu and Zn(II) phthalocyanine Reconstruction 40-99.5 µmol/g Photooxydation of sulfur-containing
compounds (35)
Mg/Al Co(II) and Zn(II) phthalocyanine Reconstruction 40 µmol/g Photooxydation of sulfide and
thiosulfate (photocalysis) (36)
Mg/Al Mn(II) phtolocyanine Reconstruction Photocatalysis (37)
Li/Al/Myristate Porphyrin-TiOx In situ hydrolysis of Ti butoxide Photochemical Assemblies (38)
Li/Al/Myristate Pyrene Absorption Photoluminescence (39,40)
Mg/Al Na - reduced Fullerene Anion exchange 1% of AEC Photoluminescence (42)
Mg/Al-Dodecylsulfate Fullerene Absorption Photoluminescence (41)
Li/Al 2-nitrohyppuric acid Nonlinear optical properties (43)
Mg/Al CdS-ZnS Anion exchange Precipitation “in situ” Photocatalysts (44)
Mg/Al Cinnamate Anion exchange Photodimerization and
Photoisomerization (45)
Mg/Al Arylacrylate, p-phenilcinnamate, 1-naphthylacrylate, Anion exchange ≈ 40% of AEC Photochemical cycloaddition
Stilbenecarboxylate (46,47)
Mg/Al Aromatic Ketocarboxylates Anion exchange 68-92% of AEC Photolysis (Norrish type reactions)
(48)
Mg/Al 4-benzoylbenzoate, 4-(2-phenylethenyl) benzoate Anion exchange ≈ 100% of AEC Photochemical cycloaddition
(49,50)
Mg/Al 4-vinylbenzoate, m- and p-phenylenediacrylates Anion exchange 32-71% of AEC Photopolymerization (51)
Mg/Al/p-toluensulfonate Indolinespirobenzopyran Reconstruction 1.3-7% (w/w) (52)
Zn/Al/p-toluensulfonate
Indigo Carmine (i.c.) and New coccine (n.c.), two dyes which are used as colour additives
for food, have been intercalated in Mg-Al LDH by anion exchange and by the direct synthesis
procedure. The PXRD patterns of the samples obtained following both procedures are very
similar. The anionic dyes were easily exchanged, starting from the nitrate (or chloride) form of
the LDH, probably because of the high tendency of these two dyes to be aggregated as a
monofilm of oriented species in the interlayer region. The values of the interlayer distance
(22.4 Å for i.c. and 16.5 Å for n.c.) support this hypothesis. The U.V. and visible reflectance
spectra of the intercalation compounds are similar to those of the pure dyes in the solid state,
suggesting that the guests are packed in the interlayer region in a manner similar to that of the
solids.25
The azoic dye methylorange has been intercalated in Zn-Al-Cl LDH by anion exchange
procedure and the ion exchange mechanism has been studied in detail (see figure 3a and 3b). A
knowledge of the structure of the host and of the composition and interlayer distance of the
intercalation compound has allowed the calculation of the packing coefficient of the dye in the
interlayer region, expressed as the ratio between the volume occupied by the methylorange
anions and the volume available to them in the interlayer space. The packing coefficient, 0.48,
is very close to that of methylorange in the solid state (0.55). In addition, a computer-generated
model of the intercalation compound has been proposed (see figure 5). The study of
fluorescence emission spectra of samples containing the chromophore on the surface of the
microcrystals or intercalated (in the presence or in the absence of co-intercalated water
molecules) has shown a considerable red shift of the λmax of fluorescence emission when
compared with the λmax of the free dye (see figure 6). If the fluorescence of methylorange
microcrystals is considered, a wide range of wavelengths (400-850 nm) is covered. These
characteristics are of interest for the design of materials for tunable dye lasers. Fluorescence
response is highly sensitive to the microenvironment of the dye. It can be seen from figure 7
that the fluorescence maximum shifted to the red as a consequence of the dehydration of the
sample and hence of the increase in the packing coefficient of the dye.21
Fluorescein and phenolphtalein, two xantenic dyes, are very different in shape and size
from methylorange. In addition, they behave as divalent anions at pH values of 8-9. Because of
their large size, intercalation by anion exchange required the use of precursors with a high
interlayer distance. The perchlorate form, [Zn0.67Al0.33(OH)2] [ClO4]0.33 0.6 H2O, with an
interlayer distance of 11.0 Å has been used to intercalate fluoresceinate anions. The anion
exchange reaction occurs with a first-order phase transition from the ClO4- phase to a phase
containing 0.11 mol of fluoresceinate per mol of the host and an interlayer distance of 16.5 Å.
The benzoate form of Zn-AL LDH, with an interlayer distance of 15.5 Å, has been used to
exchange phenolphtalein anions. The intercalation compound obtained contains 0.09 mol of
guest per mol of host and has an interlayer distance of 19.4 Å. The surface uptake was
investigated by equilibrating [Zn0.67Al0.33(OH)2] [CO3]0.165 0.4H2O with diluted solutions of the
dyes. Only carbonates present on the surface of microcrystals were exchanged.
Computer-generated models, based on the structure of the host, composition and interlayer
distance of the intercalation compounds and van der Waals dimensions of guests, showed that
both fluorescein and phenolphtalein anions are incorporated in the interlayer region as a
bi-layer of species with the main axis parallel to the layer plane.26
The photophysical characterisation was performed by determining the absorption,
excitation and fluorescence spectra and fluorescence lifetimes of the dyes under different
experimental conditions. The emission properties of the guests, adsorbed or intercalated in the
inorganic host, have been compared to those of dyes as pure solids or dissolved in solution.
Again, the emission fluorescence spectra of intercalated dyes are shifted toward that of dyes in
the solid state, while those of dyes adsorbed on the surface of the microcrystals are closer to
those of free dyes in solution. There is thus the tendency of the dyes to be arranged in the
interlayer region in a manner similar to that present in the crystals of the pure dyes. However,
the intermolecular interactions responsible for the large red shift observed when the
fluorescence maximum of the dye in solution is compared with that of the dye in the solid state,
are lower in the intercalated dyes. Diffuse reflectance laser flash photolysis experiments
performed with the fluorescinate systems has allowed the determination of absorption spectra
and decay lifetimes of the triplet state of the dye bound to the inorganic matrix.26
It should be finally mentioned the intercalation of a substituted Xanthene and Rhodamine
dyes (see Fig. 4g and 4h respectively) into Zn-Al-LDH by the reconstruction procedure.
Photophysical studies on these composites have not been reported.27
Figure 5. Computer-generated models showing the most probable arrangement of methylorange anions
between the LDH layers. (a) Hydrated sample; (b) anhydrous sample. Reprinted from U. Costantino, N. Coletti,
M. Nocchetti, G. G. Aloisi, F. Elisei, Anion exchange of methyl orange into Zn-Al synthetic hydrotalcite and
photophysical characterization of the intercalates obtained, Langmuir 15 (1999) 4454, © 1999, with permission
from The American Chemical Society.
Figure 6. Normalised emission spectra of methyl orange (1) in ethanol solution, (2) absorbed on Zn-Al-LDH
(sample a), (3) intercalated in Zn-Al-LDH (sample e) and (4) pure solid (λexc = 334 nm). Reprinted from U.
Costantino, N. Coletti, M. Nocchetti, G. G. Aloisi, F. Elisei, Anion exchange of methyl orange into Zn-Al
synthetic hydrotalcite and photophysical characterization of the intercalates obtained, Langmuir 15 (1999)
4454, © 1999, with permission from The American Chemical Society.
Figure 7. Normalised fluorescence spectra of methyl orange intercalated in Zn-Al-LDH (94%); anhydrous (full
circles) and hydrated (open circles) samples (λexc = 434 nm). Reprinted from U. Costantino, N. Coletti, M.
Nocchetti, G. G. Aloisi, F. Elisei, Anion exchange of methyl orange into Zn-Al synthetic hydrotalcite and
photophysical characterization of the intercalates obtained, Langmuir 15 (1999) 4454, © 1999, with permission
from The American Chemical Society.
LDH INTERCALATES CONTAINING LUMINESCENT INORGANIC

COMPLEXES AND THEIR PHOTOPHYSICAL PROPERTIES
The photochemistry of many complexes of transition metal ions with organic ligands has
been thoroughly investigated to produce supramolecular metallocatalysts and supramolecular
photochemical devices. Among these complexes, [Ru(bpy)3]2+ plays a special role. The
complex is thermally stable and its photochemical excitation involves the promotion of an
electron from a molecular orbital of essentially metal character to one of an essentially ligand
character, after which its oxidation is possible. Many composite systems have been developed
in which the ruthenium complex has been used for the photochemical decomposition of water
for solar energy conversion and storage. Furthermore, the excited state of the Ru-bpy complex
has a relative long lifetime that allows its complete photochemical characterisation
(steady-state and time resolved luminescence studies) and a study of the effect of the chemical
micro-environment on the fluorescent properties. The luminescence of [Ru(bpy)3]2+
incorporated in ion exchange resins, micelles, glass, zeolites and layered materials has been
investigated and information at nanolevel scale has been obtained.1
The intercalation in LDHs requires the introduction of ligands with anionic functions.
Figure 8a shows the structural formula of a Ru(II) complex with phenanthroline ligand
functionalised with sulphonic groups. The [Ru(BPS)3]4-luminescent complex has been partially
incorporated into Mg-Al-LDH by the co-precipitation procedure and subsequent hydrothermal
treatment. The product obtained has the formula [Mg2.98Al1.04(OH)8]Cl0.72 (Ru(BPS)3)0.07 and
an interlayer distance of 22 Å. This value can be predicted by the presence, in the interlayer
region, of a monolayer of [Ru(BPS)3]4- units with their C3 axes normal to the layer plane.
However, the Ru-complex moieties are not randomly distributed among the chlorides anions,
but seem to be segregated at the edges of the crystallites. In fact, the emission decay profiles of
the luminescent intercalate display multiexponential form due to excited-state self-quenching
processes. Co-intercalation with the analogous Zn(BPS) complex causes a dilution of the
emitting Ru complex with a diminution in the self quenching reaction rate.28
High-valent transition metal-oxo compounds such as trans-dioxorhenium(V) complexes
have a highly emissive excited state. The Re(V) complex, shown in Figure 8b, has been
intercalated by the co-precipitation procedure into Mg-Al-LDH. The interlayer distance of the
intercalate (9.5Å) is consistent with the effective C3 axis of the pseudo-octahedral
[ReO2(CN)4]3- complex perpendicular to the layers. The complex does not show luminescent
properties, in contrast to the strong fluorescence observed when a positive charge Re-complex
is intercalated in hectorite. Probably, fast non radiative transitions take place in the LDH
intercalate because the emitting ReO2+ core interacts, via hydrogen bonds, with the hydroxyl of
the layers.29 This is a significant example of the role of host-guest interactions on the excited
state properties of an intercalated chromophore.
PORPHYRIN AND PHTALOCYANINE-LDH INTERCALATION

COMPOUNDS AND THEIR PHOTO REACTIVITY
Porphyrins, phtalocyanines and their metallo complexes are of extraordinary importance in
many fields from biology to material science. Metalloporphyrins are responsible in
cytochromes for electron transport around the cell and in myoglobins and haemoglobins for
molecular oxygen transport around the whole organisms. Phtalocyanines and their metallo
complexes are used as dyes and efficient catalysts. They find application in material science for
non linear optical devices, optical data storage, rectifying devices and as electrochromic
substances. In addition, they are used in various processes involving visible light such as photo
oxidation reactions in solution and photosensitizers. The organization of porphyrins and
phtalocyanines in a constrain media, their proximity and relative orientation, may play an
important role in modulating their attractive properties and much work has been done to
intercalate (or include) these species in a variety of organic and inorganic hosts matrices.
Figure 8. Structural formula of some luminescent complexes.
Incorporation into LDHs requires the functionalisation of the molecules with anionic
groups. The structural formulae of the derivative porphyrin and phtalocyanines employed are
reported in Figure 9. Anionic (sulfonic and carboxylic) tetraphenylporphyrines have been
incorporated with the three mentioned procedures into the interlayer region of Zn-Al-LDHs
having different charge density. The interlayer distance of the products obtained ranges from
18.54 to 22.91 Å, indicating that porphyne anions can arrange in the interlayer region with
different orientations according to the layer charge density of the particular LDH.30
Figure 9. Structural formula of indicated porphyrin and phtalocyanines.
The anion of tetrasodium tetra(4-sulfonatophenyl) porphyne has been intercalated into a

Mg-Al-Cl LDH by the anion exchange procedure. Almost complete replacement of the Cl-
counter-ions takes place and the interlayer distance of porphyrin-LDH intercalation compound
was found to be 22.4 Å. This value is consistent with a model where the intercalated porphyrin
anions are arranged in the interlayer with their molecular planes perpendicular to the hydroxide
layers. The authors suggested the use of this intercalation compound in the photochemical hole
burning technology.31 The analogous tetra(4-carboxyphenyl) porphyrin has been intercalated
into Mg-Al and Zn-Al LDHs by the reconstruction procedure. The compounds obtained were
contaminated by the presence of a small amount of the carbonate phase, but the interlayer
distance of the porphyrin phase was similar to that of the corresponding sulfonate derivative.27
It is interesting to note that the intercalation by anion exchange of Ni(II)
phtalocyaninetetrasulfonate ions into [Li Al2(OH)6]Cl produces an increase of the interlayer
distance of 5.81Å, indicating that the phthalocyanines anions lie with their main plane parallel
to the aluminate layer.32
Cu(II) and Co(II) phtalocyanine tetrasulfonates have been intercalated into Mg-Al LDH by
the reconstruction procedure. The interlayer distance of the intercalation compounds is about
23 Å, suggesting again that guests are arranged with the molecular plane perpendicular to the
sheet. ESR spectra of the Co-derivative seem to confirm the orientation deduced from the
PXRD patterns.33
Catalytic studies indicate that these systems are efficient biomimetic catalysts. The Co
phtalocyanine-LDH complex has been found to be an excellent heterogeneous catalyst for
selective autoxidation of 2,6-di-tert-butylphenol in the presence of activated oxygen. The
catalyst was still active after 3200 catalytic turnovers.34 Zn and Co phtalocyanines intercalated
into Mg-Al LDH by the reconstruction procedure have been used for the oxidation and
photooxidation of tiols, sulfides and thiosulfates.35,36 Mn(III)
tetrakis(4-sulfonatophenyl)porphyrin intercalated by the reconstruction procedure into
Mg-Al-LDH was found to be a good catalyst for cyclooctene epoxidation.37
Li-Al-LDH, intercalated with myristate anions, [Li Al2(OH)6](OOC(CH2)12CH3), has been
used to support a photochemical assembly for the photolysis of pollutants. The assembly,
schematically depicted in Figure 10, consists of Zn-tetrakis(4-carboxyphenyl) porphyne and
semiconducting TiOx particles dispersed in myristate anions. Titanium(IV) butoxide was
intercalated into the hydrophobic interlayer of the Li-Al-myristate. The interlayer distance
increases from 21 to about 25 Å. Particles of TiOx were grown “in situ” by exposing the
myristate -Ti(IV) butoxide composite to a controlled hydrated environment in order to slowly
hydrolyze the butoxide. The metallo-porphyrin was then introduced into the interlayer region
of the Li-Al-LDH by exchanging some of the myristate anions with
Zn-tetrakis(4-carboxyphenyl)porphyne anions. At the end of this procedure the composite
contained 2% w/w of Zn and 6% w/w of Ti. The authors were not able to distinguish between
TiOx particles grown in the interlayer and those present on the surface of the LDH crystallites.
However, they found that porphyrin is intercalated with the plane perpendicular to the layers.
Furthermore, the emission spectra of the composite were very similar to those of the
Zn-porphyrin in diluted solution, where no aggregation of porphyrin species occurs. This is a
clear evidence that the Zn-porphyrin anions are randomly dispersed in the Li-Al-LDH-
myristate phase. The efficiency of the photochemical assembly was tested with the
photoreduction of viologens (a cationic viologen, heptylviologen, and a zwitterionic viologen,
propylviologen sulphonate) in the presence of EDTA as sacrifical electron donor. The detection
of viologen radical in solution was mainly attributed to the sensitised action of porphyrin on
semiconducting titanium oxide particles.38
Figure 10. Scheme of the LDH photochemical assembly. Adapted from Ref. 38.
OTHER LDH-COMPOSITES WITH PHOTOLUMINESCENCE AND NON

LINEAR OPTIC PROPERTIES
Interesting substrates with photoluminescence, non linear optics or semiconducting
properties have been intercalated or adsorbed in LDHs and the photophysical behaviour of the
nanocomposites obtained have been investigated.
The Li-Al-LDH exchanged with myristate anions (or exchanged with hexanoate anions)
has the ability to partition pyrene from a methanol / water solutions containing this policyclic
aromatic compound. No absorption of pyrene was observed in LDH exchanged with the
dicarboxylate succinate anions. This observation suggests that the uptake of pyrene requires a
hydrophobic environment having some degree of flexibility. In these conditions also the pyrene
molecules retain enough mobility to form excimers, detected from the study of the emission
spectra.39,40
Fullerene molecules have great interest in the field of chemistry, physics and material
science. Several studies deal with the immobilation of these molecules, as such or suitably
functionalized, in different host matrices, with the aim to study the effects of the
microenvironment on the optoelectronic and chemical properties of the molecules and to
prepare materials for application in optical and electronic devices. Attention of researchers has
been also addressed to LDHs, and two different routes have been followed to incorporate C60
molecules into Mg-Al-LDH. In the first route, C60 molecules have been incorporated by
dissolving the molecule into the hydrophobic interlayer region of LDH intercalated with
dodecilsulfate. After heating under vacuum the resultant material to decompose the dodecyl
sulfate, C60 molecules were sandwiched in between the hydroxide layers.41 In the second route,
fullerene was reduced with sodium to form anionic sites on the molecule and the reduced
species were exchanged in hydrotalcite. The presence of a low intensity reflection at d =16.2 Å
in the PXRD pattern of the material obtained seems to confirm that a small amount (about 1%)
of anionic fullerene has been intercalated. Strong photoluminescence of C60 incorporated
between LDH layers has been observed. This phenomenon has been attributed to the coulombic
interaction of reduced fullerene and the positive charges of the matrix. This interaction alters
the photophysical properties of the guest, reduces the inhibition of the electron transition and
enhance the fluorescence emission.42
Non linear optical (NLO) materials provide the basis for an array of active optical devices
under development in high-tech industries. A NLO chromophore should possess a high
molecular hyperpolarizability and should be aligned in a non-centrosymmetric assembly, in
order to present non linear phenomena such as second harmonic generation. Intercalation
compounds in which the non centrosymmetric guests give rise to ordered arrangements of
dipoles shall present the SHG phenomena. 2-nitrohyppuric acid, NO2C6H4 CONHCH2COOH,
does not present SHG in the solid state because of packing effects. It has been however found
that the intercalation compound of Mg-Al with nitrohyppuric acid exhibits second harmonic
generation: 532 nm radiation from incident 1064 nm radiation.43 Very probably, nitrohyppuric
moieties are accommodated in the interlayer region as a monolayer of oriented species to give
rise a bulk dipole moment. Intercalation compounds showing SHG effects could be obtained if
an external electric field is applied to the system during the intercalation procedure of a
non-centrosymmetric chromophore. The guest species will be, in fact, aligned in the interlayer
region with the orientation imposed by the electrical field.
The interlayer region of hydrotalcite has also been used to incorporate photo conducting
particles of CdS and or of mixtures of CdS and ZnS particles. The co-intercalation of the
Cd(EDTA)2- and S2- anions allowed the “in situ” formation of the CdS (or CdS together with
ZnS) particles. The composites, irradiated with visible light in the presence of sodium
thiosulfate as sacrificial donor, were capable of efficient hydrogen evolution.44
ORGANIC PHOTOCHEMISTRY INSIDE THE LDH

INTERLAYER REGION
Light was recognized early as powerful reagent for the development of organic synthesis.
As already described, the excitation of a substrate by irradiation can produce photolytic
breakage of bonds, with the formation of radicals and induces photoionization, isomerization or
cyclization. It also greatly enhances the rate of reactions even at low temperatures. A key
problem of organic photochemists is to perform photochemical reactions with high selectivity.
The use of monochromatic radiations, or better, a laser source, allows the excitation of specific
states with high precision and thus the direction of the reaction path. Another way to reach
specificity and stereoselectivity is to perform photoreactions in organized media.17 Numerous
papers describe photoreactions in different host systems (urea and thiourea, cyclodextrins,
micelles, zeolites, layered solids). The interlayer region of LDHs provides a particular
microenvironment for reaction of photoactive species and classical photodimerization,
photoisomerization and photocycloaddition reactions in LDHs have been reported.
The reactions of trans-cinnamic acid in the crystalline state are well known examples of
[2+2] photodimerization and such reactions are strictly controlled by the packing arrangement
of the molecules in the crystal. It was thus interesting to study the photodimerization of
cinnamate anions when accommodated in the interlayer region of LDH, to compare the results
with those obtained from solid sodium cinnamate and also to have information concerning the
arrangement of cinnamate anions inside the hydroxides. The anions have been intercalated into
a Mg-Al-Cl LDH by the anion exchange procedure and it has been found that both
isomerization and dimerization of the cinnamate anions occurs between the layers. The reaction
path and the stereoselectivity suggest an arrangement of intercalated anions similar to that in
the solid state.45 [2+2] photocycloaddition of sodium arylacrylates may give rise to a mixture of
syn head-to-head, anti head-to-head and syn head-to-tail cyclodimers (see Scheme 1). Various
arylacrylates have been intercalated into Mg-Al-LDH by the ion exchange procedure and
intercalation compounds have been irradiated with a Hg-lamp. It has been found that
p-phenylcinnamate yielded almost exclusively head-to-head dimers, while
phenylethenylbenzoates gave significant amounts of head-to-tail dimers. The product
selectivity was shown to be controlled by the packing of the anions in the interlayer.46 By using
Mg-Al-LDHs with different charge density, it has been possible to change the packing density
of the anions in the interlayer region and to change the selectivity. Low Al-content (x =
0.15-0.20) determines a relatively high distance between the positive charges and a low
packing density which favours the formation of anti head-to-head dimers, while syn
head-to-head dimers are mainly formed in LDH with high Al-content.47
Scheme 1
Other photoreaction widely investigated is the unimolecular rearrangement of aromatic

ketocarboxylates (Norrish type II reaction) reported in Scheme 2. In type II reactions, the
1,4-biradical obtained from the excited triplet state leads to cyclization to cyclobutanol or
elimination to olefin and ketone via intramolecular γ-hydrogen abstraction. The ratio between
cyclization and elimination products is significantly sensitive to the environment in which the
ketone molecules are accommodated.
Scheme 2
Aromatic ketocarboxylates (p-CH3C6H4CO(CH2)nCO2-, n = 4-10) were intercalated both

by ion exchange and reconstruction procedures in Mg-Al-LDH. The degree of exchange
increases with the increase of n and the interlayer distance of the intercalation compounds
ranged from ca. 26 to 31 Å. It is likely that the ketocarboxylates are accommodated in the
interlayer region as a monofilm of interdigitated species (see Figure 11). U.V. irradiation of the
intercalation compounds produces p-methylacetophenone and alkenecarboxylates (elimination
pathway) and cyclobutanols (cyclization pathway) in different ratios according to alkyl chain
length. The formation of cyclized products was substantial for n=4 and n=5 and negligible for
ketocarboxylates with longer chain length. Type II elimination products are constantly formed
as major products. These results are different from those obtained in aqueous media, where the
ratio of cyclization and elimination products is almost constant whichever of the chain length.
These different results imply that the stereochemistry of 1,4-biradicals is significantly governed
by the layered constrained media.48
Figure 11. Intercalation of ketocarboxylate in the interlayer of LDH. Adapted from Ref. 48.
Other examples of photoreactions performed in the interlayer region of Mg-Al-LDH

concern the photocycloaddition of 4-benzoylbenzoate with unsaturated carboxylates and the
photochemical hydrogen abstraction of aliphatic carboxylates by benzoylbenzoate.49 In both
cases the reagents were co-intercalated in LDH by ion exchange procedures. Photoirradiation
of a mixture of 4-benzoylbenzoate and 4-(2-phenylethenyl)benzoate yielded regioselectively
oxetanes, while hydrogen abstraction from CnH2n-1COO- co-intercalated with
4-benzoylbenzoate gave rise to a series of 1:1 adducts with high selectivity.50
Well-ordered polymers may be obtained in the interlayer region of a layered solid if
monomer guest molecules are regularly juxtaposed and if the polymerisation reaction is
suitably promoted. 4-vinylbenzoate and m- and p- phenylenediacrylates and 4-benzoylbenzoate
have been intercalated in Mg-Al-LDH in the chloride form, via anion exchange procedure.
U.V.-light irradiation of the intercalation compound containing vinylbenzoate produces the
formation of isomeric dimers, predominantly the syn-head-to-head cyclodimer. However,
polymerisation of vinylbenzoate takes place in the presence of co-intercalated benzoylbenzoate.
This latter guest generates 1,4-biradical when irradiated; probably the polymerisation is
induced by the presence of this radical. The photolysis of p-phenylenediacrylate intercalation
compound produces consecutive [2+2] cycloaddition and oligomers have been obtained having
a zig-zag structure 51 similar to that reported in Figure 12.
Figure 12. Scheme of the cycloadditive polymerization of the p-phenylenediacrylate anions in hydrotalcite
interlayer. Adapted from Ref. 51.
The molecule of indolinespyrobenzopyran is constituted of two heterocyclic parts bounded

with a central tetrahedral carbon atom. The two heterocyclic parts lie in two orthogonal planes.
As a consequence of u.v.-light irradiation the spyrane C-O bond breaks down with formation of
merocyanine, that has a planar structure with delocalizated π electrons. The merocyanine
absorbs in the visible region, and thermally reconverts in indolinespyrobenzopyran (see
Scheme 3). This system is a typical example of photochromic reaction which has been studied
in different media. Attempts have been done to intercalate sulfonated indolinespyrobenzopyran
into Mg-Al-LDH by the reconstruction procedure. The interlayer distance of the material
obtained was about 7.8 Å. The low expansion of the interlayer region indicates that the
sulfonated spyran was mainly adsorbed on the surface. This material showed
photoisomerization to merocyanine; the process is irreversible, probably because merocyanine
is stabilised in the polar environment of LDH. Co-intercalation of sulfonated
indolinespyrobenzopyran and toluene p-sulfonic acid by the reconstruction procedure in
slightly acidic medium, produced a material with an interlayer distance of about 25 Å. This
composite contains a small amount of sulfonated indolinespyrobenzopyran dispersed into the
toluene sulfonate anions present on the surface of the lamellae. In this apolar medium the
composite system exhibited reversible chromotropic effect. The yellow powder consisting of
spyran cointercalated in LDH-CH3C6H4SO3- turns to red, due to the formation of merocyanine,

when irradiated with U.V.-light. The red colour changes to yellow for successive visible light
irradiation. This cycle has been repeated several times.52
Scheme 3
LDHS IN MEDICINAL CHEMISTRY AND IN

PHARMACEUTICAL FORMULATIONS
Many inclusion compounds have found application in pharmaceutical formulations to
modify the bioavailability of drugs. For example, β-cyclodextrins are excellent biocompatible
hosts for the inclusion of a variety of guests with biological and pharmaceutical activity.53 The
inclusion in biocompatible hosts modifies the physical properties of the drugs with some
advantages: non pleasant smells or flavors are masked, the solubility is increased, and the
volatility reduced. Furthermore, the drugs can be protected from the action of light, oxygen or
water vapor and can be selectively delivered to a given target and released in a modified way. It
is also interesting to note that layered materials such as clays (kaolin, bentonite,
montmorillonites) are listed in the pharmacopoeia of different countries for their use as
excipients or adsorbents. Zirconium phosphate cartridges have been used in portable dialysis
machines for the uptake of ammonia obtained from hydrolysis of urea present in blood.54 In this
context, natural and synthetic Mg-Al hydrotalcite finds larger application for its
biocompatibility, chemical composition and ability to intercalate anionic drugs. Hydrotalcite
and mixtures of similar composition are used in medicine as antacid and antipepsinic agents,
and in many ointments and poultices for the protection of damaged skin. The most promising
aspect, however, is the use of intercalation compounds with anionic drugs to obtain sustained
release formulations. In the following we shall deal with these two aspects of hydrotalcite
medical applications, separately.
Antacid and Anti-Pepsin Activity of Hydrotalcite Formulations
To digest food, stomach produces hydrochloric acid and proteolytic enzymes, notably
pepsin. Ulcer is a sort of lesion or sore that forms in the lining of the stomach or duodenum
where acid and pepsin are present. Both duodenal or stomach ulcers are extremely common
diseases, and each year over 4 million people in US develop at least one type of ulcer and
thousands of them have surgery because of severe complications. While for many years it was
believed that inappropriate diet and stress lifestyle were cause of ulcer, it is now recognized that
an imbalance between digestive fluids (HCl and pepsin, in particular) and the ability of the
stomach to defend itself from them is the major cause of ulcer. Today, most ulcers are
recognized to result from the infection by the Helicobacter pylori bacterium. It should be
stressed, however, that the H. pylori infection produces a pattern of mucosal lesions that are
compatible with a marked inability of the stomach to protect itself from acids and proteolytic
enzymes.55 Thus, most of the current therapies for stomach and duodenal ulcer are based on
substances able to restore the physiological acidic and proteolytic environment of the stomach,
preserving tissues from expanding lesions.56 Classical prescriptions for ulcer are: (i) anti-H2
(ranitidine, cimetidine), whose effect is to block histamine, a powerful acid stimulant; (ii)
proton-pump inhibitors, omeprazole, whose effect is to raise the pH of the stomach by
completely inhibiting the final step of acid-production by the stomach. In association with
antibiotics is the therapy of choice for H. pylori-induced ulcers. (iii) mucosal protective
medicaments, which shield the stomach’s mucous from damage of acids. (iv) antacids, which
often produce substantial pain relief by neutralizing the stomach acidity but also by protecting
the mucosal from lesions.
Available without medical prescription, after decades from their introduction, antacids are
seeing a renewed interest as first-choice treatment in some ulcer diseases. Among classical
antacids, aluminium-magnesium containing compounds (hydrotalcites) are those that display
the best pharmacological profiles. For instance, it is known that hydrotalcites have the
capability of not only neutralizing acids, but also to inhibit pepsin action at pH values where the
pepsin activity is still high.57-59 More recently, when evaluated in some acid-neutralizing and
pH-buffering tests, hydrotalcite demonstrated to be endowed with the highest neutralizing
ability and steadier buffering with respect carbonate compounds or magnesium oxide.60
Furthermore, hydrotalcite has been shown to activate, in the gastric mucosa, genes encoding for
the epidermal growth factor (EGF) and its receptor, thus providing the physiological basis for
the mechanism of its ulcer healing action.61 On this basis, many commercial antacid
preparations (e.g. Talcid Bemolan, Almax, Maalox) contain hydrotalcite as the
pharmacological active component. Moreover, researches have been carried out on the
buffering capacity and efficacy with time of hydrotalcites, when compared with other antiacid
preparations,60,62-64 also taking into account the particle-size of the powders65 and the presence
of added pepsin.66 Hydrotalcite has prolonged buffering action in an optimum pH range;
moreover, the aluminium gastrointestinal adsorption is very low and its constipant action is
balanced by the presence of magnesium ions. Many patents have been issued on antacid
formulations containing hydrotalcite,67-71 claiming a better stability because of the presence of
eugenol, thymol and oil of cinnamon,72 or a prolonged gastric residence time for the presence
of hydrophobic species,73 or improved antacid properties in the presence of
dihydroxyaluminum aminoacetate,74 or of polymeric surfactants.75 Other studies deal with the
interaction of drugs with antacids based on hydrotalcite. It has been found that treatment with
antacid decreases the rate of penetration of the antibiotic clarithromycin through the gastric
mucus layer.76 Indomethacin, a non-steroidal anti-inflammatory drug, is adsorbed onto Riopan
and Rioplus (U.S. Pharmacopoeia), two antacid formulations containing magaldrate,
Al5Mg10(OH)31(SO4)22H2O. The adsorption mechanism has not been investigated; it has
however been found that the bioavailablity of the drug is significantly modified for the
contemporary administration of the two medicines.77
Many preparations contain Aspirin and antacids in the same tablet. The stability of these
formulations has been tested for long period at different temperatures and relative humidities. It
has been found that preparations containing magaldrate have reduced shelf-life in comparison
with preparations containing other antacids.78
Other Pharmaceutical Applications of Hydrotalcites

Apart from the above-mentioned applications, hydrotalcites are used in many preparations
for their property to adsorb anions, some unpleasant odorous or fat materials, and for their
alkaline character. In addition, hydrotalcite is often used as excipient in many formulations.
The great affinity of hydrotalcite, converted into the chloride form, for the uptake of
phosphate anions79,80 has suggested its use for the removal of these anions from the
gastrointestinal fluid in the prevention of hyperphosphatemia, induced during hemodialysis.81
Since hydrotalcites are soluble in the gastric fluid they should be used as drug for enteric
coating. The removal of about 600 mg of phosphorus per day requires the administration of 3 g
of hydrotalcite, three times a day.81
Hydrotalcite like compounds containing divalent or trivalent iron in the brucite sheets are
considered drugs against sideremia.82 Patents claim the use of hydrotalcites in dentifrices anti
tooth-decay,83 or as coating material of particles, e.g., nylon spherules, in topical cosmetic
preparations,84 or as a component of skin-moisturing patches containing also seaweed extracts
for use in cosmetics and skin pharmaceuticals.85 Moreover, hydrotalcites have been proposed
as excipient to improve the compressibility of crude drugs,86 in antifungal preparations87,88 and
in adhesives for transdermal delivery of oil soluble drugs.89
LDHS IN PHARMACEUTICAL FORMULATIONS AND DRUG RELEASE

It is well known that the appropriate choice of a pharmaceutical formulation improves the
physico-chemical properties of the active molecule and its bioavailability. The current trend of
pharmaceutical technology requires formulations that are able to maintain pharmacologically
active drug levels for long periods, avoiding repeated administrations and/or to localize the
drug release in its pharmaceutical target. Different controlled drug delivery systems which
provide a kinetic control or a spatial control of drug release have been designed and realized.90
Most of these systems are based on “reservoir devices” constituted by a microporous
membrane surrounding a core containing the drug or on “micro-reservoir devices” constituted
by microdispersions of the drug encapsulated into a lipophilic polymer. Supramolecular
assembly (vesicles, liposomes) with included drugs and β-cyclodextrins inclusion compounds
are also employed.
Intercalation compounds of biocompatible layered hosts with pharmaceutically active
species could provide other materials to design systems for modified drug release. The
interlayer region of a layered host may be, in fact, considered a microvessel in which the drug is
stored in an ordered way, while mantaining its individuality, and eventually protected from the
action of light and oxygen. After administration of the intercalation compound, the drug may be
released via a de-intercalation process, occurring because ion exchange or displacement
reactions. The release rate is essentially dependent on the rate of the de-intercalation process.
Mg-Al LDHs are the most suitable hosts to prove this idea, because their biocompatibility,
their ability to intercalate active molecules containing anionic functions and their collateral
antiacid properties. Hydrotalcite has already been used, but only as an excipient, in
sustained-release formulations containing nifedipine, an antihypertensive drug91 or
dextromethorphan, a psychoactive drug.92 A more systematic work has been done and is still in
progress on the intercalation of non steroidal active species possessing antiinflammatory action
(NSAID).93-96 Name, abbreviation and structural formula of active molecules taken into
account are shown in Figure 13. It may be seen that each of them contains a carboxylic group
that can be easily transformed into carboxylate, allowing an exchange process between the
hydrotalcite conterions and the active molecules in the anionic form.
Ion exchange procedures have, in fact, been used to obtain the intercalation compounds of
[Mg0.67Al0.33(OH)2] Cl0.670.6H2O with the most of NSAID molecules. It has been found that
hydrotalcite shows a marked preference for these species, probably because of their high
tendency to aggregate as a compact monofilm in the interlayer region. Figure 14 shows the ion
exchange isotherms of DIK- and IBU- anions that replace Cl- from hydrotalcite. It can be seen
that the selectivity towards DIK is very high, so that hydrotalcite could be employed for the
recovery of the drug from diluted solutions. Table 2 reports composition, interlayer distance
and the drug loading (w/w%) of the various intercalation compounds. It may be observed that
Aspirin readily transforms into salicilate (SA) anions as a consequence of intercalation, even
if the process has been carried out in anhydrous acetone. It may be also observed that the values
of the interlayer distance of the different intercalation compounds increase with the increasing
of the size of the guests. Moreover, these values are consistent with the presence in the
interlayer region of a monolayer of NSAID anions, partially interdigitated, with their principal
axis almost perpendicular to the layer plane. As an example, Figure 15 shows the probable
arrangement of DIK anions in the interlayer region of the intercalation compound. The
computer-aided model was obtained taking into account the experimental data of interlayer
distance and composition of the intercalate.93
Figure 13. Structural formula of indicated non-steroidal anti-inflammatory drugs (NSAID).
Figure 14. Anionic exchange isotherms of Mg-Al-Cl-LDH toward dichlofenac (DIK) (– –) and ibuprofen
(IBU) (–V–) anions. Experimental conditions: Concentration 0.1M, Temperature 25°C, reaction time 3 days.
Table 2. Use of Mg-Al hydrotalcites in medicinal chemistry and in pharmaceutical

formulation. References in round brackets.
Antacid and anti-pepsinic formulations (55-78)

Adsorbent of intestinal phosphates (prevention of hyperphosphatemia) (79-81)
Drugs for treatment of iron deficiency (sideremia) (82)
Dentifrices, Topical cosmetics and deodorants (83-85)
Excipients (86-89)
Drug delivery systems (91-96)
Figure 15. Computer-generated models showing the most probable arrangement of dichlofenac anions between
the LDH layers.
The intercalation compounds were encapsulated with an enteric coating and in-vitro drug
release was performed with the paddle type dissolution apparatus,96 U.S.P.XX ed., in a
simulated intestinal fluid at pH = 7.5. The release profile of the Mg-Al-DIK is shown in Figure
16. The same figure reports, for sake of comparison, the release profile of a physical mixture of
Mg-Al-Cl and dichlorofenac in the sodium form and that of a commercial controlled release
formulation (Dealgic 100). The dissolution test evidences that the release of the drug from the
intercalation compound occurs in a modified way. It has also been found that the
de-intercalation process is driven by DIK/phosphates ion exchange reaction.94
Figure 16. Release profile of dichlofenac from Dealgic 100® (–∆–), Mg-Al-DIK intercalation compound (– –)
and physical mixture of DIK and LDH-Cl (– –).
Table 3. Composition, interlayer distance and drug loading of intercalation compounds of

Mg-Al LDH with some non sterolidal anti-inflammatory drugs.
Formula d (Å) Drug loading (% w/w)

[Mg0.67Al0.33(OH)2]SA0.167 OH0.163x1H2O 15.3 22
[Mg0.67Al0.33(OH)2]IBU0.33 x0.25H2O 21.8 50
[Mg0.67Al0.33(OH)2]DIK0.33x1.1H2O 23.1 55
[Mg0.67Al0.33(OH)2]KET0.21 Cl0.12x 0.36H2O 23.7 43
[Mg0.67Al0.33(OH)2]TIAP0.22 Cl0.11x0.8H2O 23.2 42
[Mg0.67Al0.33(OH)2]TOLM0.28 Cl0.05x0.7H2O 24.7 43
[Mg0.67Al0.33(OH)2]IND0.22 Cl0.11 x1.1H2O 25.2 48
CONCLUSION
Layered Double Hydroxides offer a large number of possibilities to organize photoactive
species on the interlayer and/or on the surface of the microcrystals. Materials for non-linear
optics and for energy storage and conversion have been envisaged and numerous other
applications can be given. The development of real devices on the basis of modified LDHs,
however, still requires additional research effort and the involvement of researchers with
different competences.
Application of hydrotalcites in medicinal chemistry has already reached the commercial
area and many patents have been issued; however, the development of drug release systems
based on intercalation compounds requires much more fundamental and applied research.
On the whole, the work done has a good scientific value and contains the seeds for future
development and for a rich harvest of new discoveries.
REFERENCES
1. G. Alberti and T. Bein (Vol. Eds.) in Solid-State Supramolecular Chemistry: Two and
Three-dimensional Inorganic Networks, Volume 7 of Comprehensive Supramolecular
Chemistry, Pergamon, Elsevier Science Ltd Press, Oxford, U.K.,1996.
2. R. Schöllhorn, “Intercalation Compounds” in “Inclusion Compounds” J. L. Atwood, J. E.
D. Davies and D. D. MacNicol, eds., Academic Press, New York, 1984, Vol.1, pp. 249-349.
3. M. S. Whittingham and A. J. Jacobson (eds.), “Intercalation Chemistry”, Academic Press,
New York, 1982.
4. J. Jacobson, “Intercalation Reactions of Layered Compounds” in “Solid State Chemistry
Compounds”, A. K. Cheetham and P. Day, eds., Clarendon Press, Oxford, 1992,
pp.182-233.
5. W. Muller-Warmuth and R. Schöllhorn, eds, “Progress in Intercalation Research”, Series:
Physics and Chemistry of Materials with Low-Dimensional Structures, 17, Kluwer
Academic Publ., Dordrecht, 1994.
6. R. Setton (Ed.) “Chemical Reactions in Organic and Inorganic Constrained Systems”,
NATO ASI Series, Series C: Mathematical and Physical Sciences Vol. 165, D. Reidel
Publishing Company, Dordrecht, 1986.
7. A. J. Jacobson, Materials Science Forum 154-153 (1994) 1.
8. M. Ogawa, K. Kuroda, Chem. Rev. 95 (1995) 399.
9. F. Cavani, F. Trifiro, A. Vaccari, Catal. Today 11 (1991) 173.
10. F. Trifirò and A. Vaccari, in Solid-State Supramolecular Chemistry: Two and
Three-dimensional Inorganic Networks, Volume 7 of Comprehensive supramolecular
Chemistry, G. Alberti and T Bein ,Vol Eds., Pergamon , Elsevier Science Ltd Press, Oxford,
1996, Chap. 8.
11. A. deRoy, C. Forano, K. El Malki, and J.-P. Besse, in “Anionic Clays: Trends in Pillaring
Chemistry, Synthesis of Microporous Materials” M. I. Occelli and H. E. Robson, Eds, Van
Norstrand Reinhold, New York, 1992, Vol.2, p.108.
12. V. Rives and M. A. Ulibarri, Coord Chem. Rev. 181 (1999) 61.
13. W. Jones, S. P. Newman, New J. Chem. (1998) 105.
14. R. P. Wayne, “Principles and applications of photochemistry”, Oxford University Press,
Oxford, 1988.
15. H. Duerr and H. Bouas-Laurent (Eds.),“ Photochromism. Molecules and Systems”,
Elsevier, Amsterdam, 1990.
16. R. W. Munn and C. N. Ironside (Eds.), “Principles and Applications of Nonlinear Optical
Materials”, CRC-Press, London, 1993.
17. V. Ramamurthy, Tetrahedron 42 (1986) 5753.
18. D. R. Hines, S. A. Solin, U. Costantino and M. Nocchetti, Phys. Rev. B (2000) 11348.
19. S. Miyata, Clays Clay Miner. 31 (1983) 305
20. F. Hellferch, Ion Exchange, McGraw-Hill, New York, 1962.
21. U. Costantino, N. Coletti, M. Nocchetti, G. G. Aloisi, F. Elisei, Langmuir 15 (1999) 4454.
23. F. Rey and V. Fornes, J. Chem. Soc. Faraday Trans. 88 (1992) 2233.
25. Y. Park, K. Kuroda and C. Kato, J. Chem. Soc. Dalton Trans. (1990) 3071.
26. U. Costantino, N. Coletti, M. Nocchetti, G. G. Aloisi, F. Elisei, L. Latterini, Langmuir 15

(2000) 4454.
27. H. Tagaya, A. Ogata, T. Kuwahara, S. Ogata, M. Karasu, J. Kadokawa and K Chiba,
Microporous Mater. 7 (1996) 151.
28. E. P. Giannelis, D. G. Nocera and T. J. Pinnavaia, Inorg. Chem. 26 (1987) 203.
29. M. D. Newsham, E. P. Giannelis, T. J. Pinnavaia and D. G. Nocera, J. Am. Chem. Soc. 110
(1988) 3885.
30. S. Bonnet, C. Forano, A. de Roy, J. P. Besse, P. Maillard and M. Momenteau, Chem. Mater.
8 (1996) 1962.
31. Y. Park, K. Kuroda and C. Kato, Chem. Lett. (1989) 2057.
32. P. K. Dutta and M. Puri, J. Phys. Chem. 93 (1989) 376.
33. L. Ukrainczyk, M. Chibwe, T. J. Pinnavaia and S. A. Boyd, J. Phys. Chem. 98 (1994) 2668.
34. M. Chibwe and T. J. Pinnavaia, J. Chem. Soc., Chem. Commun. (1993) 278
35. V. Iliev, A. Ileva, and L. Bilyarska, J. Mol. Catal. 126 (1997) 99.
36. V. Iliev, L. Prahov, L. Bilyarska, H. Fischer, G. Schulz-Ekloff, D. Wöhrle and L. Petrov, J.
Mol. Catal. 151 (2000) 161.
37. L. Barloy, J. P. Lallier, P. Battioni, D. Mansuy, Y. Piffard, M. Tournous, J. B. Valim and W.
Jones, New J. Chem. 16 (1992) 71.
38. D. S. Robins and P. K. Dutta, Langmuir 12 (1996) 402.
39. P. K. Dutta and D. S. Robins, Langmuir 10 (1994) 1851.
40. P. K. Dutta and D. S. Robins, Langmuir 10 (1994) 4681
41. W. Y. Tseng, J. T. Lin, C. Y. Mou, S. F. Cheng, S. B. Liu, P. P. Chu and H. W. Liu, J. Am.
Chem. Soc. 118 (1996) 4411.
42. W. Ding, G. Gu, W. Zhong, W. Zang and Y. Du, Chem. Phys. Lett. 262 (1996) 259.
43. S. Cooper and P. K. Dutta, J. Phys. Chem. 94 (1990) 114.
44. T. Sato, H. Okuyama, T. Endo and M. Shimada, React. Solids 8 (1990) 63.
45. J. Valim, B. M. Kariuki, J. King and W. Jones, Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A
211 (1992) 271.
46. K. Takagi, T. Shichi, H. Usami and Y. Sawaki, J. Am. Chem. Soc. 115 (1993) 4339.
47. T. Shichi, K. Takagi and Y. Sawaki, Chem. Commun. (1996) 2027.
48. K. Takagi, E. Harata, T. Shichi, T. Kanoh and Y. Sawaki, J. Photochem. Photobiol. 105
(1997) 47.
49. K. Takagi, T. Shichi and Y. Sawaki, Chem. Lett. 9 (1996) 781.
50. K. Takagi, N. Saito, T. Shichi and Y. Sawaki, Chem. Lett. 4 (1999) 275.
51. T. Shichi, K. Takagi and S. Yamashita, Supramol. Science 5 (1998) 303.
52. H. Tagaya, S. Sato, T. Kuwahara, J. Kadokawa, M. Karasu and K Chiba, J. Mater. Chem. 4
(1994) 1907.
53. S. Li, W. C. Purdy, Chem. Rev. 92 (1992) 1457.
54. A. Gordon, O. S. Betler, M. Greenbaum, L. Marantz, T. Gral and M. H. Maxwell, Trans.
Am. Soc. Artif. Int. Organs 17 (1971) 253.
55. A. Schmassmann, A. Tarnawski, H. A. Gerber, B. Flogerzi, M. Sanner, L. Varga and F.
Halter, Gut 35 (1994) 896.
56. A. S. Tarnawski, R. Pai, R. Itani and F. A. Wyle, Digestion 60 (1999) 449.
57. A. C. Playle, S. R. Gumming and A. F. Llewellyn, Pharm. Acta Helv. 49 (1974) 298.
58. J. Pawlaczyk, Z. Kokot and A. Rafinska, Acta Pol. Pharm. 42 (1985) 153.
59. M. Dreyer, D. Marwinski, N. Wolf and G. H. Dammann, Arzneim.-Forsch. 41 (1991) 738.
60. M. S. Lin, P. Sun and H. Y. Yu, J. Formos Med. Assoc. 97 (1998) 704.
61. A. S. Tarnawski, M. Tomikawa, M. Ohta and I. J. Sarfeh, J. Physiol. Paris 94 (2000) 93.
62. Z. Kokot, Acta Pol. Pharm. 44 (1987) 72.
63. Z. Kokot, Pharmazie 43 (1988) 249.
64. Z. Kokot, G. Urbowicz and D. Ewertowska, Acta Pol. Pharm. 46 (1989) 272.
65. J. L. Fabregas and J. Cucala, Int. J. Pharm. 52 (1989) 173.
66. Z. J. Kokot, Acta Pol. Pharm. 48 (1991) 27.
67. S. Linke (Bayer A.-G.) German Patent 3,346,943 (1983); C.A. (1985), 103, 129118u.
68. T. Kajino,T. Okada and S. Morioka, Jpn. Kokai Tokkyo Koho JP 60,161,915 [85,161,915]
(1984), to Sato Pharmaceutical Co., Ltd.; C.A. (1986), 104, 39729k.
69. W. Jettka, B. Gajdos and M. D. Benedikt, Eur. Patent EP 715,846 (1996), to
Rhone-Poulenc Rorer Gmbh, Germany; C.A. (1996), 125, 96121.
70. T. Kito, N. Inatomi, S. Morimoto and T. Morimoto, Jpn. Kokai Tokkyo Koho JP
08,259,445 (1996), to Takeda Chemical Industries, Ltd.; C.A. (1996), 126, 37097.
71. M. Wanatabe, M. Nakao and K. Okuno, Jpn. Kokai Tokkyo Koho JP 98,163,811 (2000), to
Takeda Chemical Industries, Ltd.; C.A. 132 (2000) 185410.
72. C. Fritsch and H. G. Wetzstein (Bayer A.-G.) German Patent 3,612,086 (1986); C.A. 108
(1988) 173550f.
73. R. G. W. Spickett, J. L. F. Vidal and J. C. Escoi, Eur. Patent EP 338,861 (1988); C.A. 113
(1990) 103388p.
74. T. Makino, S. Marunaka and S. Imoto, Eur. Patent EP 638,313 (1993), to Takeda Chemical
Industries, Ltd.; C.A. 122 (1995) 170248s.
75. K. H. Bauer German Patent 98,19859231 (2000) to Regenold Gmbh; C.A. 133 (2000)
63981.
76. P. Grubel and D. R. Cave, Aliment. Pharmacol. Ther. 12 (1998) 569.
77. O. M. N. Al-Gohary and E. A. Hosny, Pharm. Acta Helv. 72 (1997) 81.
78. O. M. N. Al-Gohary and R. S. Al-Kassas, Pharm. Acta Helv. 74 (2000) 351.
79. A. Ookubo, K. Ooi and H. Hayashi, Langmuir 10 (1994) 407.
80. U. costantino, M. Casciola, L. Massinelli, M. Nocchetti and R. Vivani, Solid State Ionics
97 (1997) 203.
81. A. Ookubo, K. Ooi and H. Hayashi, J. Pharm. Sciences 81 (1992) 1139.
82. Jpn. Kokai Tokkyo Koho JP 60 06,619 [85 06,619] (1983), to Kyowa Chemical Industry
Co., Ltd.; C.A. 102 (1985) 226039f.
83. Y. Matsushima, T. Kumura, I. Kawamura and T. Kawada, Jpn. Kokai Tokkyo Koho JP 80
38,328 (1978), to Kyowa Hakko Kogyo Co., Ltd.; C.A. 93 (1980) 155851x.
84. T. Nakane, S. Nishiyama and T. Nanba Jpn. Kokai Tokkyo Koho JP 03,153,767
[91,153,767] (1989), to Shiseido Co., Ltd.; C.A. 116 (1992) 27804r.
85. N. Koide, N. Iida, M. Nishikawa and K. Inoue, Jpn. Kokai Tokkyo Koho JP 98,226,290
(2000), to Lion Corp.; C.A. 132 (2000) 170868.
86. M. Sofue and Y. Ueda, Funtai Kogaku Kaishi, 33 (1996) 638.
87. N. Doi, A. Yonetani and T. Unno, Jpn. Kokai Tokkyo Koho JP 01,275,527 [89,275,527]
(1988); C.A. 112 (1990) 145596q.
88. J. S. Woo and H. G. Yi, US Patent 99,411,510 (2000), to Hanmi Pharm. Co., Ltd.; C.A. 132
(2000) 227449.
89. M. Koide and H. Ozeki, Jpn. Kokai Tokkyo Koho JP 95,270,582 (1997), to Lion Corp.; C.A.
127 (1997) 23785.
90. Y. W. Chien, in “Novel drug delivery systems”, M. Dekker, New York, 1992.
91. N. Doi, S. Nitta, M. Kusakari and N. Takahashi, Jpn. Kokai Tokkyo Koho JP 60,225,719
[85,225,719] (1984); C.A. 104 (1986) 155998w.
92. K. Watanabe, Y. Sato and N. Kikuchi, Jpn. Kokai Tokkyo Koho JP 98,101,907 (1999), to
Shiseido Co., Ltd.; C.A. 131 (1999) 303377.
93. M. Nocchetti, Chimica dell’intercalazione in Argille Anioniche Sintetiche e in Fosfati
Lamellari, Tesi di Dottorato in Scienze Chimiche, Università degli Studi di Perugia, Italy,
1998.
94. G. Fardella, L. Perioli, V. Ambrogi, G. Grandolini, U. Costantino and M. Nocchetti, Proc.
Int. Symp. Controlled. Release Bioact. Mater., 24th(19979 1033.
95. G. Fardella, L. Perioli, V. Ambrogi, G. Grandolini, Proc. Int. Symp. Controlled. Release
Bioact. Mater. 25 (1998) 774.
96. V. Ambrogi, G. Fardella, G. Grandolini and L. Perioli, Int. J. of Pharmaceutics submitted.
Chapter 13
ENVIRONMENTAL CHEMISTRY OF
IRON(II)-IRON(III) LDHS (GREEN RUSTS)
Hans Christian Bruun Hansen
Chemistry Department, Thorvaldsensvej 40, DK-1871 Frederiksberg C.,Denmark.
Phone: +45 35 28 24 18, Fax: +45 35 28 23 98, E-mail: haha@kvl.dk
INTRODUCTION
Layered double hydroxides (LDH) composed of di- and trivalent metal cations of the same
element are not common, but exists at least for the elements Co, Ni and Fe. By far the most well
studied of these are the Fe(II)-Fe(III)-LDHs, also called green rusts (GRs) due to their intense
blue to green colours. Mixed-valence iron hydroxides formed on oxidation of Fe(II) hydroxide
or by mixing Fe(II) and Fe(III) hydroxides have been known since the start of 1900.1,2 However,
a more detailed understanding of the nature of these compounds did not appear until the
comprehensive studies of layered hydroxides by Feitknecht,3 and the investigations of iron
oxides by Bernal et al.4 who were the first to use the term "green rust". Since that time, much
have been learned about the formation and chemical reactivity of the GRs, which normally
occur as transient phases on corrosion of iron or in iron oxide transformations in terrestrial or
aquatic environments with appropriate redox conditions for the existence of both the di- and
trivalent oxidation states of iron. In geo-environments, reduction of Fe(III) to Fe(II) is normally
caused by coupling to respiration processes, suggesting that formation of GRs in these
environments will be strongly coupled to biological processes. In geo-environments GRs may
reduce pollutants such as nitrogen oxides, chlorinated solvents and nitroaromatic compounds,
and cause sorption of metal cations, oxyanions and other anions through precipitation and
anion exchange processes. Furthermore, GR may intervene in transitions between anoxic and
oxic soil conditions and thereby determine the type and nature of Fe oxides forming. Insight to
the chemistry of GRs is important for understanding Fe cycling in Nature, and those natural
attenuation and waste water treatment processes which are based on iron. This chapter will
review the chemistry of GR with emphasis on synthesis, stability and environmental
applications.
470 Hans Christian Bruun Hansen
STRUCTURE
In early investigations, Fe(II)Fe(III) hydroxides were believed to exist in the form of
hydrated magnetites (FeIIFeIII2(OH)8), also sometimes called basic ferroferrites or ferroso-ferric
hydroxides.2,5-7 Feitknecht and Keller8 showed that the green hydroxides forming on oxidation
of Fe(II) hydroxide were layered compounds of variable compositions; the structure was
thought of one with shifting layers of Fe(OH)2 and FeOCl, xH2O, a model which with some
modifications have persisted up to 1990.9,10 Two types of GRs were distinguished by Bernal et
al.:4 green rust one (GRI), with a rhombohedral unit cell, and green rust two (GRII), with a
hexagonal cell. When both indexed in the hexagonal system, GRI has three hydroxide layers in
the repeat unit, whereas GRII only has one, corresponding to polytypes 3R and 1H, respectively,
according to the classification scheme of Bookin and Drits.11 Stampfl12 demonstrated that the
powder diffractogram of a natural sample of carbonate green rust (GRCO3) was coincident with
that of pyroaurite (3R). This structural classification was confirmed by McGill et al.13
In the following the specific forms of GRs will be distinguished according to the type of
interlayer ion and not by the stacking polytype. The interlayer ion will be given as a suffix to
"GR", i.e. the chloride, carbonate and sulphate forms will be denoted GRCl, GRCO3 and GRSO4.
Iron hydroxides, oxides and hydroxide-oxides will be referred to collectively as Fe oxides.
SYNTHESIS
For laboratory studies of GR properties and reactivity, reproducible synthesis methods are
required. A number of different synthesis strategies have been investigated. In the following
three different categories of formation reactions will be distinguished.
Oxidation of Fe(0)
Controlled chemical or electrochemical oxidation of Fe(0) produces GR. Bernal et al.4

reported that GRs can be synthesized by electrolysis of Fe anodes in appropriate electrolytes.
The potentials (and pH) at which synthesis of GR is possible is delineated by the GR stability
field in E-pH stability diagrams.14 According to Vatankhah et al.,15 GRs (GRSO4, GRCO3) may
form at potentials (vs SHE) more positive than –0.3 V in Na2SO4 and NaHCO3 electrolytes at
pH 8. Refait et al.16 produced GRCl at pH 9 in 1 M KCl at a potential of –0.35 V vs SHE.
Electrolysis at current densities of 10 – 15 mA cm-2 have been reported by Petit17 and
Sagoe-Crentsil and Glasser.18 Green rusts can also be produced by chemical oxidation of Fe(0)
by dioxygen, tetrachloromethane, nitrate or other oxidants, but hitherto these methods have not
been used for synthesis of larger GR quantities.13,19-23
Environmental Chemistry of Iron(II)-Iron(III) LDHs (Green Rusts) 471
Oxidation of Fe(II)
The classical method for synthesis of GRs is by oxidation of solid Fe(OH)2 hydroxide
using dioxygen.4,8 This procedure has been studied extensively by Genin and coworkers.16,24
As an example the reaction for synthesis of GRCl can be given as:
− II III −
6Fe(OH)2 + 38 O2 + 32 Cl + ( 34 + x)H2O ↔ Fe4.5 Fe1.5(OH)12 Cl1.5xH2O + 32 OH (Eqn.1)
In order to avoid too high pH values at the end of the synthesis, the base produced by the
reaction can be consumed by adding slightly more Fe(II) to the reaction mixture than that
corresponding to half the equivalents of hydroxide; ideally, FeCl2 and NaOH should be added
in the ratio (13.5/2)/12 = 0.56 for all base to be consumed for precipitation of GR. In the case of
GRSO4 one calculates that a slightly higher ratio between FeSO4 and NaOH has to be used
(0.58). In the synthesis of GRCO3 Na2CO3 is not added until Fe(OH)2 has precipitated in order to
avoid the formation of FeCO3. The reaction is halted before the GR starts oxidizing to Fe
oxides (Fig. 1a).
Figure 1 Changes in pH, redox potential or base consumption during synthesis of GRs a) synthesis of GRSO4
and its oxidation to γ-FeOOH by air oxidation of Fe(OH)2 prepared from 0.12 M FeCl2 4H2O and 0.2 M
NaOH in 0.6 M Na2SO4 (adapted from reference 52), b) pH-stat synthesis of GRCl and its oxidation to
γ-FeOOH by air oxidation of 0.048 M FeCl2 in 0.34 M NaCl at pH 7 (adapted from reference 33), and c)
Synthesis of GRSO4 by NaOH titration of a solution of 37.8 mM FeSO4 and 3.8 mM Fe2(SO4)3 initially
acidified with H2SO4 (adapted from reference 36).
Formation of GR from Fe(OH)2 can also take place by oxidation of water, a reaction
similar to the Schikorr reaction.25,26 As it will be seen later, Fe(OH)2 is not thermodynamically
stable in water at a hydrogen pressure of 1 atm and pH 8 – 10. The formation of GRSO4 from
oxidation of Fe(OH)2 by water is given by:
2− II III −
6Fe(OH) 2 + SO 4 + 2H 2 O ↔ Fe4 Fe2 (OH)12 SO4 + H2 + 2OH (Eqn.2)
The addition of dispersing and weakly complexing agents like sugars and polyhydric
alcohols affects the apparent first-order rate of the reaction. Elemental Fe has been suggested as
a reactive intermediate.26
Another popular and reproducible synthesis method comprise oxidation of Fe(II) in
solution at constant pH.27-30 With GRSO4 as an example the synthesis follows the reaction:
2+ − 2− II III
6Fe + O 2 + 8OH + SO 4 + (2 + x)H 2O ↔ Fe4 Fe2 (OH)12 SO 4 xH 2 O (Eqn.3)
It is likely that Fe3+ formed on oxidation of Fe2+ forms a ferrihydrite-like phase which
subsequently reacts with Fe2+ (Eq. 5).31 The reaction is halted before consumption of all Fe(II)
in solution and before commencement of GR oxidation (Fig. 1b). It is seen from Fig. 1a,b that
the oxidation of GR proceeds without consumption of base or changes of pH, which suggest
that the following reaction is operative along the plateau:31-33
2+
Fe 4 Fe 2 (OH)12 SO 4 + 34 O 2 ↔ 5γ − FeOOH + Fe
II III 2−
+ SO 4 + 3 12 H2 O (Eqn. 4)
The GRCO3 is synthesized using Na2CO3 as neutralizing agent instead of NaOH. The
constant pH, often set between 7 and 7.5, is achieved by using a pH-stat. If the pH becomes too
high (> 9 – 10) a pure GR cannot always be synthesized as other phases will be more stable. For
the more soluble GRs like GRCl (see below) the GR can be synthesized more reproducible, with
a better crystallinity and at a lower pH if the concentration of the interlayer anion is kept high in
the synthesis suspension. It is generally observed that the crystallinity of the products decrease
when the rate of oxidation is increased.
Reaction of Soluble Fe(II) with Fe(III) Oxides
When freshly precipitated ferrihydrite is added to a solution of FeSO4 held at pH 7,

ferrihydrite (here represented as "Fe(OH)3") dissolves under the formation of GRSO434,35
according to the reaction:
2+ − 2− II III
2Fe(OH) 3 + 4Fe + 6OH + SO4 ↔ Fe 4 Fe 2 (OH)12 SO 4 (Eqn.5)
This is also the reaction taking place when a solution of Fe(II) and Fe(III) sulphate is
titrated with alkali; a ferrihydrite-like phase is precipitated around pH 3, which is redissolved
above pH 6.5 when GRSO4 starts to form (Fig. 1c).5,36 A reaction similar to Eq. 5 takes place
when Fe(II) is reacted with lepidocrocite.37 The term "induced hydrolysis" has been used to
characterize such reactions in which the sorption of divalent metal cations to a (hydr)oxide of
the trivalent metal cation causes hydrolysis of the divalent cation and precipitation of LDHs.38
In the case of GRs it is important that an excess of Fe(II) is reacted with Fe(III) oxide, otherwise
magnetite or other Fe oxides will form.39-42 This also explains why the Fe(III) oxide has to be
added to the Fe(II) solution and not the reverse for successfull synthesis of GR by this method.
PRODUCT CLEANUP AND STORAGE

The synthesized products normally are washed free of salts, and either freeze dried or
stored in suspension until use. All operations need to be carried out in strict exclusion of
dioxygen (and carbon dioxide if non-GRCO3 forms are synthesized), preferably by carrying out
all operations in an inert atmosphere using a glove box or Schlenk equipment. If washed with
water, the GR starts to dissolve causing precipitation of Fe(III)-containing oxides, typically
magnetite (see eq. 9 later) or sometimes lepidocrocite.29 Dissolution can be minimized if a less
polar solvent than water is used for washing, e.g. methanol or ethanol.27,29 Green rust in
equilibrium with an aqueous solution is stable for years when kept free from oxidants; however,
crystals usually become thicker on ageing as evidenced by sharpening of basal reflections in
XRD. Alternatively, GR can be stored as a freeze dried powder enabling measurements not
possible with the wet material. Furthermore, the freeze dried material is easy to handle and it
can be dosed more accurately compared with the use of suspensions.
IDENTIFICATION AND CHARACTERIZATION

Examination of GRs by different instrumental techniques is only possible if oxidation is
prevented. Actions to prevent oxidation includes working under inert or reducing atmospheres
(Ar, N2, H2) or in vacuum, freezing of samples, washing with ethanol, and stabilization through
sorption of glycerol or incorporation into polyvinyl alcohol.29,43,44 When kept in a dry
atmosphere, freeze dried samples are more resistant to oxidation compared with wet samples.29
Synthetic GRs form hexagonal platy particles with diameters in the range 0.1 – 10 µm and
thickness up to 0.2 µm (Fig. 2). Green rusts formed by natural corrosion of steel can form
particles up to mm size.12 The GR particles can be more or less intergrown.45,46 The specific
surface area of freeze dried materials can be determined by nitrogen BET analysis, and for a
GRCO3 Williams and Scherer47 found a specific surface area of 33 m2 g-1. The compounds show
typical LDH X-ray diffraction patterns (Fig. 3). It is normally observed that basal reflections
are very intense due to a strong preferred orientation of the tabular particles in the sample
mounts. As for other LDHs, the interlayer spacing depends on the size, charge, and structure of
the interlayer anion (Table 1).
Figure 2 SEM micrograph of GR crystals formed by oxidation of Fe(0) with CCl4 (Scherer et al., 1999).
Reprinted from M. M. Scherer, B. A. Balko and P. G. Tratnyek, The role of oxides in reduction reactions at the
metal-wate interface, in Mineral-water interfacial reactions: Kinetics and mechanisms, D. L. Sparks and T. J.
Grundl Eds., Symp. Ser. 715, p. 301, © 1999, with permission from the American Chemical Society.
Figure 3 Typical X-ray diffraction traces of GRSO4, GRCl and GRCO3 scanned as glycerol smears. Only
d-spacings for basal reflections shown (nm).
Table 1. Compositions of synthetic, unoxidized, hydrated GRs and their layer thickness.
Interlayer Fe(II):Fe(III)a Layer thicknessb Comment Reference

anion (nm)
SO42 2-2.4 1.09 – 1.12 4,29,31,36,48-53
SO32- 3 0.78 Oxidizes to GRSO4 54
Cl- 3 0.80 4,29,30,31,55
Br-- (3) 0.76-0.81 4,29
I- (3) 0.83-0.84 29
CO32- 2 0.75 Narrow interlayer 24,29,39,43,56,57
NO3- 1.2 0.77-1.10 Oxidizes 21,29,45
ClO4- 1.5 1.10 Unstable 29
HxPO4(3-x)- (2) 1.04 Transforms to vivianite 35
SeO42- 2 1.09 Oxidizes 58
Oxalate 3 0.79 Oxalate planar in interl. 59
LAS 2 3.00 Hydrophobic interlayer 60
Cysteine - 1.0 No XRD evidence 61
a. Fe(II):Fe(III) ratio in the metal hydroxide layer.
b. The thickness of the metal hydroxide layer plus interlayer determined from the basal spacings in XRD.
The green to bluish colours of GRs due to Fe(II)-Fe(III) charge transfer are in accordance
with a sorption maximum located around 650 – 780 nm in UV-Vis spectra.25,43 A pronounced
pleochroism has been reported for the GRCO312 similar to what is observed for carbonate forms
of other LDHs. In IR spectra, GRs show similar features as other LDH compounds with an
intense OH stretching vibration in the range 3300 - 3500 cm-1 and three to four skeletal
vibrations in the region 400 – 800 cm-1.18,27,39,62,63 Composite interlayer anions as sulphate and
carbonate gives rise to characteristic absorptions around 1110 cm-1 and 1360 cm-1, respectively.
In Raman spectra two absorption bands at about 430 cm-1 and 510 - 520 cm-1 attributed to the
stretching modes of Fe(II)-OH and Fe(III)-OH, respectively, appear to distinguish GRs from
other Fe oxides.14,23,64 Mössbauer spectroscopy is a very useful tool for characterization of iron
distribution and oxidation states in GRs.
Complete analyses of the chemical composition of GRs have seldom been carried out.
Often only the Fe(II):Fe(III)-ratio and the interlayer anion content has been determined. Thus,
it is unknown to which extent hydroxyl groups may have dissociated a proton to form oxo
bridges, if hydroxyls of the hydroxide sheets have been substituted for other anions, and the
exact amount of water being present in the interlayer.36 For a number of GRs with interlayers of
tetrahedral anions like sulphate and perchlorate, two different hydration states exist giving rise
to layer thickness of 1.1 nm and 0.8 nm for the hydrated and non-hydrated forms,
respectively.29 There is not an ideal Fe(II):Fe(III)-ratio in the metal hydroxide layers which is
determined by the structure, but ratios close to 2:1 or 3:1 are often observed (Table 1). Such
ratios can be rationalized based on electrostatic considerations.65 The lowest and highest
Fe(II):Fe(III) ratios at which the GR structure is stable is not known precisely but probably is in
the range 3:1 to 1:1.8,27,66,67 However, it appears that freshly precipitated synthetic GRs always
have Fe(II):Fe(III) ratios varying between 3:1 and 2:1.
THERMODYNAMIC STABILITY
In order to delineate the stability fields of GRs or predict their possible reactions,
thermodynamic data on GRs are needed. Up to now only a few estimates have been produced. In the
following data the Gibbs free energy of formation of GRs will be discussed.
POTENTIOMETRY
Potentiometric measurements have been used extensively by Genin and coworkers for the
determination of ∆Gfo(GR).16,24,52,66 Typically, simultaneous measurements of pH and the
electrochemical potential of an inert metal electrode are recorded in systems where GR is
formed by oxidation of Fe(OH)2 or where GR is oxidized to an Fe(III) oxide. The ∆Gfo(GR) is
estimated by use of the Nernst equation with the recorded potentials and the pertinent
equilibrium reaction. E.g., on formation of GRSO4 by oxidation of Fe(OH)2 the following half
cell reaction is anticipated52 (interlayer water omitted):
2− II III
6Fe(OH) 2 + SO 4 ↔ Fe 4 Fe 2 (OH)12 SO 4 (Eqn.6)
The corresponding Nernst expression and Eo value is given by:

0 2−
E = E + 0.0296log(SO4 ) (Eqn.7)
0 0 0 0 2−
E = 1
2F (∆G f (GR SO4 ) − 6∆G f (Fe(OH) 2 ) − ∆Gf (SO4 )) (Eqn.8)
Because the redox potential (E) and the activity of SO42-, (SO42-), are known from
experiment, the ∆Gfo(GR) can be calculated. A similar calculation can be carried out for GRSO4
oxidation to Fe(III) oxide, in this case lepidocrocite. A necessary prerequisite of the method is
of course that the measured electrochemical potentials represent true equilibrium potentials. By
the above mentioned method ∆Gfo values have been determined for different interlayer forms
of GRs (Table 2).
Table 2. Standard Gibbs free energies of formation for GRs.
GR formulaa ∆Gfo (kJ mol-1) Methodb Reference

II III
Fe 4Fe 2(OH)12SO4 -3790 Redox potentialc + ion act. 68
FeII4FeIII2(OH)12SO4 -3668 Solubility 36
FeII4FeIII2(OH)12SO4 -3791 Solubility 60
FeII3FeIII(OH)8Cl -2146 Redox potentialc + ion act. 14
FeII4FeIII2(OH)12CO3 -3590 Redox potentialc + ion act. 14
FeII6FeIII2(OH)16SO3 -4516 Redox potentialc + ion act. 54
FeII6FeIII2(OH)16C2O4 -4672 Redox potentialc + ion act. 16
a. Because of the uncertainty in the amount of interlayer water, the estimated ∆Gfo values refer to GRs
without water included.
b. All estimates are based on equilibria between GR and some other solid phase, such as Fe(OH)2, γ-FeOOH,
ferrihydrite or magnetite.
c. Redox potential of the pertinent Fe(II)-Fe(III) couples measured by an inert metal electrode against a
reference electrode
SOLUBILITY MEASUREMENTS
The solubility product of GRs cannot be determined directly, as the solubility of Fe3+ in
aqueous suspensions of GR is too low to be measured. Therefore, the solubility of Fe3+ has to
be determined indirectly through equilibrium with another phase. E.g., on formation of GRSO4
by reaction of Fe(II) with ferrihydrite (Eq. 5), one may assume that the Fe3+ activity is
controlled by the solubility of ferrihydrite.36 Unfortunately, the solubility of ferrihydrite is
variable and the resulting ∆Gfo(GR) estimate not very precise. Recently we have evaluated
another approach. When GRSO4 is slowly titrated with acid, the GR dissolves according to the
reaction:
II III + 2+ 2−
Fe 4 Fe 2 (OH)12 SO 4 + 4H ↔ Fe 3O4 + 3Fe + SO 4 + 8H2 O (Eqn. 9)
The magnetite formed is well crystallized and the final products of titration thus
well-defined. The ∆Gfo(GRSO4) can be determined using:
(Fe 2 + ) 3 (SO 24− )

∆G 0f (GR SO 4 ) = ∆G )f (Fe 3 O 4 + 3∆G 0f (Fe 2+ ) + ∆G 0f (SO 24− ) + 8∆G 0f (H 2 0) + RT ln
(H + ) 4
(Eqn. 10)
A typical titration curve from such experiment is shown in Fig. 4. A pure GRSO4 suspended
in 0.1 M Na2SO4 is slowly titrated with H2SO4 under argon. When all GRSO4 has been titrated to
magnetite, a sharp decline in pH is observed. From measurements of pH, the activity of Fe2+
and the known activity of SO42- the ∆Gfo(GRSO4) can be estimated according to Eq. 10. The
estimate is close to the value determined by potentiometry (Table 2).
Figure 4 Titration of GRSO4 suspended in 80 mL of 0.1 M Na2SO4 with 1.00 M H2SO4 under argon. The
initial concentration of Fe(II)GR was 10 mM and the titration lasted approx. 5000 min. The end product was
magnetite.
SOLUBILITY AND STABILITY DIAGRAMS

The estimated ∆Gfo(GR)values allows for calculation of the solubility products of the
various GR forms. For dissolution of GRSO4:
II III 2+ 3+ - 2−
Fe 4 Fe 2 (OH)12 SO 4 ↔ 4Fe + 2Fe + 12OH + SO 4 (Eqn. 11)
the solubility product is given by:

2+ 4 3+ 2 − 12 2−
K sp = (Fe ) (Fe ) (OH ) (SO 4 ) (Eqn.12)
When the GR formulas are written all with 8 Fe atoms per formula unit, and the ∆Gfo
values determined potentiometrically (Table 2) are used in conjunction with ∆Gfo values from
Wagman et al.,69 the respective pKsp values for GRSO4, GRCl and GRCO3 are 146.3, 135.6 and
149.1. Thus, at the same activities of the interlayer anion, Fe3+ and pH the GRCl turns out as the
most soluble and GRCO3 the least soluble. Boclair and Braterman70 estimated the solubility
products of different Fe(III)-M(II) chloride LDHs (M = Mg, Co, Ni, Zn, Mn) by base titration
of mixed Fe(III)-M(II) salt solutions. Their data demonstrated a good linear correlation
between the pKsp of the M(OH)2 and the pKsp of the corresponding LDH. According to this
correlation, the pKsp of the GRCl should be close to 125 for a GRCl with an Fe(II):Fe(III) ratio of
2:1. Using a similar titration technique, Hansen et al.36 found pKsp(GRSO4) of 124.6, a value
which fits reasonable well into the linear correlation of Boclair and Braterman. However, all
other ∆Gfo data in Table 2 leads to pKsp (GR) values completely off line. This inconsistency has
not yet been resolved. One possible explanation is that the equilibrium between Fe(OH)3 and
GR anticipated by Hansen et al.36 is not valid, and that in general the GRs are less soluble than
predicted from the above mentioned linear relationship for Fe(III)-M(II) compounds due to
some additional stabilization of the GR structure, e.g., due to Fe(II)-Fe(III) charge transfer.
Another way to diagram the thermodynamic stability of the GRs is to delineate the
chemical conditions at which they will transform to other phases such as Fe2+, Fe3O4 or
Fe(OH)2. An example is given in Fig. 5 for the GRSO4 system; here pH and the redox potential
are used as the two main variables characterizing the system. When magnetite is excluded from
the system, the stability field of GRSO4 is relatively large, depending on activities of Fe2+ and
SO42- (Fig. 5a). However, if magnetite is present at low Fe2+ and SO42- activities (10-3) GRSO4
has no stability field and is metastable. At higher activities of Fe2+ and SO42-, GRSO4 has a
stability field in magnetite-containing systems (Fig. 5b). A similar diagram can be drawn for
GRCl. Reduction of sulphate is not included. Under sulfidic conditions GRs will dissolve due to
precipitation of Fe(II) sulfides. Based on the available thermodynamic data, it can be concluded
that GRSO4 and GRCl can have distinct but restricted stability fields; at decreasing activities of
Fe2+ or interlayer anion they become metastable towards magnetite. The GRCO3 is metastable in
presence of FeCO3.14
Figure 5 Stability diagram for the Fe-H2O-O system including GRSO4. a) Magnetite not included, activity of
Fe2+, Fe3+ and SO42- all set at 10-3, b) Magnetite included, activity of Fe2+, Fe3+ and SO42- set at 10-3, 10-2
and 10-1, respectively. Sulphate reduction not included. ∆Gfo(GRSO4) = -3791 kJ mol-1, all other
thermodynamic data from reference 69.
Reactivity
The GRs participate in similar types of reactions as other LDHs, but in addition GRs are
relatively strong reductants and transform to Fe oxides when oxidized or moderately heated.
The high reactivity of GRs as reductants opens for an interesting chemistry in relation to
environmental applications, natural attenuation processes and Fe cycling.
Coprecipitation
The GRs can substitute Fe(II) or Fe(III) for other di- or trivalent cations in the metal
hydroxide layers. Theoretically, all the Fe(II) can be substituted by other divalent metal cations,
e.g., Ni(II) or Co(II). Tamaura and coworkers have studied the incorporation of different metal
cations into GRSO4 during its precipitation.37,71 Acidic cations are most readily incorporated and
may show higher preference for the solid than Fe(II) or Fe(III). Thus waste waters containing
Cd, Cu, Pb, Zn, Co and Ni cations can be cleaned by addition of FeSO4 and base to precipitate
GR.72 Similarly, it has been demonstrated that acid mine drainage water can be cleaned by the
same method simply by neutralizing the water with alkali; no addition of Fe compounds is
required as the mine water already contains much Fe and other cations which fit into the metal
hydroxide layers.73 Isomorphous substitution of tetravalent uranium and technetium into
GRCO3 during electrochemical synthesis of GR from Fe anodes has been described by Roh et
al.74 The precipitated GR sludges can be converted to ferrites by heating or oxidation, thus
encapsulating the metal cations in a much more stable solid than GR.50,75 The ferrites can be
collected magnetically and used for refining of the metals.72
Ion Exchange
Anions can sorb to the GR interlayer through ion exchange. The general anion affinity
sequences for LDH are likely to hold for GRs also. Thus, carbonate is preferably sorbed over
sulphate as evidenced from syntheses where both anions were present simultaneously.76 In
sulphate media GRCl transforms to GRSO4.29,30,76 Lewis et al.29 showed that the 3:1
Fe(II):Fe(III)-ratio of the GRCl was kept constant during exchange with sulphate, indicating
that a complete dissolution-reprecipitation process is not taking place during anion exchange.
Orthophosphate can exchange for sulphate in GR, but the product is unstable and transforms to
vivianite (Fe3(PO4)2 8H2O).35 A similar reaction is found to take place in presence of arsenate.77
Anionic surfactants are easily inserted in LDH interlayers78 in a similar way as cationic
surfactants are incorporated into phyllosilicate clays. Linear alkyl-benzene-sulphonates (LAS)
show high affinity for the GR interlayer and exchange efficiently for sulphate at solution LAS
concentrations as low as 1 mM (Fig. 6). The strong sorption affinity of LAS is in contrast with
its low charge/size ratio, and demonstrates that non-electrostatic forces such as van der Waals
forces between alkyl chains are important for LAS sorption. On LAS intercalation the layer
thickness expands from 1.1 nm to 3.0 nm (Fig. 6). The GRLAS has a hydrophobic interlayer
created by the alkyl chains of the LAS and thus acts as an efficient sorbent of non-polar
compounds like tetrachloromethane.79
Oxidizing anions can sorb into the interlayer from which they can oxidize Fe(II) in the GR.
E.g., NO3- can exchange for Cl- in GRCl.30 Nitrate can only exchange for sulphate under forced
anion exchange, e.g., by precipitation as BaSO4.45 Similar reactions may take place if GRs are
used as reductants of other anionic oxidants like selenate and chromate (see below).
Redox Reactions
The redox potentials listed in Table 3 show that GRs are strong reductants of similar
strength as Fe(OH)2, but stronger than Fe2+ in solution. The reducing strength is higher with
formation of Fe3O4 than formation of γ-FeOOH. The half cell redox potentials decrease with
pH. Furthermore, the relatively high external surface areas and very large internal surface areas
suggest that redox reactions with GRs may not be too slow.
Figure 6 Exchange of SO42- with linear alkyl-benzene-sulphonates (LAS) in the interlayer of GR

demonstrated by desorption of SO42- and adsorption of LAS. Inserts show rational series of basal reflections
from the GRLAS with d-spacings in nm.
Table 3 Comparison of redox potentials for half cells comprising Fe(II)-Fe(III) couples (25oC)
Half cella Eo (V) E7 (V)b

+ 2- II III
6H +SO4 + 6 γ-FeOOH → Fe4 Fe2 (OH)12SO4 0.58 -0.09
+ 2- - II III
4H + SO4 +4H2O + 2Fe3O4 + 2e → Fe4 Fe2 (OH)12SO4 0.33 -0.59
4H+ + Cl- +4H2O + 2Fe3O4 + 2.5e- → Fe4.5IIFe2.5III(OH)12SO4 0.18 -0.59
H+ + γ-FeOOH + e- → Fe(OH)2 0.16 -0.08
3H+ + γ-FeOOH + e- → Fe2+ + 2H2O 0.85 -0.22
a. ∆Gfo (GRSO4) set to –3791 kJ mol-1. Other thermodynamic data from reference 69.
b. Redox potential calculated at pH 7 and an activity of SO42- or Cl- of 10-3.
Oxygen
Oxidation of Fe(II) in aqueous solution by dioxygen in the pH-range 6.5 – 9 proceeds via
GR phases unless the presence of strong ligands prevents GR formation. Depending on the rate
of oxidation, the nature of the GR, pH, temperature, the concentration of Fe(II) in solution and
other solution variables, different Fe oxides can form. The most common oxidation products
are magnetite/maghemite, lepidocrocite, goethite and ferrihydrite. Akaganeite and δ-FeOOH
can also form (Fig. 7).32,39,80,81 The chemistry of the phase transformations of iron oxides have
been reviewed recently by Cornell and Schwertmann,82 and here only a few general comments
will be given. However, the trends observed with respect to product dependence on oxidation
rate and other reaction parameters are useful to bear in mind in studies of GR reactions with
other oxidants than dioxygen.
Figure 7 Formation of Fe oxides from GRs
Slow oxidation, higher temperatures and higher pH leads to magnetite/maghemite,

whereas more rapid oxidation at lower temperatures and pH gives lepidocrocite or goethite.83
Taylor33 showed that lepidocrocite was formed at the expense of magnetite when the Cl/Fe ratio
in the synthesis suspensions was increased. Although lepidocrocite may be the final oxidation
product, magnetite may form transiently.84 Rapid oxidation of GR leads to δ-FeOOH.85
Ferrihydrite also forms on rapid oxidation and in particular if crystallization inhibitors such as
silicic acid are present.86 Akaganeite is confined to systems with high chloride contents and
forms via chloride GRs.87 Goethite is the dominating product when GRCO3 is slowly
oxidized.39,88 However, goethite also forms from GRSO4 or GRCl predominantly in systems
containing relatively high concentrations of soluble Fe(II) (high initial Fe(II)/OH- ratios), or at
high pH.55,82,89,90 The specific mode of GR oxidation determines particle size, morphology and
reactivity of the Fe oxides formed. Receipes for the formation of acicular goethite and
lepidicrocite with GRSO4 and GRCl as intermediate phases, have been given by Kumazawa et
al.91 and Kurokawa and Senna.92
Nitrate and Nitrite
Nitrate is reduced stoichiometrically to ammonium by GR which in turn is oxidized to

magnetite.28,30,93 In case of GRSO4 the reaction is given by:
II III − − 2− +
Fe4 Fe2 (OH)12 SO4 + 14 NO3 + 32 OH ↔ SO4 + 14 NH4 + 2Fe3O4 + 6 14 H2O (Eqn.13)
The reaction is found to be first order with respect to Fe(II) in GR (Fe(II)GR) (Fig. 8). Thus,
at constant concentration of nitrate the rate of formation of ammonium is given by:
d[NH +4 ]
= k obs • [Fe(II)]GR (Eqn.14)
dt
Figure 8 Reduction of NO3- to NH4+ by GRCl in non-buffered suspensions (pH 8.2 – 6.2) at a NO3-
concentration of 14.3 mM and room temperature. Fe(II)sol denotes Fe(II) in solution and Fe(II)GR the Fe(II) in
GRCl. Solid lines represent fits by first-order rate equation (from ref. 30).   NH4+; ( ) Fe(II)sol; ( )
Fe(II)GR. Rerpinted from H. C. B. Hansen, S. Guldberg, M. Erbs and C. Bender Koch, Kinetics of nitrate
reduction by green rusts: effect of interlayer anion and Fe(II):Fe(III) ratio, Appl. Clay Sci. 18 (2001) 81, @
2001, with permission from Elsevier Science.
Experiments with different interlayer forms of GRs having approximately the same
particle size show that nitrate is reduced about 30 times faster with GRCl than GRSO4 and GRCO3
(Table 4). A similar observation has been made on forced exchange of sulphate with nitrate in
GRSO4 causing the rate to increase about 30 times.45 These observations are consistent with the
rate of reaction being controlled by the accessibility of nitrate to reactive sites of the
Fe(II)-Fe(III) hydroxide layers. Nitrate cannot exchange for carbonate or sulphate in the GR
interlayers; hence oxidation can only proceed from external surfaces and inwards. However,
nitrate can exchange for chloride and therefore both external and internal sites becomes
accessible in GRCl (Fig. 9). Another feature of the nitrate reduction process is that the GR
particles are not becoming gradually oxidized as the reaction progresses, reflecting that
oxidized parts of the GR particles are immediately converted to Fe3O4. For the reaction
between nitrate and GRSO4, the activation energy is about 84 kJ mol-1.45
Table 4 Rate constants for reduction of nitrate by GRSO4 ([NO3-] = 14.3 mM, 25 oC)
Interlayer ion Fe(II):Fe(III)a kobsb (x 10-5 s-1) Comment Reference
SO42- 2.0 0.95 51
SO42- 3.0 4.70 GRCl → GRSO4 30
SO42- 2.0 32.8 Forched exchange 45
Cl- 3.0 30.8 30
CO32- 2.0 1.48 93
Ctrl ∼0 Fe(II) in solution 51
a. Initial Fe(II):Fe(III) ratio in GR

b. kobs relates to d[NH4+]/dt = kobs·r·[Fe(II)]GR where r is the stoichiometric ratio between NH4+ produced and
Fe(II)GR consumed ( (∆[ NH 4+ ] / ∆[Fe(II)] GR ).
Figure 9 Rates of nitrate reduction and nitrate accessibility to GR surface sites. For GRSO4 and GRCO3 access
is via external surface sites only whereas for GRCl (and forced nitrate exchange of GRSO4) internal surface
sites can also be approached.
Nitrite is reduced about 100 times faster by GRs than nitrate. Also the products are
different. At low nitrite concentrations GR is oxidized to magnetite whereas higher nitrite
concentrations give rise to lepidocrocite.60 The main reduction products of nitrite is nitrous
oxide and probably some dinitrogen as well; only little ammonium is produced.36,60 This is in
strong contrast to the reaction with nitrate, where ammonium is the only product, and may
indicate that either the reaction pathways of the nitrate and nitrite reductions are different, or
that higher concentrations of intermediates in the nitrite reaction enables other reactions to take
place. E.g., in the nitrite reaction higher concentrations of nitroxyl ions may occur. After
protonation these can combine and form nitrous oxide:
2HNO ↔ N 2 O + H2 O (Eqn.15)
Another possibility is the reaction between nitrite and ammonium with formation of
dinitrogen.94 Thus, if ammonium is formed during the nitrite reduction it could react with nitrite
with formation of dinitrogen:
NH +4 + NO −2 ↔ N2 + 2H 2 O (Eqn.16)
More studies are needed to clarify the mechanisms of the nitrite and nitrate reductions. An
interesting aspect is how electrons are transferred from Fe(II) in the GR to the nitrogen; and
how this is coupled to the formation of magnetite. Magnetite may not form directly from the
GR, but could form as a reaction product of Fe(III) hydroxy clusters with Fe(II) in solution. The
GR is not thought to be a good conductor of electricity and thus the reactive N-O species
probably have to move from one site to another before complete reduction is achieved.
Selenium(IV/VI), Chromium(VI) and Other Inorganic Oxidants
Myneni et al.95 demonstrated that Se(VI) either as selenate coprecipitated with GR or as

selenate added to GRSO4 becomes reduced. The oxidation product of the GR was primarily
magnetite. By use of XANES spectroscopy, the main Se products were found to be amorphous
clusters of Se(0); with the coprecipitated samples Se(IV) was detected as intermediates. In
some experiments traces of Se(-II) was observed. The process was further studied by Refait et
al.,58 but in contrast to the previous work where Fe(II)GR was always in large excess, these
authors used systems with Se(VI):Fe(II) ratios of 2, i.e., more Se(VI) was added than could be
reduced even to Se(IV). Iron(II) hydroxide was oxidized by selenate to ferrihydrite and
lepidocrocite; a GR with selenate in the interlayer and an Fe(II):Fe(III)-ratio varying between 2
– 2.7 formed as an intermediate. The Fe oxide products were found to contain Se(VI) and
Se(IV). It seems likely that in this study Se(VI) was not reduced beyond Se(IV), as all reducing
equivalents were consumed for the Se(VI) → Se(IV) reduction. At lower Se(VI):Fe(II)GR-ratios
Se-containing spinels are formed.77 This study also showed that selenite was reduced much
faster than was selenate. It can be concluded that GRs represent strong reductants of Se(IV) and
Se(VI) and that product distributions will depend on the ratio of Se to Fe(II)GR.
Chromium(VI) is reduced to Cr(III) by GRs in a very fast reaction.47,96 The Cr(III)
produced is incorporated into the ferrihydrite which form as an oxidation product of the GR.
Williams and Scherer47 have shown that the reduction of chromate by GRCO3 at pH 7 follows
first order kinetics with respect to Cr(VI) at higher GR surface area concentrations according
to:
d[Cr(VI)]
= k • [Cr(VI) ]• AGR (Eqn.17)
dt
where k = 7.3 10-4 L m-2 s-1 and AGR is the surface area concentration of GRCO3. The rate of
reaction is several magnitudes higher than the reaction between GRCO3 and nitrate mentioned
above. The authors also showed that chromate sorption to the GR interlayer is insignificant and
thus only external surfaces of GRCO3 seems to be exposed to the oxidant. In a study of
chromate sorption to chloride, forms of non-oxidizable LDHs chromate was not found to
exchange for interlayer chloride, indicating that GRCl may not neccesarily react faster with
chromate than GRCO3 does.97
Preliminary work on GR oxidation by perchlorate shows that in the presence of 14 mM

NaClO4 no oxidation can be observed for GRSO4 over a period of 100 h, whereas GRCl seems to
oxidize slowly as determined from the net decrease in Fe(II)GR over time corresponding to a
reaction rate of 2.3 10-9 ± 0.4 10-9 M s-1. This rate is about 25 times slower than when nitrate is
used as an oxidant. With arsenate no oxidation of GRSO4 is observed in the presence of 10 mM
Na3AsO4 over a period of 100 h. However, addition of arsenate causes solution Fe(II)
concentrations to become very low, indicating that precipitation is taking place. XRD of the
solids show the presence of Fe(II)-arsenates (Fe3(AsO4)2 8H2O).77 This reaction sequence is
similar to what has been observed in GRSO4 – phosphate systems.35
Organic Oxidants
It is well known that hydrocarbons containg chloro- or nitrosubstituents can be reduced in

the presence of Fe(II) sorbed to Fe(III) oxide surfaces suggesting that similar redox reactions
may occur in the presence of GRs.98,99 Erbs et al.100 found that when an excess of
tetrachlormethane was added to GRSO4 chloroform and minor amounts of hexachloroethane
were produced; magnetite was formed as the oxidation product. The rate of the reaction, which
was first order with respect to Fe(II)GR was similar to the rate observed for nitrate reduction by
GRSO4. O'Loughlin and Burris,101 also working with reduction of tetrachloromethane by GRSO4,
found that addition of Cu(II) to the reaction suspensions (about 2.5 % of the Fe added) gave rise
to a much faster reduction and that fully dehalogenated methane and C2 – C5 alkanes and
alkenes were produced. In another study where an excess of GRSO4 was reacted with 5 different
polyhalogenated ethanes, the corresponding ethenes were produced through reductive
β-elimination.102 On longer reaction times (300 – 1200 h) ethene and ethane were produced.
Also in this study a marked catalyzing effect of Cu(II) was observed giving rise to 10 – 160
times higher reduction rates compared to systems with no Cu (Fig. 10). The study also showed
that bromosubstituted alkanes were more readily reduced than the chlorosubstituted
counterparts, and that reduction rates increased with the number of halogens in the alkanes. The
catalyzing effect of Cu(II) is also known from reduction of nitrate by Fe(II).103 In a similar
study Lee and Batchelor104 found that during 60 d GRSO4 reduced halogenated ethenes to less
halogenated ethenes, including ethene. In addition, acetylene and ethane were detected.
Magnetite formed as an oxidation product of GR. It was also found that synthetic magnetite
could act as a reductant of the chlorinated ethenes, suggesting that the magnetite formed in the
GR suspensions may act as reductant when the reducing equivalents in the GRs have been
consumed. It can be concluded that GRs are able to reduce chlorinated alkanes and alkenes to
their fully dehalogentated compounds, but that reaction rates are strongly dependent on the type
of compound and the presence of catalysts such as Cu(II) in the GR. Studies are needed to
describe product distributions as function of reactant concentrations, time, pH and interlayer
form of GR.
Ongoing investigations of GR reduction of nitroaromates (nitrobenzene, nitrophenole,
nitrobenzoic acid) show that the reaction is fast and of similar nature as the reactions with Fe2+
sorbed to Fe(III) oxides.99
GREEN RUSTS IN NATURAL ENVIRONMENTS

In the laboratory GRs are readily formed from mixed Fe(II)-Fe(III) systems and it is
expected that formation of GRs should be a common process in natural anoxic, non-acid
aqueous and terrestrial systems. However, the high reactivity of the GRs including its
oxidation by dioxygen during sampling, handling and analysis is probably the main reason that
GRs have not very often been identified in mineralogical analyses. Our current understanding
of GR occurences in natural environments is therefore far from being complete.
The most unquestionable identifications of GRs originates from corrosion sheets and
tubercles of iron. Large crystals of GRCO3 have been identified in drinking water pipes by
means of XRD and microscopic examination.12,105 In marsh sediments concretions formed by
corrosion of iron fragments was found to contain well crystalline GRSO4.106 Sulphate-GR has
also been observed on steel sheets in contact with seawater in harbours by means of Mössbauer
spectroscopy.107 Mössbauer spectroscopy indicated that GRCO3 was present in anoxic ochre
sludges.108 Iron(0) has gained popularity in remediation of groundwaters polluted with
chlorinated solvents, nitroaromatics, nitrate, etc. Oxidation of Fe(0) by such organic oxidant
results in GR formation, at least as transient phases.22,23,46
Figure 10 Reduction of hexachloroethane to tetrachloroethene by GRSO4 in absence (•) and presence (♦) of
100 µM Cu2+. Approx. starting concentrations were 3.5 mM GRSO4 and 20 µM hexachloroethane (Based on
data from ref. 102).
Microbial oxidation of organic matter and concomitant reduction of Fe(III) to Fe(II) is a

necessary prerequisite for the formation of GRs in most geoenvironments. Fredrickson et al.109
observed precipitation of GR (probably GRCO3) in batch experiments with microbial reduction
of ferrihydrite. The GR was identified as hexagonal crystals showing a GR XRD pattern. It is
likely that microbially produced mineral reductants or surface adsorbed Fe(II) may represent
better reductants of polyhalogenated compounds, nitroaromatics, azocompounds etc. than the
intercellular enzymatic reduction pathways.99,110,111 Green rust may represent one of such very
reactive biominerals. A hypothetical reduction sequence may be depicted as:
CH2O GR Red. pollut.
CO2 FeOOH Ox pollut.

(Eqn.18)
The occurence and geochemistry of GR in anoxic soil layers have recently been reported
by Trolard et al.,112 Génin et al.,14 and Bourrié et al.7 Mössbauer spectra of bluish iron-rich soil
materials were shown to have similar quadrupole splittings and isomer shifts as synthetic GRs,
although the Fe(II):Fe(III) ratios were lower than those observed for synthetic GRs. Raman
spectra of the soil samples supported the presence of GR. Only small amounts of chloride,
sulphate or carbonate could be identified in the samples suggesting the presence of other
interlayer ions. Hydroxide was postulated as the interlayer ion, and the formulas
[Fe3(OH)6]+[OH]-, [Fe2(OH)4]+[OH]- and [Fe3(OH)6]2+[(OH)2]2- were proposed for the soil
GRs. The Fe2+ activities and pH of the soil waters ranged between 10-4.5 – 10-7 and 5.15 – 6.35,
respectively. There are at least two properties of the proposed soil GRs which do not fit into the
knowledge gained so far from studies of synthetic GRs and LDHs. First, hydroxide is not very
likely as the interlayer anion, as the anoxic more or less water saturated environments contains
carbon dioxide which is expected to react immediately with the hydroxide in the interlayer to
form bicarbonate or carbonate.113 Second, the pH and the Fe2+ activity of the soil waters are
below the pH at which GRs normally are found to precipitate (> 6.5). In a study of Fe(II)
mineral formation in an aquifer caused by an increased input of organic matter from the soil
surface, Banwar114 found that the groundwater was undersaturated with respect to GRSO4.
However, if the solubility products listed elsewhere had been used, the groundwater would be
supersaturated with respect to GRSO4 and probably with GRCO3 as well.
Arden5 thought, that the 'ferroso ferric hydroxide' Fe3(OH)8 (= Fe3O4⋅4H2O =
[Fe3(OH)6]2+[(OH)2]2-) was the actual compound controlling Fe2+ activities in Fe(II)- Fe(III)
hydroxide suspensions. However, by repeating Ardens experiments Hansen et al.36
demonstrated that GRSO4 and not Fe3(OH)8 was the actual compound precipitating. Recently,
based on mesurements of Fe2+ activities, pH and electrochemical potentials in reduced soil
suspensions Brennan and Lindsay115 postulated that "amorphous magnetite" controlled Fe(II)
solubility. For the reaction:
+ − 2+
Fe 3O 4 (amorphous) + 8H + 2e ↔ 3Fe + 4H2 O (Eqn.19)
a log K of 40.7 was determined. In reduced rice soils Ponnamperuma et al.6 determined a
log K of 47.1 for Eq. 19 but with Fe3O4 substituted by Fe3(OH)8. For this reaction the values
reported by Bourrié et al.7 gives log K 45.8 (9 oC). The widely vayring estimates demonstrate
that the solubility of the hypothetical Fe3O4(amorphous) or Fe3(OH)8 phases is not well defined.
In order to clarify the existence of such phases in geoenvironments direct measurements of the
compounds stoichiometry, structure and their equilibrium properties in natural as well as

synthetic systems are needed.
It is hypothesized that GRs may have played significant roles under more reduced
conditions on Earth, and may have constituted an important mineral phase in the Archean ocean
contributing to the formation of banded iron formations.116 Green rusts have also been used in
models describing the formation of Martian nanophase Fe oxide particles.117
REFERENCES
1 W. Ostwald, Grundlinien der Anorganischen Chemie. Verlag Wilhelm Engelmann,
Leipzig, (1900) pp. 577-578.
2 E. Deiss and G. Schikorr, Z. Anorg. Allg. Chem. 172 (1928) 32.
3 W. Feitknecht, Fortschr. Chem. Forsch. 2 (1953) 670.
4 J.D. Bernal, D.R. Dasgupta and A.L. Mackay, Clay Miner. Bull. 4 (1959) 15.
5 T.V. Arden, J. Chem. Soc. (1950) 882.
6 F.N. Ponnamperuma, M.T. Estrella and T.Loy, Soil Sci. 103 (1967) 374.
7 G. Bourrié, F. Trolard, J.-M.R. Génin, A. Jaffrezic, V. Maitre and M. Abdelmoula,
Geochim. Cosmochim. Acta 63 (1999) 3417.
8 W. Feitknecht and G. Keller, Z. Anorg. Chem. 262 (1950) 61.
9 J.M.R.Génin, D. Rezel, P. Bauer, A. Olowe and A. Beral, in Electrochemical methods in
corrosion research, Duprat, M. (ed.) Materials Science Forum vol. 8, Trans Tech Publ.,
Switzerland (1986) 477.
10 A.A. Olowe, J.M.R. Génin and P. Bauer, Hyperfine Interact. 46 (1989) 437.
11 A.S. Bookin and V.A. Drits, Clays Clay Miner. 41 (1993) 551.
12 P.P. Stampfl, Corr. Sci. 9 (1969) 185.
13 I.R. McGill, B. McEnaney and D.C. Smith, Nature 259 (1976) 200.
14 J.-M.R. Génin, G. Bourrie, F. Trolard, M. Abdelmoula, A. Jaffrezic, P. Refait, V. Maitre,
B. Humbert and A. Herbillon, Environ. Sci. Technol. 32 (1998) 1058.
15 G. Vatankhah, M. Drogowska and H. Menard, J. Appl. Electrochem. 28 (1998) 173.
16 P. Refait, M. Abdelmoula and J.-M.R. Génin, Corr. Sci. 40 (1998) 1547.
17 J.-C. Petit, C. R. Acad. Sci. A 251 (1960) 878.
18 K.K. Sagoe-Crentsil and F.P. Glasser, Cement Concrete Res. 23 (1993) 785.
19 G. Butler and J.G. Beynon, Corr. Sci. 7 (1967) 385.
20 J. Kassim, T. Baird and J.R. Fryer, Corr. Sci. 22 (1982) 147.
21 J.R. Gancedo, L. Martinez and J.M. Oton, Anal. Quim. 79 (1983) 470.
22 M.M. Scherer, B.A. Balko and P.G. Tratnyek, in Mineral-water interfacial reactions:
Kinetics and mechanisms, (Sparks, D.L. and Grundl, T.J., eds) Symp. Ser. 715, ACS,
Washington, DC, (1999) pp. 301 – 322.
23 P.M.L. Bonin, W. Jedral, S. Odziemkowski and R.W. Gillham, Corr. Sci. 42 (2000) 1921.
24 S.H. Drissi, P. Refait, M. Abdelmoula and J.M.R. Génin, Corr. Sci. 37 (1995) 2025.
25 J. Bessière, M. Perdicakis and B. Humbert, C.R. Acad. Sci. Ser. II Fasc. C- Chimie 2
(1999) 101.
26 G.N. Schrauzer and T.D. Guth, J. Am. Chem. Soc. 98 (1976) 3508.
27 J. Vins, J. Subrt, V. Zapletal and F. Hanousek, Collect. Czech Chem. Commun. 52 (1987)
93.
28 H.C.B. Hansen, C.B. Koch, H. Nancke-Krogh, O.K. Borggaard and J. Sørensen, Environ.
Sci. Technol. 30 (1996) 2053.
29 D.G. Lewis, in Soils and Environment. Soil Processes from Mineral to Landscape Scale
(Auerswald, K.; Stanjek, H.; Bigham, J.M., eds.) Adv. GeoEcol. 30 (1997) 345.
30 H.C.B. Hansen, S. Guldberg, M. Erbs and C. Bender Koch, Appl. Clay Sci. 18 (2001) 81.
31 U. Schwertmann and H. Fechter, Clay Miner. 29 (1994) 87.
32 A. Solcova, J. Subrt, J. Vins, F. Hanousek, V. Zapletal and J. Tlaskal, Coll. Czech. Chem.
Commun. 46 (1981) 3049.
33 R.M. Taylor, Clays Clay Miner. 32 (1984) 167.
34 R.M. Taylor, U. Schwertmann and H. Fechter, Clay Miner. 20 (1985) 147.
35 H.C.B. Hansen and I.F. Poulsen, Clays Clay Miner. 47 (1999) 312.
36 H.C.B. Hansen, O.K. Borggaard and J. Sørensen, Geochim. Cosmochim. Acta 58 (1994)
2599.
37 Y. Tamaura, Inorg. Chem. 24 (1985) 4363.
38 R.M. Taylor and R.M. McKenzie, Clays Clay Miner. 28 (1980) 179.
39 R.M. Taylor, Clay Miner. 15 (1980) 369.
40 Y. Tamaura, K. Ito and T. Katsura, J. Chem. Soc., Dalton Trans. (1983) 189.
41 S. Mann, N.H.C. Sparks, S.B. Couling, M.C. Larcombe and R.B. Frankel, J. Chem. Soc.,
Faraday Trans. I 85 (1989) 3033.
42 E. Tronc, P. Belleville, J.-P. Jolivet and J. Livage, Langmuir 8 (1992) 313.
43 H.C.B. Hansen, Clay Miner. 24 (1989) 663.
44 C. Bender Koch, Hyperfine Interact. 117 (1998) 131.
45 H.C.B. Hansen and C. Bender Koch, Clay Miner. 33 (1998) 87.
46 B. Gu, T.J. Phelps, L. Liang, M.J. Dickey, Y. Roh, B.L. Kinsall, A.V. Palumbo and G.K.
Jacobs, Environ. Sci. Technol. 33 (1999) 2170.
47 A.G.B. Williams and M.M. Scherer, Preprint of Extended Abstracts, 220th ACS National
Meeting, Washington DC (2000), 40 (2), 666.
48 A.H. Cuttler, V. Man, T.E. Cranshaw and G. Longworth, Clay Miner. 25 (1990) 289.
49 Y. Tamaura, M. Saturno, K. Yamada and T. Katsura, Bull. Chem. Soc. Jpn. 57 (1984)
2417.
50 Y. Tamaura, T. Yoshida and T. Katsura, Bull. Chem. Soc. Jpn. 57 (1984) 2411.
51 C.B. Bender Koch and H.C.B. Hansen, in Soils and Environment. Soil Processes from
Mineral to Landscape Scale. (Auerswald, K, Stanjek, H.; Bigham, J.M., eds), Adv.
GeoEcol. 30 (1997) 373.
52 J.-MR. Génin, A.A. Olowe, P. Refait and L. Simon, Corr. Sci. 38 (1996) 1751.
53 T. Kanzaki and T. Katsura, J. Chem. Soc., Dalton Trans. (1986) 1243.
54 L. Simon, J.-M.R. Génin and P. Refait, Corr. Sci. 39 (1997) 1673.
55 P. Refait and J.-M.R. Genin, Corr. Sci. 34 (1993) 797.
56 G.W. Brindley and D.L. Bis, Nature 263 (1976) 353.
57 E. Murad and R.M. Taylor, Clay Miner. 19 (1984) 77.
58 P. Refait, L. Simon and J.-M.R. Génin, Environ. Sci. Technol. 34 (2000) 819.
59 P. Refait, A. Charton and J.-M.R. Génin, Eur. J. Solid State Inorg. Chem. 35 (1998) 655.
60 H.C.B. Hansen, unpublished data.
61 R.M. Cornell and W. Schneider, Polyhedron 8 (1989) 149.
62 T. Misawa, S. Wataru and S. Shimodaira, Bull Chem. Soc. Jpn. 42 (1969) 3339.
63 K.K. Sagoe-Crentsil and F.P. Glasser, Corrosion 49 (1993) 457.
64 N. Boucherit and A.H.L. Goff, Faraday Discuss. Chem. Soc. 94 (1992) 137.
65 G.W. Brindleyand S. Kikkawa, Amer. Mineral. 64 (1979) 836.
66 J. Detournay, L. de Miranda, R. Derie and M. Ghodsi, Corr. Sci. 15 (1975) 295.
67 E. Murad and R.M. Taylor, in Industrial Applications of the Mössbauer effect, (Long, G.J.
and Stevens, J.G., eds), Plenum Publ. Comp., New York (1987), pp. 585-593.
68 P. Refait, C. Bon, L. Simon, G. Bourrié, F. Trolard, J. Besiere and J.-M.R. Génin, Clay
Miner. 34 (1999) 499.
69 D.D. Wagman, W.H. Evans, V.B. Parker, R.H. Schumm, I. Hlow, S.M. Bailey, K.L.
Churney and R.L. Nuttall, The NBS tables of chemical thermodynamic properties.
Selected values for inorganic and C1 and C2 organic substances in SI units. J. Phys.
Chem. Ref. Data 11, (1982) Suppl. 2.
70 J.W. Boclair and P.S. Braterman, Chem. Mater. 11 (1999) 298.
71 Y. Tamaura, Bull. Chem. Soc. Jpn. 58 (1985) 2951.
72 Y.Tamaura, Y.; Katsura, T.; Rojarayanont, S.; Yoshida, T.; Abe, H., Wat. Sci. Tech. 23
(1991) 1893.
73 R.M. Taylor, R.W. Arthur, I.D. Ennis and R.G. Robins, EPD Congress. The Minerals
Metals & Materials Soc., TMS Warrendale PA (1998), pp. 367-379.
74 Y. Roh, S.Y. Lee, M.P. Elless and J.E. Foss, Clays Clay Miner. 48 (2000) 266.
75 O.P. Perez and Y. Umetsu, Hydrometallurgy 55 (2000) 35.
76 P. Refait, S.H. Drissi, J. Pytkiewicz and J.-M.R. Génin, Corr. Sci. 39 (1997) 1699.
77 J. Dickow, Reduction of arsenate and selenate by sulphate green rust. Thesis, Chem.
Dept., Royal Vet. Agricult. Univer., Copenhagen (2001) (in Danish).
78 H. Kopka, K. Beneke and G. Lagaly, J. Coll. Interf. Sci. 123 (1988) 427.
79 D.K. Kaldor, Sorption of tetrachloromethane to iron(II)-iron(III) hydroxides (green rust)
B.Sc. thesis, Chemistry Department, Royal Vet. & Agricult. Univ., Copenhagen (2000)
49 pp. (in Danish).
80 T. Misawa, K. Hashimoto and S. Shimodaira, Corr. Sci. 14 (1974) 131.
81 R.M. Taylor and U. Schwertmann, Clay Miner. 10 (1974) 299.
82 R.M. Cornell and U. Schwertmann, The iron oxides. Structure, properties, reactions,
occurence and uses. VCH Verlagsgesselsch., Weinheim (1996), 570 pp.
83 S. Hamada and K. Kuma, Bull. Chem. Soc. Jpn. 48 (1976) 3695.
84 R. Srinivasan, R. Lin, R.L. Spicer and B.H. Davis, Coll. Surfaces A 113 (1996) 97.
85 A.A. Olowe, Y. Marie, P. Refait and J.-M.R. Génin, Hyperf. Interact. 93 (1994) 1783.
86 Z. Karim, Soil Sci. Soc. Am. J. 50 (1986) 247.
87 P. Refait and J.-M.R. Génin, Corr. Sci. 39 (1997) 539.
88 L. Carlson and U. Schwertmann, Clay Miner. 25 (1990) 65.
89 Y. Tamaura, P.V. Buduan and T. Katsura, J. Chem. Soc., Dalton Trans. (1981) 1807.
90 A.A. Olowe and J.-M.R. Génin, Corr. Sci. 32 (1991) 965.
91 H. Kumazawa, T. Inami, H.-M. Cho and E. Sada, Chem. Eng. Comm. 113 (1992) 91.
92 H. Kurokawa and M. Senna, Powder Technol. 103 (1999) 71.
93 H.C.B. Hansen and C.B. Koch, C.B., in Clays for our future. Proc. 11th Int. Clay Conf.,
Ottawa, Canada, 1997. (Kodama, H.; Mermut, A.R.; Torrance, J.K., eds.) ICC-97
Organizing Committee, Ottawa, Canada (1999), 295.
94 J.C. Fanning, Coord. Chem. Rev. 199 (2000) 159.
95 S.C.B. Myneni, T.K. Tokunaga and G.E. Brown Jr., Science 278 (1997) 1106.
96 S. Loyaux-Lawniczak, P. Refait, J.-J. Ehrhardt, P. Lecomte and J.-M.R. Génin, Environ.

Sci. Technol. 34 (2000) 438.
97 B. Houri, A. Legrouri, A. Barroug, C. Forano and J.-P. Besse, J. Chim. Phys. 96 (1999)
455.
98 S.B. Haderlein and K. Pecher, K., in Mineral/Water intefacial reactions: Kinetics and
mechanisms (Sparks, D.L. and Grundl, T., eds), Symp. Ser. 715, ACS, Washington, DC,
(1999) pp. 342-356.
99 T.B. Hofstetter, C.G. Heijman, S.B. Haderlein, C. Holliger and R.P. Schwarzenbach,
Environ. Sci. Technol. 33 (1999) 1479.
100 M. Erbs, H.C.B. Hansen and C.E. Olsen, Environ. Sci. Technol. 33 (1999) 307.
101 E.J. O'Loughlin and D.R. Burris, Preprints of Extended Abstracts, 220th ACS National
Meeting, (2000), Washington DC 40 (1), 62.
102 E.J. O'Loughlin and D.R. Burris, Preprints of Extended Abstracts, 220th ACS National
Meeting, (2000) Washington DC 40 (2), 635.
103 R.J. Buresh and J.T. Moraghan, J. Environ. Qual. 5 (1976) 320.
104 W. Lee and B. Batchelor, Preprint of Extended Abstracts, 220th ACS National Meeting,
(2000), Washington DC, 40 (2), 338-340.
105 O.V. Tuovinen, K.S. Button, A. Vuorinen, L. Carlson, D.M. Mair and L.A. Yut, Amer.
Water Works Assoc. J. 72 (1980) 626.
106 M.R. Al-Agha, S.D. Burley, C.D. Curtis and J. Esson, J. Geol. Soc. London 152 (1995)
157.
107 J.-M.R. Génin, A.A. Olowe, B. Resiak, M. Confente, N. Rollet-Bendbouzid, S.
L´Harridon and D. Prieur, Hyperfine Interact. 93 (1994) 1807.
108 C. Bender Koch and S. Mørup, Clay Miner. 26 (1991) 577.
109 J.K. Fredrickson, J.M. Zachara, D.W. Kennedy, H. Dong, T.C. Onstott, N.W. Hinman
and S.-M. Li, Geochim. Cosmochim. Acta 62 (1998) 3239.
110 M.L. McCormick and P. Adriaens, Preprint of Extended Abstracts, 220th ACS National
Meeting, Washington DC (2000), 40 (2), 357.
111 K.F. Hayes, P. Adriaens, E.C. Butler and M.L. McCormick, Preprint of Extended
Abstracts, 220th ACS National Meeting, Washington DC (2000), 40 (2), 336.
112 F. Trolard, J.M.R. Génin, M. Abdelmoula, G. Bourrié, B. Humbert and A. Herbillon,
Geochim. Cosmochim. Acta 61 (1997) 1107.
113 S. Koritnig and P. Süsse, Tschermaks Min. Petr. Mitt. 22 (1975) 79.
114 S.A. Banwart, Geochim. Cosmochim. Acta 63 (1999) 2919.
115 E.W. Brennan and W.L. Lindsay, Soil Sci. Soc. Am. J. 62 (1998) 930.
116 K. Kuma, W. Paplawsky, B. Gedulin and G. Arrhenius, Orig. Life Evol. Biosphere 19
(1989) 57.
117 A. Banin, T. Ben-Shlomo, L. Margulies, D.F. Blake, R.L. Mancinelli and A.U. Gehring,
J. Geophys. Res. 98 (1993) 20831.
INDEX
366, 368, 370, 372, 374, 376, 377, 378

catalytic partial oxidation, 303
A
catalytic total oxidation, 304
AEC, 253, 254, 258, 260, 265, 268, 271, 391 cation distribution, 39, 49, 57, 61, 67, 68, 69, 82,
anionic clays, 1, 19, 39, 94, 131, 132, 139, 174, 84, 86, 218, 219
229, 251, 261, 285, 294, 300, 306, 310, 312, Charge Equilibration Method, 97
313, 314 CHT, 252, 253, 254, 255, 256, 260, 261, 262, 265,
anionic dyes, 273, 388, 390, 392 267
anionic exchange, 1, 5, 9, 18, 20, 26, 32, 115, 234, cinnamaldehyde, 369, 370, 371, 373
239, 253, 255, 262, 263, 265, 266, 267, 269, Claisen-Schmidt condensation, 293
271, 272, 273, 275 coalingite, 87, 150
anionic exchange capacity, 20, 253, 255, 262, 272, coherent scattering domains, 48
273 coke concentration, 331, 332, 333, 334, 338, 342,
350, 352, 353
coke deposition, 327, 331, 332, 333, 335, 336, 338,
B
339, 343, 356, 363
basal spacing, 5, 6, 7, 8, 18, 19, 20, 21, 22, 24, 27, coke formation, 152, 303, 305, 306, 324, 327, 331,
31, 32, 129, 162, 170, 172, 173, 175, 176, 178, 338, 339, 340, 342, 343, 344, 349, 350, 354,
179, 209, 210, 272, 276, 277, 281, 310, 311, 355, 356, 357, 363
418 consistent valence forcefield, 112
BHMBS, 178, 179 coprecipitation, 8, 9, 10, 11, 14, 15, 16, 17, 18, 24,
brucite layers, 26, 29, 31, 40, 41, 79, 87, 88, 210 26, 42, 88, 151, 152, 178, 222, 230, 261, 310,
brucite-like layers, 1, 3, 8, 12, 27, 39, 40, 42, 45, 323, 327, 328, 344, 359, 362, 364, 365, 366,
46, 48, 49, 52, 55, 57, 58, 61, 62, 63, 64, 68, 70, 367, 368, 370, 372, 373, 375, 376, 377, 388
71, 74, 76, 77, 78, 79, 80, 81, 82, 84, 85, 86, 87, CP, 195, 202, 205
88, 89, 115, 116, 119, 121, 122, 129, 133, 144, CPO, 303, 304, 305, 306
151, 229, 233, 241, 243, 248, 347 cross-polarisation, 193, 195, 205
crystallinity, 10, 14, 16, 88, 113, 120, 122, 149,
162, 231, 247, 265, 266, 269, 271, 272, 327,
C 328, 366, 388, 389, 416
CAL, 369, 370, 371 CSDs, 48
calcination, 27, 29, 33, 116, 117, 120, 121, 122, CTO, 304
123, 124, 125, 126, 127, 129, 131, 132, 133, CVFF, 112
174, 178, 179, 182, 230, 232, 233, 234, 238, cyclodextrine, 277, 279
243, 247, 248, 253, 256, 258, 260, 268, 272,
275, 280, 286, 287, 288, 289, 291, 293, 296, D
298, 299, 300, 301, 303, 304, 305, 307, 308,
312, 324, 325, 326, 327, 334, 335, 339, 344, DAS, 196
347, 348, 356, 358, 359, 361, 363, 364, 365, DBS, 271, 272, 279
496 Index
DDS, 271, 276, 277, 278, 279 Forcefield II, 98, 107, 108
DEA, 360, 362 forcefields, 96, 97, 107
decarbonation, 120, 121, 123, 126, 184, 290, 293 Fourier transform Infrared Emission Spectroscopy,
decomposition, 14, 34, 82, 115, 119, 120, 122, 123, 142
124, 125, 126, 128, 129, 130, 133, 153, 193, Fourier-transform infrared, 141
211, 216, 229, 243, 245, 290, 291, 296, 298, FTIR, 25, 26, 28, 141, 142, 150, 181, 183, 361,
300, 301, 302, 308, 309, 311, 312, 324, 335, 362, 373
339, 344, 357, 360, 363, 372, 374, 375, 377, FTIR spectroscopy, 141, 142, 362
378, 395
dehydroxylation, 22, 30, 33, 120, 121, 123, 124,
G
125, 126, 129, 130, 142, 183, 184, 197, 203,
311 GBL, 364, 365, 366, 367
delamination, 34, 35 GHSV values, 304, 306
dimethylformamide, 298 glycerol saturation, 55
disordered cation distribution, 49, 66, 74, 84 grafting, 22, 28, 29, 30, 119, 129, 133, 208, 233,
DMF, 298 383
dodecylbenzenesulfonate, 271 green rusts, 216, 217, 227, 413, 426
dodecylsulfate, 271, 272, 273, 276, 278 GRI, 414
Doppler effect, 215 GRII, 414
DOR, 196 GRs, 216, 413, 414, 415, 416, 417, 418, 419, 420,
double rotation, 196 422, 423, 425, 426, 427, 428, 429, 430, 431
Dreiding forcefield, 97, 106, 108
DRIFT, 163, 165
H
DSC, 116, 117, 125, 207
DTG, 116, 117, 120, 123, 124, 125, 129, 133 HDSs, 88
dynamic angle spinning, 196 hexacyanoferrate anions, 238, 241
HMW alcohols, 307
E HT anionic clays, 285, 286, 287, 288, 289, 290,
293, 294, 295, 296, 298, 299, 300, 303, 306,
EDTA, 126, 282, 398, 399 310, 311, 312, 314
EEI, 361, 362 HT compounds, 139, 253, 260, 285, 286, 287, 288,
EGF, 404 289, 290, 291, 296, 300, 310, 311, 312, 314
electrochemistry, 34, 383 HTs, 139, 268
epidermal growth factor, 404 hydrogenation, 152, 286, 287, 289, 290, 294, 307,
EPR, 193, 209, 210, 211 308, 323, 324, 325, 326, 327, 331, 332, 333,
ESFF, 111 335, 338, 339, 342, 344, 349, 350, 356, 357,
ethylene glycol, 55, 56, 231, 232 358, 359, 360, 361, 362, 363, 364, 365, 366,
EXAFS spectroscopy, 298 367, 368, 369, 370, 371, 372, 373, 374, 376,
377, 378
F hydrogenation catalysts, 286, 323, 326
hydrohonessite, 53, 76, 77, 78, 152, 160
FCCU, 287, 296 hydrotalcite-like, 1, 10, 57, 78, 79, 90, 112, 115,
Fe(II), 163, 164, 165, 166, 209, 216, 217, 219, 220, 117, 118, 122, 128, 150, 153, 199, 200, 202, 208,
222, 363, 413, 414, 415, 416, 418, 419, 420, 223, 229, 230, 234, 246, 251, 253, 256, 267,
421, 422, 423, 424, 425, 426, 427, 428, 429, 272, 273, 274, 327, 328, 344, 346, 357, 359,
430, 431 360, 364, 366
Fe(III), 163, 164, 165, 166, 202, 209, 216, 217, hydrotalcite-type, 149, 150, 160, 198, 313, 344,
219, 220, 221, 222, 226, 227, 251, 267, 268, 345
274, 346, 363, 413, 416, 418, 419, 420, 421, hydroxyl double salts, 88
423, 426, 427, 428, 429, 430, 431
Fischer-Tropsch reactions, 148, 184
I
fluid catalytic cracking units, 287
Forcefield I, 97, 98, 107, 108 IC, 384, 385
Index 497
IES, 142, 183, 184, 186 203, 204, 205, 206, 207, 208
induced hydrolysis, 15, 18, 416 Maxwell-Boltzmann distribution, 95
infrared spectroscopy, 121, 140, 141, 142, 143, MEA, 359, 360, 361, 363
153, 158, 178, 186, 238 mean squared displacement, 98
interlamellar anions, 3, 8, 9 Meerwein-Ponndorf-Verley reduction, 293, 294
interlamellar domains, 1, 2, 3, 5, 8, 19, 21, 25, 29, mesityl oxide, 289
197 metallic cations, 1, 2, 3, 4, 8, 10, 12, 22, 28, 31, 33,
interlamellar species, 3, 5, 7, 33 336, 343
interlayer anions, 39, 57, 62, 64, 72, 74, 77, 78, 85, methyl isobutyl carbinol, 289
88, 94, 97, 98, 99, 100, 110, 115, 116, 119, 124, methyl isobutyl ketone, 288, 289, 373
127, 130, 133, 144, 150, 174, 181, 216, 219, Mg3Al-LDH, 98, 103, 109, 110, 111, 112
226, 229, 241, 254, 290, 306, 324, 419 MgAl-LDH, 107, 108, 277
interlayer cation, 80, 85, 88, 94 MIBC, 289
interlayers, 25, 39, 40, 42, 44, 45, 46, 48, 49, 52, MIBK, 288, 289, 373
53, 54, 55, 57, 58, 59, 60, 61, 62, 63, 64, 67, 72, microporosity, 24, 144, 164, 231, 233, 234, 238,
73, 74, 77, 78, 79, 80, 81, 82, 87, 88, 89, 90, 102, 241, 245, 248
103, 115, 176, 210, 238, 241, 246, 419, 426 molybdates, 166, 167, 233
Internal Conversion, 384 monoethylamine, 359, 360
Intersystem Crossing, 384 Monte Carlo simulations, 94
IR spectroscopy, 89, 129, 230, 265, 361 MOPAC semi-empirical molecular orbital method,
ISC, 384, 385 97
IUPAC classification, 230, 241, 243 motukoreaite, 53, 77, 78, 85
MPA, 361
MSDs, 99, 100, 101, 106, 107
J
MSO, 289
Jablonsky diagram, 384, 385
N
K
natural gas, 286, 302
Keggin anions, 12 Nernst equation, 419
Ni-Co-Zn-Al catalyst, 341, 342, 343
NIR, 141
L
NLO, 399
LAS, 418, 423, 424 NMR, 25, 26, 89, 113, 120, 125, 150, 193, 194,
layered double hydroxides, 23, 24, 25, 26, 27, 28, 195, 196, 197, 198, 199, 200, 201, 202, 203,
29, 30, 31, 32, 35, 94, 133, 139, 175, 193, 194, 204, 205, 206, 207, 208, 209, 210, 211, 212
197, 205, 206, 229, 244, 251, 257, 258, 276, NMR spectrum, 195, 196, 197, 199, 201, 203, 204,
277, 285, 313, 323 205, 206
LDH compounds, 10, 11, 12, 40, 50, 61, 419 NNN, 216, 217, 218
LDH polytypes, 40, 64, 74, 80 non linear optics, 383, 399
LDH structures, 3, 44, 61, 71, 82, 125, 227 non-steroidal anti-inflammatory drugs, 406
Lennard-Jones 6-12 potential, 96 NSAID, 405, 406
linear alkyl-benzene-sulphonates, 424
long-range cation order, 43, 71, 84, 86 O
Lorentzian doublet, 218
Ocl, 275, 279
OHT, 275, 277, 278, 279, 280, 281, 282
M
100 supercell reflection, 70
MA, 364, 365, 366, 367, 368 organoclays, 269, 275, 279, 280
magic-angle spinning, 193, 194, 211 organohydrotalcites, 275, 279
maleic anhydride, 364, 365 oxidation, 33, 122, 123, 129, 130, 131, 133, 151,
manasseite, 79 152, 164, 165, 209, 210, 215, 216, 217, 219,
MAS, 193, 194, 195, 196, 197, 199, 200, 201, 202, 221, 222, 226, 227, 241, 294, 295, 298, 303,
498 Index
304, 305, 308, 311, 312, 330, 350, 375, 383, 140, 142, 311
395, 397, 413, 414, 415, 416, 417, 419, 420, SCR, 287, 298, 302
423, 424, 425, 426, 428, 429, 430 second harmonic generation, 386, 399
selective catalytic reduction, 287, 298
SEM, 10, 35, 244, 331, 417
P
SHG, 386, 399
peak intensity, 78 shigaite, 53, 77, 78, 85
penthylamine, 361 short-range cation order, 86, 87
pepsin, 403, 404 silicate layers, 26, 27, 30
pesticides, 261, 270, 279 silicates, 24, 28, 30, 31, 61, 89, 128, 172, 173, 191,
phenylphosphonic acid, 126, 180, 202, 204, 206 204, 208
phosphates, 20, 33, 170, 255, 383, 407 SNG, 325
phosphonates, 5, 178 SOL, 369
photochemistry, 383, 384, 395, 409 specific surface area, 23, 116, 120, 229, 230, 233,
PILCs, 273 234, 238, 241, 243, 324, 327, 328, 335, 339,
pillared interlayer clays, 273 340, 345, 346, 350, 374, 375, 377, 378, 383,
PO, 286 417
poly(styrene sulphonate), 125 SSAs, 231, 238
polyoxometalates, 33, 130, 173, 174, 194, 207, stacking, 1, 4, 5, 6, 7, 8, 18, 25, 32, 40, 50, 57, 62,
209, 233, 239 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 82, 84,
POM, 238, 243, 291, 310, 311, 312 90, 246, 414
powder X-ray diffraction, 11, 48, 93, 101, 109, stacking faults, 40, 50, 71, 72, 73, 74, 75, 76, 80,
111, 113, 259 82, 84, 90, 246
PPA, 180 stoichiometry, 15, 17, 68, 70, 71, 84, 86, 219, 431
propylene oxide, 286 synthetic natural gas, 325
PSS, 125, 180
PXRD, 13, 18, 22, 24, 93, 102, 116, 117, 119, 120, T
126, 128, 350, 388, 392, 397, 399
Taylor expansion, 95
R TCP, 262, 264, 265
TEA, 361, 362
radiactive anions, 260 TEM, 35, 230, 241, 244, 360, 361, 375
radial distribution function, 97, 98, 105 temperature-programmed desorption, 360
Raman spectroscopy, 140, 142, 167, 186 temperature-programmed reduction, 131, 132,
Raman spectrum, 148, 150, 155, 156, 158, 159, 342
160, 161, 163, 165, 166, 167 TEOS, 172
RDF, 98, 105, 106 terephthalate, 20, 94, 101, 102, 103, 104, 105, 106,
redox reactions, 33, 423, 429 107, 167, 170, 176, 199, 234, 238, 239, 240,
rehydration, 20, 118, 125, 204, 222, 256, 258, 290 241
Rietveld refinement, 50, 84, 93, 111 tetraethylorthosilicate, 172, 204
Rietveld technique, 50, 84 tetrahydrofuran, 365
thermal decomposition, 39, 115, 116, 117, 119,
121, 122, 123, 124, 125, 126, 127, 128, 129,
S
130, 197, 203, 204, 210, 243, 247, 285, 286,
SA, 365, 367, 405 290, 300, 310, 311, 314, 324, 328, 373, 374,
SAED, 89 376, 377
SAL, 369, 370 THF, 295, 365, 366, 367
salicilate, 405 TNP, 176, 262, 263, 264, 265, 266, 267, 268
salt-oxide method, 15, 17 TOF, 362
saturated alcohol, 369 TPD, 117, 360
saturated aldehyde, 369 TPR, 130, 131, 132, 133, 328, 335, 337, 343, 348,
Scaning Electron Microscopy, 244 354, 360, 362, 366, 370, 372
scattering, 54, 62, 63, 64, 67, 68, 84, 85, 86, 106, Transmission Electron Microscopy, 244
Index 499
trinitrophenol, 176, 260, 265, 266, 274 206, 210, 229, 230, 234, 246, 251, 273, 285,
392
U wermlandite, 53, 78, 85
UAL, 369 X
unit cell parameters, 45, 49, 50, 76
unsaturated alcohol, 294, 368, 369, 378 XAFS, 20
unsaturated aldehyde, 294, 368, 369, 371, 378 XAS, 87, 88, 130
UOL, 369 X-ray absorption spectroscopy, 87, 88
urea method, 14 X-ray diffraction, 8, 10, 16, 17, 34, 48, 99, 100,
112, 116, 118, 144, 155, 159, 167, 170, 175, 176,
179, 183, 185, 186, 230, 233, 243, 244, 253,
V
257, 265, 268, 270, 272, 329, 336, 340, 346,
vanadates, 129, 166, 167, 170, 233 348, 351, 388, 417, 418
X-ray Rietveld structure refinement, 4, 5
XRD, 40, 48, 49, 50, 55, 57, 61, 62, 63, 64, 65, 66,
W
67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80,
water molecules, 2, 3, 5, 13, 19, 20, 22, 28, 33, 34, 81, 84, 85, 86, 87, 88, 89, 90, 119, 153, 163, 185,
39, 44, 45, 48, 53, 54, 62, 79, 82, 85, 88, 96, 97, 198, 203, 204, 205, 206, 207, 209, 210, 221,
98, 100, 101, 102, 103, 104, 105, 106, 107, 109, 226, 268, 285, 298, 300, 307, 327, 328, 335,
111, 112, 115, 117, 121, 129, 144, 149, 150, 151, 346, 350, 354, 359, 360, 362, 365, 366, 368,
152, 155, 159, 162, 164, 174, 181, 197, 201, 370, 372, 375, 416, 418, 429, 430

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LAYERED DOUBLE HYDROXIDES:

PRESENT AND FUTURE

Nova Science Publishers, Inc.

NOTICE TO THE READER

LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

ISBN 978-1-61209-289-8 (eBook)

Published by Nova Science Publishers, Inc. New York

Layered Double Hydroxides (LDH), hydrotalcite-like (HTl), hydrotalcite-type (HTt),

Koch reports the application of Mössbauer spectroscopy to the characterization of LDHs;

LAYERED DOUBLE HYDROXIDES: SYNTHESIS AND

Trivalent metal ratio

Metal cations in the layers

Structure of the layers

Figure 3.-Flattening of the M(OH)6 octahedron in a [Zn-Al] LDH.

composition of main layers Zn3/4Al1/4(OH)2 Zn2/3Cr1/3(OH)2

- halides : fluoride, chloride,…

Figure 4.-Evolution of basal spacing with intercalated anions.

Table 2.-Rietveld structure refinement of a [Zn-Cr-Cl] LDH.

space group R-3m a = 3.124 Å reliability :RI = 4.53 %

Figure 5.-Disposition of interlamellar species in a [Zn-Cr-Cl] LDH.

A Nomenclature for LDHs

- Hydrotalcite, Manasseite Mg, Al

The mechanism of coprecipitation is ideally based on the condensation of hexa-aquo

Origin of Interlamellar Anions

- temperature in the reactor,

displays the same powder X-ray diffraction patterns characteristic of a quasi-amorphous

A very wide range of anions are reported in the literature :

Which MII/MIII ratio ?

Table 3.- Chemical composition range of various LDH

MII-MIII-X pHformation MII/MIII (R) range

Which hydration state ?

Addition rate or aging

The urea method

LDHs with two divalent or trivalent metal cations

Other Preparative Methods and Comparison

Salt - oxide method

MIIO + xMIIIXm-3/m + (n+1) H2O → MII1-xMIIIx(OH)2Xm-x/m · nH2O + x MIIXm-2/m

The [Zn-Cr-Cl] system.

The "salt-oxide method" is a simple solid-liquid reaction. Experimentally, this method

3ZnO + CrCl3 + (n+3) H2O → Zn2Cr(OH)6Cl·nH2O + ZnCl2

Preparation of other LDH

Comparison of Preparative Methods

POST SYNTHESIS MODIFICATION OF LDHS

This thermodynamic system is bivariant in isothermal and isopressure conditions. It can be

successfully done via 0.33[Mg-Al-C6H4(CO2)2] 32 and 0.33[Mg-Al-C7H7SO3].33 Figure 12 shows

Washing and drying process

Figure 12.-Schematic representation of polyoxometalate exchange via terephthalate compound in an LDH.

Grafting of anions onto LDH layers

The last 3R “7.1 Å” phase in Figure 13 diagram corresponds to an irreversible

Examples: Modification of oxoanions intercalated LDHs.

The structure of the 0.670.32[MII-MIII-X]8.922H interlamellar domains is described as an

One first group of LDHs ([Zn-Cr-SO4], [Zn-Al-SO4], [Cu-Cr-SO4], [Zn-Al-CrO4],

These structural post-synthesis modifications lead to an interesting improvement of the

Polycondensation of Silicate in [Zn-Al] and [Zn-Cr] LDHs

Intercalation of Silicate Species in [Zn-Cr] and [Zn-Al] LDH45

Pillaring of Silicate Sheets on Double Hydroxides Layers45

Removal of intrinsic water molecules and OH condensation are confirmed by a strong

- nanoscale reactors with stereoselective reactivity,

Calcination and reconstruction

We only give here a few examples.

Delamination of LDH by use of surfactants

Delamination process example

Dispersion of (DS)-Zn2Al, (Zn2Al(OH)6)(C12H25SO4·nH2O), in methanol, ethanol,

CRYSTAL STRUCTURE AND X-RAY IDENTIFICATION