Review

pubs.acs.org/CR

Catalysis by Doped Oxides

Eric W. McFarland and Horia Metiu*,

Department of Chemical Engineering, and Department of Chemistry and Biochemistry, University of California, Santa Barbara,
California 93106, United States
9.1. Introduction 4403
9.2. The Eect of LVDs on the Energy of Oxygen-
Vacancy Formation 4403
9.3. The Presence of an LVD Makes the Surface
More Reactive 4405
9.3.1. General Comments 4405
9.3.2. Methane Activation: Does the
BrnstedEvansPolanyi Rule Work
For It? 4405
9.4. The Electronic Structure of an Oxide Doped
with an LVD 4406
9.5. Comparison with Experiments 4407
10. The Eect of High-Valence Dopants (HVDs) 4407
CONTENTS 10.1. Introduction 4407
10.2. HVDs in Irreducible Oxides 4408
1. Introduction 4392
10.3. HVDs in Reducible Oxides 4409
2. Historical Note 4393
10.4. The Stability of High-Valence Dopants 4409
3. Synthesis Methods for Doped Oxides 4393
11. Same-Valence Dopants (SVDs) and Flexible-
3.1. Introduction 4393
Valence Dopants (FVDs) 4410
3.2. Solid-State Synthesis 4393
12. Two Case Studies: Oxidative Dehydrogenation
3.3. Incipient Wet Impregnation 4394
of Ethylbenzene and Ethane 4410
3.4. Coprecipitation 4394
12.1. Introduction 4410
3.5. SolGel Synthesis 4394
12.2. Oxidative Dehydrogenation: Generalities 4410
3.6. Combustion Synthesis 4395
13. The Oxidative Dehydrogenation of Ethylben-
3.7. Ultrasonic Spray Pyrolysis (USP) 4395
zene to Styrene 4411
3.8. Electrochemical Synthesis 4395
14. Oxidative Dehydrogenation of Ethylbenzene to
4. Characterization Methods for Doped Oxides 4396
Styrene Using CO2 as an Oxidant 4411
4.1. Introduction 4396
14.1. Introduction 4411
4.2. X-ray Diraction (XRD) 4396
14.2. Ethylbenzene Dehydrogenation in the
4.3. Synchrotron Radiation 4396
Presence of CO2, Catalyzed by Doped
4.4. X-ray Photoelectron Spectroscopy (XPS) 4397
Oxides 4411
4.5. X-ray Fluorescence Spectroscopy (XRF) 4397
14.2.1. Experimental Results 4411
4.6. Atomic Absorption Spectroscopy (AAS) 4397
14.2.2. Are These Results Consistent with
4.7. Ultraviolet Optical Spectroscopy (UVVis) 4397
What We Know from Calculations? 4412
4.8. Raman Spectroscopy 4397
15. Oxidative Dehydrogenation of Ethylbenzene to
4.9. Fourier Transformed Infrared Spectroscopy
Styrene by Using Oxygen and Doped Oxide
(FTIR) 4397
Catalysts 4413
4.10. Probing Metal Oxides with Electrons 4398
16. Oxidative Dehydrogenation of Ethane to Ethyl-
4.11. Low-Energy Ion Scattering (LEIS) 4398
ene 4414
4.12. Secondary Ion Mass Spectrometry (SIMS) 4398
17. Background Information on NiO 4414
4.13. Thermal Gravimetric Analysis (TGA) and
18. Ethane Oxidative Dehydrogenation with Oxy-
Dierential Scanning Calorimetry (DSC) 4398
gen Catalyzed by Zr-Doped NiO 4415
4.14. Temperature Programmed Desorption
19. Ethane Oxidative Dehydrogenation to Ethylene
(TPD) and Temperature Programmed Re-
Catalyzed by Nb-Doped NiO 4416
action (TPR) 4398
19.1. Background Information about Nb and Its
5. Computational Methods 4399
Oxides 4416
6. Strong AcidBase Interactions 4400
7. A Classication of DopantOxide Pairs 4401
8. The MarsVan Krevelen Mechanism, the Oxygen
Vacancy Formation, and Doping 4401 Special Issue: 2013 Surface Chemistry of Oxides
9. Oxide Catalysts Doped with Low-Valence Dop- Received: October 19, 2012
ants (LVDs) 4403 Published: January 27, 2013

2013 American Chemical Society 4391 dx.doi.org/10.1021/cr300418s | Chem. Rev. 2013, 113, 43914427
Chemical Reviews
19.2. Computational Results on Nb-Doped NiO 4416
19.3. The Preparation of NiO and Nb-Doped NiO 4417
19.4. Catalytic Performance of NiO for ODH of
Ethane to Ethylene 4417
19.5. Catalytic Performance of Nb-Doped NiO for
Ethane ODH 4418
19.6. NbOx Clusters Supported on NiO 4418
19.7. Long-Term Stability of the Nb-Doped NiO
Catalyst 4418
19.8. The Inuence of Doping and of the
Method of Preparation on Surface Area
per Gram 4418
19.9. Chemical Characterization of Nb-Doped
NiO 4418
19.10. Ethane ODH by NiO Doped with Li, Mg,
Al, Ga, Ti, Ta, or Nb 4419
19.11. Ethane ODH on Doped NiO: Conclusions 4419
20. Brief Concluding Remarks 4419
Author Information 4420
Corresponding Author 4420
Notes 4420
Biographies 4420
Acknowledgments 4420
References 4421
1. INTRODUCTION
Metal oxide catalysts have numerous industrial applications.17
In addition, oxides catalyze many important reactions whose
conversion or selectivity is too low to be commercially
interesting. We review here experiments and calculations
whose goal was to improve the catalytic activity of an oxide
by substituting a small fraction of the cations of a host oxide
with a dierent cation. We call this substitutional doping or
doping. The substitution disrupts chemical bonding at the
surface of the host oxide, and optimists hope that this will
modify favorably its catalytic activity. The active centers in such
a system could be either the oxygen atoms near the dopant or
the dopant itself.
This is not the only kind of creative disturbance that can
activate the surface of an oxide. The catalytic activity of a small
(molecular size) cluster MeOx (where Me is a cation, O is
oxygen, and x is usually unknown) supported on the surface of
another oxide (or any other insulator) is often very dierent
from that of the bulk oxide of Me. For example, VOx clusters
supported on ceria8,9 are more active for methanol oxidation
(and many other reactions) than either V2O5 or CeO2. The so-
called inverse catalysts are similar. They consist of a very thin
oxide lm supported on a metal surface.1030 In this system, as
in the other two mentioned above, we place the oxygen atoms
in unusual bonding situations with the intention of improving
their ability to catalyze oxidation reactions.
Substitutional cation doping is not the only possibility. One
can imagine that replacing some anions with other anions may
also be benecial. There is evidence that the presence of small
amounts of halogen in the feed or on the oxide surface
improves its catalytic activity (more often the selectivity).3153
We do not know of any work that has proven that the
improvements come from the substitution of some of the
oxygen atoms with halogens. Anion doping is benecial for
changing the optical properties of photocatalysts as reviewed
recently by Kudo.54
4392
Review
In this Review, we discuss only oxidation catalysis by
substitutional cation doping of binary oxides (oxides with the
formula MexOy), and leave out complex oxides (e.g., perov-
skites, vanadates). This is an emerging eld, which is rapidly
evolving and is very far from maturity; therefore, it is not
advisable to attempt the kind of exhaustive review typical of
mature elds. Instead, we concentrate on the main ideas and
the major diculties of the eld, try to sort out its prospects,
suggest future lines of research, and examine the extent to
which computations aid the search for better doped-oxide
catalysts. Rather than attempt to cover all work on catalysis by
doped oxides, which is rather vast and fragmentary, we examine
in some depth a few examples on which data are more
abundant and the research is more extensive and more
systematic. One example deals with the oxidative dehydrogen-
ation (ODH) of ethylbenzene to styrene, by using oxygen or
CO2 as oxidant. The other example examines the ODH of
ethane with oxygen. We decided that piling up more examples
would not bring more clarity to our understanding of the
subject. This decision was made easier by our awareness of the
nite nature of our time, energy, and intellectual resources.
We note that we present scientic research rather than focus
on eorts directed toward nding the best commercial catalyst.
This means that some aspects that are essential for deciding
whether a catalyst is commercially promising are not addressed
in this article. An excellent discussion of the criteria that a
commercial catalyst for oxidative dehydrogenation must meet
can be found in Chapter 5 of the book by Centi, Cavani, and
Triro.7
As we worked on this article, several themes became central.
On the experimental side two facts imposed themselves on us:
The performance depends strongly on the method of
preparation; and it is dicult to provide convincing proof
that a doped oxide has been prepared. For this reason, we
devoted a section to the methods of preparation and one to the
methods of characterization.
There has been considerable computational work on various
properties of doped oxides. There are inherent limitations in
this work. First, we know that the computational methods
usable in practice do not give accurate total energies. Second,
we do not know, at the atomic level, the morphology or the
composition of an oxide catalyst under working conditions. The
latter is a shortcoming of the experiments. We could perform
useful calculations on any morphology or any surface
composition, if we knew what they are. Unfortunately,
experiments are not likely to provide this information soon,
despite the great progress made lately in operando microscopy
and spectroscopy. For these reasons, we believe that
computations are most useful, at this time, if they look for
qualitative trends and qualitative rules for catalyst design. They
should help increase the probability of nding better oxide
catalysts. This opinion has guided the way we examined the
computations and organized the presentation of their results.
The calculations performed so far provide a classication of the
dopantoxide pairs based on the common properties obtained
by computations. One of the questions we ask in this Review is:
Are there hints in the experiments that these rules are obeyed?
Given the uncertainties in the experiments, we can only say that
many experimental results are in accord with the qualitative
suggestions made by computations.
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Chemical Reviews
2. HISTORICAL NOTE
It is very likely that doped oxide catalysts have been used before
the concept was formulated explicitly. Most oxide catalysts have
low levels of impurities that may be substitutional dopants; if
they segregate at the surface, they can aect the catalytic activity
without our knowledge even though their net concentration is
very low. Furthermore, most industrial catalysts have small
amounts of additives that prevent coarsening, provide
mechanical stability, prevent the evaporation of the catalyst,
increase conversion, increase selectivity, or poison an
unwanted reaction (one way of achieving selectivity). It is
possible that catalysis by doped oxides is as old as catalysis by
oxides, but we were not aware of the fact.
It is not our intention to provide an accurate or
comprehensive history of the subject. Paravano5557 seems to
be the rst scientist who prepared substitutionally doped oxide
intentionally, to boost the performance of an oxide catalyst. He
studied the oxidation of CO by NiO with a variety of dopants.
While at that time it was not possible to prove that doped
oxides were prepared, at least the intention was to do so. The
inspiration came from work that showed that doping changes
the electronic properties of oxides (mainly the conductivity and
the adsorption spectrum). The premise was that an additive
that changed conductivity was likely to aect catalytic
chemistry, especially for reactions in which electron transfer
might be involved. Cimino et al.58,59 studied N2O decom-
position on solid-solutions of NiO and MgO; by solid-
solutions, they meant substitutional doping. They hoped that
by diluting the Ni ions in the surface of NiO, they can modify
the catalytic activity of Ni.
The idea of using substitutional doping of oxides in catalysis
languished until around 1985 when Lunsford60 showed that Li-
doped MgO is a selective catalyst for oxidative coupling of
methane to ethylene. This was followed by a large number of
studies6177 in which very stable oxides (e.g., MgO, CaO,
La2O3, Sm2O3, etc.) were doped with low-valence dopants to
perform oxidative coupling of methane. Several older reviews of
this subject are available.7880 We will not review oxidative
methane-coupling by oxides containing alkali dopants for two
reasons. First, this reaction is performed at very high
temperature (between 600 and 900 C), and the structure of
the doped-oxide catalyst is aected by this.81 Therefore, this is
not a good system for comparison to theory. Second, two
excellent papers have reviewed the subject recently,81,82 and we
have nothing to add to their analysis.
We are aware of only two articles that review catalytic
chemistry of doped oxides (besides the ones mentioned in
connection with oxidative methane coupling). One, by Cimino
and Stone,83 is mainly concerned with oxides more complex
than the binary oxides studied here. The other, by Hegde,84
concentrates on the considerable amount of work done in his
group in Bangalore.
3. SYNTHESIS METHODS FOR DOPED OXIDES
3.1. Introduction
There is an extensive literature on catalyst preparation8589 to
which we add several books edited by Pernicone and
collaborators. We review here those methods of preparation
that were used to make doped oxides and selected examples in
which an eort was made to prove that doped oxides were
obtained and that their physical and chemical properties dier
from those of the undoped host oxide.
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Review
No matter which method is used, it is dicult to prove that
the material synthesized is a doped oxide with the dopant in the
surface or the subsurface layer (which is the model used in
calculations). While doped oxides are targeted, the preparation
method may produce a system whose surface consists of very
small oxide clusters of the dopant, supported on the surface of
the host oxide. Such clusters are catalytically active.8,9 Being
very small, they have physical and chemical properties dierent
from those of the dopants bulk oxide. Because of this, it is
dicult to distinguish them from a doped oxide. It is also
possible that the as-prepared catalyst is a doped oxide that,
under reducing reaction conditions, is converted to very small
metallic dopant clusters supported on the host oxide. The
physical and chemical properties of such clusters are dierent
from those of a bulk metal, and it is dicult to distinguish them
from a doped oxide.
Our preferred strategy, for establishing that a doped oxide
was obtained, is to use three methods of preparation: one that
aims at making a doped oxide, one that intends to make small
dopantoxide clusters on the host oxide, and one that makes
very small metallic clusters of the dopant, supported on the
host oxide. If these three preparations have dierent chemical
and physical properties, we are more condent that one of
them is a doped oxide.
It is likely that many doped oxides are thermodynamically
metastable. If this is the case, the preparation method should be
designed to prevent the system from going to equilibrium. It is
more likely that this goal is reached if the preparation method
starts with a homogeneous mixture of the precursors and the
calcination temperature is low enough to prevent dopant
diusion and aggregation.
Finally, we note that the same doped oxides (same dopant,
same host oxide, same proportions) synthesized using dierent
precursors (e.g., chloride, or nitrate, or acetate, or oxalate, etc.),
or dierent calcination temperature and time, often have very
dierent catalytic activities.90,91
These uncertainties in the outcome of the preparation also
appear in work in which the bulk properties of a doped oxide
are utilized. Work with doped YAG (yttrium aluminum garnet)
metal oxide phosphors, made by a solid-state method, or by
coprecipitation, or by solgel, has shown that even if a
homogeneous doped oxide is produced, the impurities, the
defects, and the morphology are dierent and depend on the
precursors used and the synthesis method. These often lead to
dierences in physical properties and performance.92
3.2. Solid-State Synthesis
Molecular compounds (salts, oxides, etc.) of the host oxide and
of the dopant are mechanically intermixed as solid particulates
and then heated to high temperature, in oxygen, to allow the
dopant to diuse in the host oxide. This method is suitable
when the doped oxide is the thermodynamically stable phase.
The method starts with two phases, and the rate of forming a
homogeneous phase increases when the particles are smaller
and the temperature is higher. There are only a few examples
where a substantial eort was made to prove that a doped oxide
was prepared. In one example,93 a mixture of La2O3, SrCO3,
TiO2, and Ta2O5 was prepared in the desired stoichiometry,
then ball-milled in ethanol with zirconia balls for 12 h. The wet
mixture was dried and calcined in air at 1350 C for 6 h.
Further ball-milling for 12 h followed by a nal heating in air at
1460 C formed a solid solution of Sr0.9La0.1Ti1xTaxO3. XRD
measurements for materials with x = 0.00, 0.01, 0.03, 0.05
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Chemical Reviews
detected a single-phase strontium titanate structure, with a
lattice constant shift consistent with substitutional doping.
3.3. Incipient Wet Impregnation
Wet impregnation exposes the host oxide to a liquid containing
the precursor of the dopant. The mixture is then dried and
heated in air. It is hoped that heating causes surface doping
rather than a separate phase of the oxide of the dopant or a
submonolayer of the dopant oxide on the host oxide.
Copper-doped ceria catalysts were prepared by impregnating
ceria (prepared by calcining ceria nitrate in air) with a copper
nitrate solution. The particles were dried at 120 C for 12 h and
calcined in air, at 500 C, for 4 h.94 When the Cu loading was
below 3% by weight, no crystalline copper oxide phases were
observed in XRD. Rietveld analysis determined that the
material had ceria structure with a small lattice constant shift,
which is considered evidence that some Cu ions substituted Ce
ions in the CeO2 lattice. Above 3% Cu loading, phase
separation was observed. The amount of copper oxide phase
increased with the calcination temperature. The doped material
was more active for CO oxidation than the undoped oxide.
This method of preparation is not always successful. An
example of failure is provided by the following preparation of
Ni-doped ceria.95 A 0.5 M solution of Ni(NO3) in water was
added to ceria powder. The suspension was stirred at room
temperature for 0.5 h to make sure that the pores of ceria are
lled with liquid. After being stirred, the solvent was evaporated
at 110 C and dried for 12 h. The resulting solid was calcined at
450 C in air for 5 h. For low nominal Ni concentration, the
XRD showed only the uoride structure on CeO2 with no shift.
This was considered an indication that no Ni is present in the
bulk of the particles. The XPS signals are similar to those of
bulk NiO. The catalytic activity of the NiCeO2 system for
ethane ODH is much higher than that of CeO2 or NiO. It is
assumed that the catalyst consists of NiOx spread on the ceria
surface, although the presence of substitutionally doped Ni
could not be excluded.
3.4. Coprecipitation
This method starts with a solution of salts of the host cation
and of the dopant, which are treated with a chemical that
precipitates simultaneously both cations. The precipitate is
washed, dried, and calcined at high temperature. An alternative
is to precipitate the solid salts by evaporating the solvent. An
interesting example of this method is provided by the work of
Zhao and Gorte.96 They prepared a large number of doped
ceria catalysts and used them for n-butane combustion. The
coprecipitation was carried out by dissolving Ce(NO3)4
together with a precursor for the dopant, which was either a
nitrate (for Gd, Y, La, Sm, Yb, Pr dopants), or a chloride (for
Nb, Ta dopants), or an oxynitrate ZrO(NO3)2 (for Zr dopant).
The solvent was evaporated, which caused coprecipitation, and
the residue was calcined at 600 C in air. The Nb-doped ceria
was also prepared by the coprecipitation of an aqueous solution
of Ce(NO3)4 and NbCl5 by treatment with NH4OH. The
precipitate was washed, dried, and calcined in air at 600 C.
The two Nb-doped ceria samples have dierent n-butane
combustion rates: the rate for the sample made from hydroxide
was 5% higher. The eective activation energies were also
dierent (85 kJ/mol for the sample obtained from the
coprecipitated hydroxides and 105 kJ/mol for the other
sample).
Avgouropoulos et al.91 prepared Cu-doped CeO2 by
coprecipitation and by combustion (see below a description
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of the combustion method) and compared the catalytic
performance of the solids obtained by the two methods, for
the selective oxidation of CO. The coprecipitation method
started with an aqueous solution of Cu(NO3)23H2O and
Ce(NO3)26H2O to which a Na2CO3 solution was added
dropwise, under continuous stirring. The pH was kept below
6.0. The precipitate was ltered, washed, dried at 110 C for 12
h, and calcined for 4 h in owing air at 650 C. While the Cu/
(Cu+Ce) atomic ratio in the precursor solution was 0.143, the
same ratio in the surface region (derived from XPS) was 0.61;
Cu accumulates in the surface region probed by XPS. CuO
XRD peaks are observed in the sample prepared by
coprecipitation or impregnation, but not in the one prepared
by combustion.
Other experiments have shown that one is not guaranteed to
obtain a doped oxide by coprecipitation. Muhammed and co-
workers97 prepared 10% doped ceria catalysts for oxygen
storage by coprecipitation of oxalates. Eleven dierent dopants
were investigated. All samples formed doped oxides except for
the one that attempted to use Co as a dopant but ended with a
separate Co3O4 phase. Teller et al.98 synthesized Sb2O4 doped
with Mo (1.5 at. %) or V (5 at. %) by coprecipitation and by
intermixing and grinding the two oxides. They found no
dierence in the properties of the catalysts prepared by the two
methods. Neutron diraction showed that the Sb2O4 lattice was
unchanged, and EXAFS showed the Mo atoms were
surrounded by 35 nearest O atoms and gave bond lengths
that excluded the possibility that Mo is sitting at Sb site. They
concluded that Mo is trapped interstitially in the Sb oxide. The
same measurements were used to conclude that the V atom
substitutes the asymmetrical site of Sb. The fact that
intermixing and grinding produces a material with the same
properties as coprecipitation is not entirely unexpected; one
can think that coprecipitation is just another way of mixing the
two solids.
3.5. SolGel Synthesis
In this method, the precursors are chosen so that they make a
gel having a uniform distribution of the cations (of the host
oxide and of the dopant). Liu et al.99 have prepared Ce1xFexO2
(x = 0.10.5) by the citric acid solgel method. Citric acid
powder was added to a solution of cerium and iron nitrate. The
water was evaporated at 80 C with stirring, and the resulting
gel was dried (in this particular example, microwaves were
used) and calcined at 700 C, in air, for 4 h. The XRD
measurements showed that the material with x = 0.1 has ceria
structure. The UVvis spectra had no signal typical of iron
oxide. Segregation of Fe3O4 is observed for x > 0.1.
Temperature programmed reduction with hydrogen shows
that Ce0.9Fe0.1O2 is more reducible than CeO2 and is a better
methane combustion catalyst than either undoped ceria or all of
the other iron containing preparations (i.e., those with x > 0.1).
Another interesting example is provided by work in Leerts
group. Solutions of Mg(OCH3)2 in methanol (0.4 M),
containing sucient LiNO3 to obtain 0, 1, 3, and 5 wt % Li
in MgO, were mixed with a watermethanol solution (0.8 M of
water). The mixture was kept for 24 h at room temperature to
form a wet gel. The gel was dried at 50 C, in vacuum, for 7 h,
then calcined in air for 1 h. The XRD measurements detected a
Li2CO3 phase, which is hardly detectable in the 1 wt % material
but clearly visible in the others. However, not all Li forms a
carbonate. For the 1 wt % sample, 40% of the Li present in
precursor was incorporated in MgO, presumably as a
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Chemical Reviews
substitutional dopant. The 5 wt % sample incorporated 16% of
the Li. The 1 wt % material is a fairly good catalyst for propane
ODH at 650 C, having 45% conversion of propane and 73%
selectivity for a mixture of propene and ethylene. A particularly
valuable aspect of this work is the analysis of the process of gel
formation.
3.6. Combustion Synthesis
In this method, a suitable organic fuel is added to a saturated
aqueous solution of the desired metal salts. This mixture is
heated until it ignites, causing a rapid, self-sustaining
combustion reaction (see Figure 1), which produces a ne,
Figure 1. Combustion synthesis. Reprinted with permission from ref
84. Copyright 2009 American Chemical Society.
dry, powder. Patil and other research groups have carried out
the synthesis of various single, doped, and mixed ceramic oxides
using as fuels urea, hydrazines, glycine, methylpyrazoles, or
diformylhydrazine.100,101 Hegde and colleagues have used
combustion synthesis to prepare several doped ceria
catalysts.102,103 One of them, Pd-doped ceria, was characterized
by XPS (ESCA), XRD, and EXAFS, and no evidence of mixed
phases was detected.102 Bera et al.104 synthesized 3 at. % Cu-
doped ceria catalysts for NO reduction with NH3 or CO, using
combustion synthesis from solutions of (NH4)2Ce(NO3)6,
Cu(CO3)2, Cu(OH)2, and C2H6N4O2 (oxalyldihydrazide, as
the fuel). Characterization using Rietveld rened XRD, EPR,
XPS, and EXAFS was consistent with the presence of a doped
oxide alone. Copper-doped ceria was also synthesized by
Avgouropoulos et al.105 using urea as the fuel for a nitrate-
containing solution, and by Rao et al.106 using hydrogen
peroxide for fuel. The materials made by Raos team were
characterized by XRD, EPR, and temperature programmed
reduction (TPR) and, in contrast to the materials made using
oxalyldihydrazide as the fuel, showed nely dispersed Cu2+
species on the surface at low copper content, but Cu2+ in the
form of dimers and clusters at large Cu concentrations. It was
concluded that little of the Cu2+ was in the bulk. Athawale et al.
used microwave heating to initiate combustion synthesis of
silver-doped lanthanum chromite catalysts, with urea as fuel.101
Urea fuel is appealing because it contains no carbon.
3.7. Ultrasonic Spray Pyrolysis (USP)
Ultrasonic nebulization was introduced by Skrabalak and
Suslik107 who used ultrasound to produce droplets of the
4395
Review
solution containing the desired precursors. This can be rapidly
heated in a furnace (see Figure 2) to form doped oxides. Misch
Figure 2. The apparatus for ultrasonic spray pyrolysis (USP).
Reprinted with permission from ref 107. Copyright 2006 American
Chemical Society.
et al.108 prepared, by this method, Pd-doped ceria and used it to
catalyze methane partial oxidation and dry reforming. The
precursor solution consisted of Ce(NO3)36H2O and Pd-
(NO3)22H2O dissolved in water in the appropriate molar
ratios. The solution was nebulized, and the mist was carried by
compressed air into a furnace held at 500 C. The powders
produced in the furnace were collected in sparged liquid traps
containing 4:1 H2O/EtOH. The solvent was evaporated at 80
C overnight. The XRD measurements indicated that Pd-doped
ceria was produced. However, under reaction conditions the
catalyst evolved into metallic Pd clusters supported on ceria.
3.8. Electrochemical Synthesis
This method is not commonly employed for synthesizing solid
heterogeneous catalysts, but it has been used to produce doped
metaloxide photoelectrocatalysts, and dierent character-
ization methods have proved that doped oxides can be
produced. Both cathodic and anodic depositions have been
used, and the nal doped oxide is formed by calcination. In an
investigation of iron oxide doped with 00.5 at. % aluminum,
Kleiman-Shwarsctein et al. deposited lms from electrolytes
with mixtures of iron and aluminum chloride salts using cyclic
voltammetry with the applied voltage ramped.109 A hydroxide
solid lm was deposited, which was calcined at 700 C in air. X-
ray diractometry showed that the Fe2O3 lms were single-
phase hematite. Considerable morphological dierence be-
tween the doped and undoped lms was seen in SEM. A similar
synthesis was performed by the same authors110 to produce
Fe2O3 doped with Mo and Cr and by Hu111 for Fe2O3 doped
with Pt. In Hus work, in addition to XRD, depth proling by
ion etching of the material while performing XPS showed that
Pt was homogeneously distributed in the oxide.
None of these methods are guaranteed to produce doped
oxides, but all of them will work if the preparation conditions
are chosen with care. It seems to us that the combustion
method and the ultrasonic spray pyrolysis are more likely to
make a doped oxide, because the solid is formed very rapidly
and there is no time for dopant segregation. In most cases, the
chance of making a doped oxide is substantially increased if the
dopant concentration is low. While for every system there is an
optimum dopant concentration, in most cases concentrations
higher than 0.3 molar fraction lead to ill-dened and inactive
materials.
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Table 1. Characterization Methods for Doped Metal Oxides

surface specic resolution notes refs
photons XRD no
EXAFS, NEXAFS/XANES no synchrotron E < 0.1 eV 112, 113
XPS yes inelastic MFP 110 nm, >1 at. % 114
XRF no Z > 10 115, 116
AAS no 116
UVvis no 117, 118
Raman no 119
FTIR adsorbates yes 101, 120, 121
DSC/TGA no 122
electrons SEM yes
TEM yes
EELS yes 0.1 eV (TEM) 123
EDS yes inelastic MFP
atoms/chemical SIMS yes 124
LEIS yes 115, 125
TPR/TPD yes NH4,H2,CO,18O 126, 127

4. CHARACTERIZATION METHODS FOR DOPED
OXIDES
4.1. Introduction
The substitution of a dopant atom in a metal oxide host, even at
very small concentrations, can have profound eects on the
properties of the host, including alterations in electronic and
transport properties, morphology changes, and lower phase
transition temperature. Ultimately, when making doped-oxide
catalysts, we hope to improve their functional performance. If
the performance is improved, we would like to show that the
improvement is due to dopant substitution so that we might
develop a more general understanding of the connection
between dopantoxide pairing and catalytic activity. The
methods of characterization need to answer the following
questions. Is the active catalyst a homogeneously doped oxide
with some dopant in the surface layer? Are we sure that the
dopant did not make very small oxide clusters on the surface?
Can we rule out the presence of two phases? Are we sure that
catalytic activity is not due to impurities in the precursors?
What dierences in activity are caused by dierent methods of
preparation of doped oxides with the same nominal
composition?
It is dicult to establish beyond doubt that (1) a true
homogeneously doped oxide has been synthesized, and (2) it
is the homogeneously doped phase that is responsible for the
observed catalytic activity.
Below we discuss methods that have been frequently used in
research on catalysis by doped oxides to help answer the
questions posed above. Because we are interested in catalysis,
our primary interest is in the properties of the surface.
Nevertheless, it is helpful to show (i) that a material that is
homogenously doped in the bulk has been synthesized (e.g., by
XRD), and (ii) that the surface composition is the same or
dierent from that of the bulk (e.g., by XPS). We will mention
only characterization methods that use photons, electrons, or
chemical behavior (Table 1).
4.2. X-ray Diraction (XRD)
It is generally accepted that a doped oxide should have the
structure of the host oxide (e.g., Ti-doped ceria should have the
uoride structure of the undoped ceria). Rietveld analysis is
used to determine whether doping caused a small shift in the
lattice parameter. These are necessary conditions for proving
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that a doped oxide has been prepared. XRD can identify
whether or not a single crystalline phase is present to within the
resolution of the instruments (typically >1%). Peak widths are
t to the DebyeScherrer equation to determine crystallite size.
Shifts due to substitutional doping are often interpreted using
Vegards rule, which states that there is a linear relationship
between the concentration of a substitutional dopant and the
change in the lattice parameter. There is no theoretical basis for
Vegards rule, and many violations have been documented. As
an added complication, the lattice parameters of small
nanocrystals depend on crystallite size, and one is not sure
whether the observed lattice parameters shift is due to doping
or to the small size of the crystallites.
4.3. Synchrotron Radiation
The synchrotron provides tunable X-ray radiation having 6
orders of magnitude greater intensity than laboratory sources.
The frequency is tunable, and ultrafast time-resolved pulses of
X-ray beams with small angular divergence are available. The
beamline spectrometers are routinely capable of resolution
below 0.1 eV and below 1 meV in certain cases.
High intensity allows the performance of X-ray diraction in
situ, on a time scale comparable to that on which structural
changes occur in a catalyst. For example, Rodriguezs group128
has used this technique to show that metallic Ni clusters are
formed from NixCe1xO2, under reaction conditions.
The monochromatic, high-intensity, coherent X-ray beams
allow the investigation of solid-state catalysts both ex situ and in
situ by examining the various aspects of energy dependent X-
ray absorption. Dierent techniques explore dierent energy
regimes. XANES (X-ray absorption near-edge spectroscopy)
and NEXAFS (near edge X-ray adsorption ne structure) refer
to the same measurements but dierent energy ranges.129,130
An X-ray photon is adsorbed to make a core hole, and as a
result the sample emits photons and Auger electrons, whose
energy and intensity are measured. The technique provides
information about the empty states of the system, the oxidation
state of the atom, and its coordination.
EXAFS (extended X-ray absorption ne structure) is used to
determine the geometry and the chemical composition of the
atoms surrounding the atom that emitted the photoelec-
tron.129,130
In studies of ceria doped with Ba, La, Y, Hf, or Zn, used as a
catalyst for the watergas shift reaction, Linganiso and co-
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workers used XANES under TPR reaction conditions to show
that the dopants increased the reducibility of ceria with
hydrogen.112 In work with K-doped MoVSbO, for selective
oxidation of propane and propylene, Balsko et al.113 were able
to demonstrate with XANES that the presence of the potassium
on the surface resulted in partial oxidation of surface Sb3+ to
Sb5+; however, despite the use of FTIR, XRD, XPS, and EPR, in
addition to XANES, there was no unequivocal evidence
presented that the catalyst was atomically doped with K rather
than intermixed with potassium oxides present on the surface.
EXAFS has been used to study the bulk properties of doped
oxides, and it is capable of providing the location of the dopant
in the solid (e.g., substitutional or interstitial) and the positions
of its neighbors.102,104,131134
4.4. X-ray Photoelectron Spectroscopy (XPS)
This technique does not require synchrotron radiation and is
widely used for the characterization of doped oxide catalysts. It
provides information on atoms located within 24 times the
electron inelastic mean free path (110 nm).114 The surface
composition and oxidation state may be determined if the
species of interest are present at the surface in concentration
greater than approximately 1 at. %. XPS is generally performed
in vacuum and is typically ex situ; thus the oxidation states
measured may not reect the electronic environment under
reaction conditions. When used in conjunction with XRD and
other means of determining bulk ratios of host:dopant atoms,
XPS data can (i) determine the surface concentration of the
dopant, and (ii) provide the oxidation states of the atoms
located on the surface or in several layers near the surface. In an
investigation of Pt-doped Fe2O3, Hu et al. synthesized doped
polycrystalline lms by electrochemical codeposition, and then
conrmed that homogeneous solid solution was obtained by
both XRD and by performing XPS as a function of time while
etching the material with an ion beam.111 Recent work by
Rajesh et al. demonstrated that ionic Pt was substituted on Ce
sites of a doped BaCeO3 perovskite prepared by coprecipitation
for the watergas shift reaction.135 High-resolution electron
microscopy along with XRD with Rietveld renement and
neutron diraction were used to conrm the structure. The
XPS data supported the presence of Pt2+ substituting Ce4+ sites,
which was consistent with the observed linear decrease in cell
volume and increase in oxygen vacancies with increase in Pt
concentration. No metallic Pt was observed either pre- or
postreaction, but an increase in the surface concentration of
Pt4+ after the reaction was noted.
4.5. X-ray Fluorescence Spectroscopy (XRF)
In XRF, an X-ray beam is used to excite core electrons of the
atomic constituents in the sample, which decay through the
emission of X-rays with energies characteristic of the element.
Use of energy dispersive spectrometers (EDX, EDS) or
wavelength dispersive spectrometers (WDX, WDS) allows
energy resolution sucient for quantitative elemental character-
ization, provided sucient source intensity is available. XRF is
used for establishing the concentration of dopants in the bulk
of the catalyst. The technique can detect strongly absorbing
atomic species at low (ppm) concentrations within metal
oxides. In their investigation of methane partial oxidation on
yttrium-stabilized zirconia, Zhu et al. found by XRF that all of
their metal oxide catalysts had 0.0051.17 mol % titania and
hafnium oxide contamination.115 Surface analysis using LEIS
did not have sucient sensitivity to detect whether or not the
Ti or Hf species were present on the surface.
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4.6. Atomic Absorption Spectroscopy (AAS)
In this technique, light absorption is used to identify the atoms
produced by the atomization (e.g., by using a ame) of the
doped oxide. In their investigations of doped rare earth oxides,
Korf and colleagues used AAS to identify alkali promoters
added by wet impregnation of Sm2O3, CaO, or MgO used for
the oxidative coupling of methane.65,116 In both studies, the
volatility and migration of monovalent Na and Li species
downstream in the reactors and the stability of the divalent Ca
promoters were established by AAS of the catalysts before and
after reaction.
4.7. Ultraviolet Optical Spectroscopy (UVVis)
UVvis can be used to establish the presence of isolated
dopant cations within a metal oxide. The spectra of the metal
ions are interpreted by ligand eld theory: ions with tetrahedral
coordination are readily dierentiated from octahedrally
coordinated ones. Bruckner used in situ UVvis and EPR to
characterize lanthanum- and chromium-doped alumina and
zirconia, which catalyze the dehydrogenation of propane to
propene.117 The UVvis data showed that the as-synthesized
catalyst exhibited Cr3+ dd UVvis absorbance at 630 nm in
addition to a charge transfer bands from Cr6+ at 370 nm.
Furthermore, EPR indicated the presence of Cr5+. Under the
reducing environment of the propane dehydrogenation, even
below reaction temperatures, the in situ characterization
showed that both the Cr5+ and the Cr6+ were reduced to
Cr3+. Zirconia stabilization in the cubic and tetragonal phases
rather than monoclinic is of importance in maintaining an
activated catalyst. Lopez et al. used UVvis characterization of
Mn-doped zirconia catalysts, prepared by coprecipitation, for
the oxidation of phenanthrene and isopropanol.118 At 10%
doping, XRD conrmed that the Mn4+ substitutes for the Zr4+
and stabilized the catalyst against the monoclinic phase
transition. The UVvis data support the presence of a solid
solution of Mn in ZrO2 at 10% substitution and show the
presence on Mn2O3 at loadings greater than 10%.
4.8. Raman Spectroscopy
In studies of Ce-doped CoCr2O4 catalyst for methane
oxidation, Cr was substituted by Ce from 2% to 100%, and
the material was characterized by Raman, XRD, and XPS. XRD
suggested that a single phase solid solution was produced up to
10% substitution. Raman spectra were used to identify
vibrations associated with pure phase materials and with the
doped chromite.119 In situ measurements of Raman spectra
under reaction conditions were combined with catalyst
reactivity characterizations to evaluate the eect of alkali
doping on the reducibility of vanadia supported on titania.136 It
was found that reducibility of the vanadia correlates with the
Raman spectrum of the vanadyl group.
4.9. Fourier Transformed Infrared Spectroscopy (FTIR)
The vibrational frequencies of metaloxygen bonds is sensitive
to the presence of dopant species at modest concentrations,
and infrared spectroscopy has been used to support the fact
that a doped oxide was prepared.101 Athawale and colleagues
compared the IR spectra of silver-doped lanthanum chromite
catalysts, prepared by combustion synthesis, to undoped
samples where literature values for the frequencies of the O
M and OMO vibrations were known. They inferred from
the presence of new and shifted peaks in the absorption
spectrum that Ag was present as a substitutional dopant. In situ
FTIR has been used to determine catalytic mechanism by
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observation under reaction conditions, and various applications
of this technique have been reviewed by Vimont120 and by
Lamberti et al.137 Sharma et al.138 showed the methanation of
carbon oxides on ruthenium-doped ceria. The Ru-doped ceria
catalyst did make methane from CO2 and H2 but not from CO
and H2. Hydroxyls were not observed by FTIR, when the feed
was CO and H2, whereas they were abundantly present when
the feed was CO2 and H2.138 Infrared spectroscopy can be used
in the study of doped oxides by adsorbing molecules on the
doped and the undoped oxides. Shifts in the vibrational
frequencies of the adsorbate document the presence of the
dopant in the surface. An example is provided by the work of
Corma,139,140 who used shifts in the vibrational frequency of
adsorbed CO to propose that CO oxidation by Auceria is due
to ionic rather than metallic gold. It was proposed later that the
ionic Au is likely to be a substitutional dopant.141,142
The in situ IR is one of the many operando methods
(reviewed by Banares121), which combine the spectroscopic
characterization of the material and adsorbed species with
simultaneous measurement of catalytic activity/selectivity, and
which was reviewed by Banares.121
4.10. Probing Metal Oxides with Electrons
Electron microscopy provides morphological information and
under favorable conditions good instruments can detect single
atoms.143 Many oxides are insulators, and care must be taken,
when electrons are used to probe them, to avoid surface
charging and surface damage. In an investigation of barium
promoters on Ru metal catalysts, the Ba atoms were imaged in
situ, and it was shown that it forms a BaO phase on the Ru
metal nanoparticle, rather than dope the metal.144 Typically, in
doped oxides the dopants are present in concentrations around
5%. Promoters such as alkali metals are frequently applied by
investigators, and high-resolution electron microscopy has
shown that alkali-metal promoters can form isolated islands
on metal nanoparticle catalysts and are not be dopants.144 Wu
et al., in a study of Zr-doped NiO for oxidative dehydrogen-
ation of ethane, veried by XRD that below 10% Zr there was
no ZrO2 phase separation, and the material had the NiO
structure with a changed lattice parameter, which suggested that
Zr is a dopant.126 The authors then performed HR-TEM and
were able to visualize the atomic lattice of the nanocrystalline
materials and measure the lattice spacing to show that it agreed
with the XRD observations. At lower spatial resolutions,
scanning electron microscopy (SEM) can be used to identify
distinct crystalline structures or, qualitatively, the presence of
multiple phases.
The monochromatic electron beams from TEM or SEM can
be used for spectroscopic measurements at dierent sites of the
sample to determine the local electronic and atomic structure
and composition. Electron diraction (ED, EDS) and electron
stimulated X-ray emission spectroscopy (EDX) can be
performed as well as measurements of the inelastic electron
energy loss (EELS) from the incident beam. High-performance
electron spectrometers are limited to an overall energy
resolution (determined by the electron sources) of 0.52 eV.
In a systematic study of a large group of V/Mn/Fe oxides,
EELS spectra, obtained from a 500 keV SEM, were correlated
to the metal ion oxidation states.123 The results were sensitive
to model ts and showed that care is required for getting
meaningful data from SEM electron sources. No method exists
that can unambiguously and universally determine oxidation
states from EELS for all compounds.
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4.11. Low-Energy Ion Scattering (LEIS)
LEIS is capable of determining the mass of the atoms in the
surface layer by analyzing the energy loss of ions that have
collided with the surface. Calibration relationships are
constructed to obtain quantitative results. The experiments
require vacuum, and the sample must be free of all
environmental contamination to obtain meaningful data.
Often the surface is cleaned by sputtering prior to the LEIS
measurement. Less than 1% of a monolayer is inadvertently
sputtered in the time it takes to obtain LEIS data. In their
evaluation of yttrium-stabilized zirconia catalysts for methane
partial oxidation, Zhu et al. used LEIS on the freshly prepared
catalysts to determine the surface composition.115 They found
that the surfaces of several samples were contaminated with F,
Na, K (or Ca), Al (or Si), and Cr (or Mn). The elements in
parentheses indicate an uncertainty in the mass of the surface
impurity. None of the contaminants were intentionally added.
Because the precursors used to make doped oxides are often
99.99% pure, it is possible that the 0.01% impurities may
accumulate at the surface and inadvertently dope the oxide.
These unknown dopants can interfere with the ones added
intentionally. Moreover, the unknown dopants can act to
compensate the chemical eect of the dopants added
intentionally.145 LEIS is a particularly useful probe for doped
oxide, and it is unfortunate that it is not more widely available.
4.12. Secondary Ion Mass Spectrometry (SIMS)
Elemental composition as a function of distance from the
surface can be obtained by bombarding the sample with
energetic ions. A pulsed beam of ions (typically Cs or Ga)
bombards the surface, and the mass of the ejected ions is
measured. Successive layers are removed and analyzed in the
process. Debecker et al. used a combination of XRD and SIMS
to evaluate the dierences in ternary Si/Al/Mo mixed oxide
catalysts prepared by solgel and wet impregnation meth-
ods.124 XRD showed the samples prepared by wet impregna-
tion to be phase separated, when Mo content was as low as 8%,
whereas even at 20% Mo the solgel samples were
homogeneous. Oxide clusters containing more than one Mo
were removed by SIMS from the surface of the wet
impregnation samples, while only isolated Mo atoms were
detected from the solgel prepared samples.
4.13. Thermal Gravimetric Analysis (TGA) and Dierential
Scanning Calorimetry (DSC)
Besides being used to examine coke production and desorption
of impurities, the examination of phase transition temperatures
and crystallization phenomena using DSC/TGA can help
identify the formation of mixed phase materials and provide
support that a doped oxide has been synthesized. De la Rosa
and co-workers122 used DSC to study La-, Mn-, and Fe-doped
zirconia prepared by solgel synthesis and used as trichloro-
ethylene combustion catalysts. A shift in the crystallization
temperature of the doped material, determined by DSC,
indicates that the dopant is incorporated in the bulk.122
4.14. Temperature Programmed Desorption (TPD) and
Temperature Programmed Reaction (TPR)
TPD can be used by adsorbing molecules on the doped oxide,
heating the sample, and measuring the composition of the gas
desorbed from the surface. TPD with the as-prepared catalyst is
used to determine the temperature at which O2 desorbs, or the
temperature at which carbonates or hydroxyls present on the
surface produce CO2 and water, respectively. Furthermore,
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specic reactions (e.g., the oxidation of an alkane by a doped
oxide) can be monitored as the temperature is ramped up. Such
measurements are particularly useful when a doped oxide is
compared to the undoped one, or when comparing samples
having the same host-oxide and various dopants.
Wu and co-workers126 showed that O2 desorbs from Zr-
doped NiO at much lower temperature than from undoped
NiO. They also used TPR to monitor the oxidative
dehydrogenation of ethane and found that Zr-doped NiO is
more selective than NiO but has lower ethane conversion.
Temperature programmed reaction provides a quick,
preliminary way of testing whether a dopant aects strongly
the reducibility of an oxide, its acidity, or its ability to perform a
given reaction.
5. COMPUTATIONAL METHODS
Computing accurately the catalytic properties of doped oxides
requires a detailed knowledge of the morphology and the
composition of the surface under reaction conditions. At this
time, the experiments are unable to provide this information.
One could imagine trying to use computations to determine the
state of the catalyst by creating a large number of models,
calculating their free energy, and studying catalysis with the
model having the lowest free energy. This is impractical: a lot of
computer time is needed because we have little guidance from
experiments, and too many possibilities will have to be
considered. In addition, this will give the equilibrium state of
the catalyst, which is of limited usefulness; we need the state of
the catalyst under steady-state reaction conditions, and this is
governed by kinetics. Trying to calculate activation energies and
reaction rate for all possible structures and reactions in a given
system is possible in principle, but it is far beyond the current
computing capabilities.
Chemists have lived with uncertainty throughout their
history, and the situation described above is not rare nor
does it imply that we should abandon using computations. A
possibility, which we follow, is to look for situations in which
knowledge of simple rules or trends can improve our ability of
predicting whether a catalyst or a class of catalysts is promising
for a particular reaction. For example, alkane activation
catalyzed by doped oxides is fertile ground for this approach.
The rate-limiting step is the breaking of the CH bond. One
can compare the activity of dierent catalysts for this process by
calculating the activation energy for CH bond breaking. This
makes the time needed for screening catalysts for this reaction
comparable to the time of doing the experiments, which is an
important practical consideration. In the case of doped oxide
catalysts, there are a number of fundamental, qualitative
questions. Among the many possible oxidedopant combina-
tions, which one has the lowest activation energy for breaking
the CH bond? Can we classify the dopantoxide pairs in a
useful way that might allow us to guess, without elaborate
calculations, what catalyst to try for alkane activation? Is there a
simple understanding of how a dopant aects catalytic activity?
Finally, computations have the advantage that they can easily
make new materials and explore their catalytic activity. If they
are promising, the experimentalists might attempt to synthesize
them.
To do useful computations on a catalytic system, one has to
deal with systems with a large number of electrons and perform
a large number of calculations for all possible adsorption sites
and reaction paths. In practice, only density functional theory
(DFT) is ecient enough to satisfy these requirements. In
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almost all cases, the surface is modeled by a slab of nite
thickness in one direction and periodic in the other two. It is
also possible to make small oxide cluster models, which allow
the use of more accurate quantum chemistry methods.
Experiments on gas-phase clusters146 and on mass-selected
clusters supported on solid surfaces147158 show that the
catalytic activity of very small clusters depends strongly on their
size. Therefore, a calculation using a cluster model has to
increase the cluster size until its catalytic properties no longer
change with size. If the size becomes too large, one has to resort
to DFT. If it is too small, one can do accurate calculations, but
the model is inaccurate.
The ordinary GGA-DFT (GGA stands for generalized-
gradient approximation) does not give the correct electronic
structure for most oxides of transition metals and rare-earth
metals. Some objections to GGA-DFT have to do with the
values of the orbital energies. The energy dierence between
LUMO and HOMO (the band gap) given by GGA-DFT is
always substantially smaller than the measured value. Experi-
ments (UPS, EELS) observe that lled states are present in the
gap when oxygen vacancies are present, while in GGA-DFT
calculations the vacancy-induced states are at the bottom of the
conduction band. One could argue that orbital energies should
not be compared to observable quantities. Strictly speaking this
is true; however, one must be concerned when GGA-DFT
calculations predict that Ti2O3 is a metal, while experiments
show that it has a band gap of 1 eV. In addition to the above
shortcomings, we add the fact that the d- or f-bands in these
oxides are much wider than in experiments. This means that, in
the calculations, the electrons in the d- or f-orbitals are
delocalized instead of being localized on the cations as the
experiments assert.
Because we have very few precise binding energy measure-
ments on well-dened, clean oxide surfaces,30,159164 it is not
clear to what extent GGA-DFT makes errors when calculating
total energy dierences, which are the quantities most
important to catalysis.
A temporary palliation is provided by the DFT+U
method165167 in which a Hubbard-like correction is added
to the DFT theory to prevent the delocalization of the d- or f-
orbitals of the cations. Many versions of the theory have been
published,168174 but the implementation available in the VASP
programs is most widely used. Unfortunately, there is no
agreement on how to pick the value of the Hubbard parameter
U. Because catalysis is controlled by total energy dierences, we
prefer to chose the value of U that ts the energy of some
reaction involving the oxide.175,176
In principle, one expects U to depend on the cationcation
distance and on the positions and the nature of the surrounding
anions. In practice, one assumes that U is a property of the
cation, which is a ill-dened approximation. Despite these
shortcomings, the consensus is that calculations on transition
metal oxides or rare-earth oxides must use spin-polarized, DFT-
GGA+U, not GGA. It is prudent, however, to test that the
qualitative conclusions reached by the calculations do not
change when the value of U changes within a reasonable range.
Watson and Nolan have suggested that a Hubbard correction
ought to be used for the p-orbitals of oxygen. Because this is
important in connection with low-valence dopants, we defer the
discussion of this issue for that section.
An alternative to GGA+U is to use a hybrid functional such
as B3LYP177 or HSE.178186 Both methods add some Hartree
Fock exchange energy to the GGA functional. This removes
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some of the interaction of the electron with itself, a feature that
plagues GGA-DFT. Both methods have been tested extensively
for molecules and less so for oxides. The conclusion is that they
are better than GGA and probably than GGA+U. Unfortu-
nately, they require more computer time than GGA+U and are
less practical (although possible) if one plans to perform all of
the calculations needed when one studies adsorption and
reactions on the surface of a slab. When possible, they should
be used to test the key reaction steps in the GGA+U
calculations. Some comparisons between GGA+U and HSE
are available.187190 For example, the energy of oxygen vacancy
formation obtained by HSE diers from that given by PBE+U
by 0.3 eV for CeO2(110), by 0.4 eV for CeO2(100), and by 0.8
eV on CeO2(111). These results suggest again that one should
use calculations mostly for qualitative results and trends. In the
example above, the qualitative conclusion that CeO2(111) is
not as good an oxidant as Ce(100) or CeO2(100) is likely to be
safe.
Another shortcoming of GGA-DFT is its inability to describe
van der Waals interactions. This is particularly important for
binding of polarizable molecules to metals (which are very
polarizable)191195 and less so for oxides that have a large band
gap. However, in the case of alkane interactions with siliceous
zeolites, for example, the van der Waals interactions are the
only interactions, and obviously they cannot be ignored. In
calculating reaction energies, some of the van der Waals
interactions cancel out but not completely. It is therefore
preferable to use versions of DFT that include the van der
Waals interaction, but this has been done infrequently for
oxides.
The quantum calculations performed on heterogeneous
catalysts use a Hamiltonian that does not contain spin-
dependent terms (such as the spinorbit coupling). In this
case, the exact wave function of the system must be an
eigenstate of the square of the total spin operator, S2, of the
electrons and of the projection Sz of the same operator on the
z-axis. Quantum mechanics also tells us that if the Hamiltonian
is truly spin independent, then the rate of transition between
electronic states with dierent spin (e.g., from a singlet to a
triplet) must be zero. We say that such transitions are spin-
forbidden.196,197 Transitions that are spin-forbidden take place
in practice because the correct Hamiltonian contains spin-
dependent operators. However, these operators have small
matrix elements, and therefore the rates of spin-forbidden
transitions are small. The consequences of these statements are
well understood by people who apply quantum chemistry to
radicals, or to organometallic compounds, or to en-
zymes.198208 With few exceptions,209211 they have been
ignored in surface science and catalysis.
Because the exact wave function must be an eigenstate of S2
and Sz, density functional should use only densities derived
from wave functions satisfying this restriction. Unfortunately,
we do not know how to impose this constraint. We have
suggested209 that, as a temporary solution, one should assume
that reactions in which the spin polarization (i.e., the number of
spins up minus the number of spins down) of the reactants
is dierent from that of the products are slow. This is based on
the observation that such reaction would require ipping one
or more spins and there are no magnetic elds in the system
strong enough to make this process fast. Of course a reaction
that does not require spin-ipping but has a very high activation
energy can be slower than a reaction in which the spin is ipped
but the crossing of the states with dierent spins takes place at
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low energies. An example of this is provided by calculations
done by Goodrow et al.211 who showed that in the conversion
of methanol to formaldehyde, the dehydrogenation of the
methoxide is much slower than a spin-forbidden transition
invoked in another step of the mechanism. Therefore, the spin-
forbidden transition is not rate-limiting for that particular
reaction.
A long-debated issue in quantum chemistry is how to assign
electron charges to an atom that is part of a molecule. There is
no perfect method for doing this, but we prefer the one
proposed by Bader,212 which was implemented eciently by
Henkelman, Jonsson et al.213,214 To the extent that this
denition is accepted (and we nd it logically satisfying), the
Bader charges are the real charges of the atom in a solid or a
molecule. We emphasize this because we also use formal
charges in this Review, following the bad but useful habit of
many people in the eld. Formal charges do not exist. They are
dened by deciding arbitrarily that oxygen in an oxide has the
charge 2 and then determining the charge of the cation so
that the oxide is electrically neutral.
6. STRONG ACIDBASE INTERACTIONS
Over the years, many people have attempted to correlate
catalytic activity with the acidity or the basicity of oxides.215219
There is no doubt that in cases where hydrocarbon cations are
intermediates, Bronsted acidity of a catalyst is essential.220 In
other cases, one constructs a basicity scale by using the binding
energy of CO2. The stronger it binds CO2, the more basic is the
oxide. The acidity is determined by measuring the binding
energy of ammonia or pyridine or by measuring the shift in the
vibrational frequency of CO.137 One then attempts to correlate
the catalytic activity of a variety of oxide catalysts, for a given
reaction, with the basicity or the acidity of the surface.216,217
In a recent article,221 we have shown that a large number of
computational results can be qualitatively rationalized by a
simple rule: the interaction between a Lewis acid and a Lewis
base coadsorbed on the surface is surprisingly strong. We will
not repeat the arguments here, but we will make use of this rule
to guide us.
While the denition and the classication of various aspects
of Lewis acidity and basicity can become very complex,222 we
use here the simplest possible denition. If two compounds
come in contact or react, the one that receives electrons is a
Lewis acid and the one that donates them is a Lewis base.
While the concept of Lewis acid and base is very old,223 its use
was limited by the fact that in most cases we did not know how
the electrons ow when two compounds come in contact.
Because of the work of Bader,212 we now have the means of
calculating213,214 how the electrons are distributed over each
atom in a molecule and therefore determine which molecule is
an acid and which is a base. We emphasize that acidity and
basicity are properties of a pair: a compound can be acid when
interacting with one molecule and a base when interacting with
another. For physicists, the name of electron donor (base) or
electron acceptor (acid) may be more familiar.
This concept is of interest here because the fragments
formed by the dissociative adsorption of alkanes, the high-
valence dopants, the oxygen vacancies, and the Ti3+ and Ce3+
cations, are bases and the low-valence dopants, the Ce4+ and
Ti4+ cations, and O2, Br2, Cl2, and other electronegative
adsorbates, are acids. The rule we found by examining the
results of many calculations is that if we coadsorb on the surface
of an oxide a Lewis base with a Lewis acid, the binding energy
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of the pair exceeds substantially the sum of the binding energy
of the compounds alone on the same surface. Thus, the
presence of a Lewis base on a surface (e.g., a hydroxyl, an
adsorbed CH3 radical, a K atom) increases the binding energy
of a Lewis acid (e.g., a Au atom or an oxygen molecule). The
presence of a Lewis acid on the surface (e.g., a dopant having a
lower valence than the cation it substitutes in the host oxide)
lowers the energy of formation of an oxygen vacancy because
the oxygen vacancy is a base and its formation benets by a
large acidbase interaction. We will make use of this concept
throughout this Review.
7. A CLASSIFICATION OF DOPANTOXIDE PAIRS
As we have explained already, the role of a dopant is to disrupt
the chemical bonds in the surface of the doped oxide to make
either the dopant or the oxygen atoms near the dopant engage
more readily (than the undoped oxide) in chemical reactions.
By reviewing the existing DFT calculations, we have come up
with a tentative classication of the dopantoxide pairs.
We call a dopant a low-valence dopant (LVD) when its
valence in its own stable oxide is lower than the valence of the
cations it substitutes in the host oxide. For example, a La atom
substituting a Ce atom in CeO2 is an LVD because lanthanum
oxide has the formula La2O3. The chemistry of doped oxides in
which the dopants valence is lower than that of the substituted
cation by one is predictable. Their most interesting feature is
that they activate the oxygen atoms near them and make them
more reactive. The LVDs make the doped oxide a better
oxidant than the undoped host oxide, and therefore they
promote the rst step in the Marsvan Krevelen catalytic
oxidation mechanism.
We call a dopant a high-valence dopant (HVD) when its
valence in its stable oxide exceeds that of the cation it
substitutes. An example is La dopant in CaO, because La is
trivalent in its own oxide. The HVDs chemical properties
depend on whether the host oxide is reducible or not. If the
host oxide is irreducible (MgO, La2O3, Ta2O5, etc.) and the
dopants valence is larger by one unit than the cation it
substitutes, the dopant makes the oxygen atoms in the surface
of the host less reducible and therefore less active. However,
the dopant adsorbs O2 from the gas phase and activates it. A
reductant can react with this oxygen and undergo oxidation.
Unlike in the Marsvan Krevelen mechanism, the oxygen atom
in the oxidation product originates from the gas phase, not
from the surface. If the valence of the dopant is much higher
than that of the replaced cation, complications arise, and we
examine these in the section dedicated to HVDs.
If the host oxide is reducible (CeO2, TiO2, etc.), the dopant
may donate electrons to the host cations (e.g., reducing Ce4+ to
Ce3+), and this will aect the properties of the system. Because
of this, we classify the HVDs in reducible oxides separately
from those in the irreducible ones.
To decide a priori the valence of a dopant, we use the oxides
the dopant forms. Mg is divalent because the only stable oxide
is MgO, and Ta is pentavalent because Ta2O5 is its only stable
oxide. On the other hand, Nb has three stable oxides, Nb2O3,
NbO2, and Nb2O5. We cannot decide a priori whether Nb in
Nb-doped ZrO2 is a low-valence or a high-valence dopant. Of
course, one can analyze the results of the DFT calculations to
assign a valence to Nb in Nb-doped zirconia. However, this
defeats our purpose, which is to provide a classication that
allows us to predict qualitatively the eect of a dopant without
performing calculations.
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There are of course the cases in which the dopant and the
cation it substitutes have the same valence. We do not have
sucient computations on the chemistry of such systems, and
our tentative suggestion is that they do not have a very large
eect on the chemistry of the host oxide. An exception may be
the case when the oxide of the dopant is much more stable than
the host oxide and the oxygencation bond length in the two
oxides are dierent. An example of this might be NiO doped
with Mg.
8. THE MARSVAN KREVELEN MECHANISM, THE
OXYGEN VACANCY FORMATION, AND DOPING
It is widely accepted224,225 that most oxidation or oxidative
dehydrogenation reactions catalyzed by oxides take place
through a Marsvan Krevelen226 mechanism. In such reactions,
the gases introduced in the reactor contain a reductant (e.g., an
alkane, CO, H2) and an oxidant (e.g., O2, CO2, N2O). In the
Marsvan Krevelen mechanism, the reductant is oxidized by
the oxygen atoms from the oxides surface layer (not by
adsorbed oxygen or by gas-phase oxygen). When the oxidation
products desorb, they leave behind oxygen vacancies. The role
of the gas-phase oxidant, introduced with the feed, is to
annihilate the oxygen vacancies (to reoxidize the surface). In
most cases, the reoxidation of the surface is very fast, and
therefore the rate-limiting step is the reaction of the reductant
with the surface oxygen. We assume that there is a connection
between the ability of surface oxygen to act as an oxidizing
agent and the energy Ev required for forming an oxygen
vacancy. To be precise, Ev is the energy of the reaction
Ox Ox v + 1/2 O2 (g)
where Ox is the oxide (doped or not) and Oxv is the oxide with
an oxygen vacancy on the surface. The assumption is that the
smaller is Ev, the better oxidant is the surface. Once we accept
this idea, we can calculate Ev for a quick screening of the
oxidative power of various oxides (doped or undoped).
Moreover, if we want to make an oxide a better oxidant, we
should look for modications that make Ev smaller. However,
one must keep in mind that a very small Ev means that the
surface is a good oxidant, but it is not necessarily a good
oxidation catalyst. To complete the catalytic cycle, the gaseous
oxidant (oxygen, CO2, N2O) must be able to reoxidize the
surface. If oxygen is too easy to remove from the surface layer,
it will be dicult to put back. Therefore, in designing an
oxidation catalyst, we must follow a moderation principle: we
should modify the surface to make Ev small, but not too
small.141
For this and other reasons, there is an extensive literature in
which Ev was calculated.141,142,145,187189,221,227262 Pirovano,
Homann, and Sauer263 have written an excellent review of
these calculations summarizing the situation up to 2007.
According to the crude electron-pair Lewis theory of the
chemical bond,264 removing an oxygen atom from the surface
leaves behind two unpaired electrons. This means that an
oxygen vacancy is a strong Lewis base. The fate of these
electrons depends on whether the oxide is irreducible or
reducible. Here, we say that an oxide is irreducible if the cation
in it does not make an oxide in which it has a lower valence
(e.g., CeO2 is reducible because Ce2O3 exists and is stable;
MgO is irreducible because Mg2O does not exist). This means
that the cations in the irreducible oxides will not lower their
formal charge in the presence of electron donors. When an
oxygen vacancy is made on the surface of an irreducible oxide,
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the unpaired electrons, left behind when the oxygen atom is
removed, are localized at the vacancy site.258,260 This of course
assumes that the oxide does not have electron-accepting
impurities. In the presence of O2 in the gas phase, the oxygen
vacancy in an irreducible oxide adsorbs O2 strongly. We expect
this, because O2 is a strong Lewis acid and the vacancy is a
strong Lewis base.
In the materials science literature, there have been extensive
discussions regarding the charge of an oxygen vacancy in the
bulk.265267 The model used in these discussions assumes that
when the oxygen vacancy is formed the oxide is in contact with
an electron reservoir whose properties are described solely by
its Fermi level (chemical potential). The vacancy is in chemical
equilibrium with a gas-phase oxygen reservoir and the electron
reservoir. If the Fermi level of the electrons is very low, the
vacancy will donate electrons to the electron reservoir and the
vacancy is positively charge. In the opposite limit, it is
negatively charged. The concentration of vacancies and their
charge depends on oxygen pressure and temperature and on
the Fermi level of the reservoir. The model is silent regarding
the physical nature of the reservoir. Unless the oxide is in
contact with a bulk metal, which will provide the reservoir, we
must assume that the reservoir consists of impurities (electron
donors or acceptors) or other defects. The question is
whether the model is useful for the study of oxygen vacancies at
the surface of an oxide. We believe that it is not, for two
reasons. First, in the presence of oxygen (which is the only case
of interest for oxidation catalysis), the vacancies will adsorb an
O2 molecule, and this is the stable structure. Such adsorption is
not relevant to bulk vacancies. Second, if the electron reservoir
consists of electron donors or acceptors, the energy of vacancy
formation will depend on how far the vacancy is from the
nearest donor. This is a local (chemical) eect: the energy
needed to make a vacancy near the donor is dierent from the
energy to make it far from the donor. This means that the
Fermi energy is not the only parameter in the problem.
Calculations of Ev at dierent distances from various donors
or acceptors show that this distance dependence if very
substantial, with the oxygen atoms near the dopant being the
easiest to remove.258
Oxygen vacancies in reducible oxides have interesting
properties. They have been studied for CeO2 and TiO2,
which are oxides that can change their oxidation state easily
from 4+ to 3+. This means that the Ce4+ or the Ti4+ cations act
as Lewis acids. Because an oxygen vacancy is a Lewis base and
the cations are Lewis acids, the formation of an oxygen vacancy
on these oxides is facilitated by a strong acidbase interaction.
The unpaired electrons created when the vacancy is formed will
occupy orbitals localized on the cations, reducing
them.188,259,268,269 The oxygen atoms neighboring the reduced
cation are displaced from their normal locations (which they
have when the cation is Me4+). The ensemble consisting of
the reduced ion plus the displaced oxygen atoms is called a
polaron. In DFT calculations, polarons are formed only if one
uses GGA+U theory, with a suciently high value of U (usually
between 3 and 5 eV), or hybrid functionals (e.g., HSE or
B3LYP).
Thus, the creation of an oxygen vacancy causes the formation
of two polarons. This polaron pair can be located on any pair of
cations, and we describe next how one can control these
locations. We use TiO2 as an example, but the procedure can be
applied to ceria and presumably to any other reducible oxide.
First, one makes an oxygen vacancy in the surface and one
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optimizes the geometry to obtain a minimum energy. The
polarons will be made at some location that is determined by
the initial state prior to geometry optimization. To locate a
polaron on a specic Ti atom, we displace slightly the
neighboring oxygen atoms away from it and optimize the
electronic energy (while keeping the oxygen atoms xed in the
displaced position).259 After optimizing the electronic energy,
we allow the oxygen atoms to adjust their position to minimize
the total energy. The end result is that this particular Ti atom
has the formal charge +3 and the polaron is stabilized at the
desired location. One can then use the same procedure to form
a second polaron (the O-vacancy provides two electrons) on
another Ti atom of our choice. Polaron formation lowers the
energy of vacancy formation by an amount that depends on the
location of the polarons. This dependence is fairly dramatic on
rutile.259 Until recently, it was assumed that the unpaired
electron reduce two Ti4+ ions located next to the oxygen
vacancy, which is a plausible but incorrect. It turns out that 80
possible polaron-pair locations have been studied,259 and all
have lower energy than in the case when both electrons are
located on the two Ti atoms neighboring the vacant site.
Depending on the value of U, the polaron formation lowers the
formation energy of an oxygen vacancy by at least 0.5 eV.259 If
one performs GGA calculations, the two unpaired electrons in
TiO2(110) are spread out over several atoms surrounding the
vacancy,270 and the cations are no longer Lewis acids. As a
result, the energy of vacancy formation is higher.
One of the most puzzling results of the calculations is the
large magnitude of Ev. A few examples from our work are Ev
= 3.3 eV for ZnO (1010),271 3.28 eV for NiO(011), 6.44 eV for
La2O3(001),145,272 5.77 eV for CaO(001),145 3.5 eV for
TiO2(110),259 3.00 eV for CeO2(111),145 and 6.38 eV for
LaOCl(001). The order of magnitude of the values reported
here is consistent with that reported in calculations by other
authors on these and other oxides. The last step in the synthesis
of almost all oxide catalysts is calcination in air or oxygen, for 4
or 5 h, at temperatures between 400 and 500 C. The large
values of Ev suggest that there should hardly be any oxygen
vacancies on the surfaces of most oxides. However, this
statement is softened if we consider the thermodynamic
equilibrium between a surface with oxygen vacancies on it and
gaseous oxygen. The entropy of the nal state (reduced oxide
plus O2 in the gas) is much larger than the entropy of the initial
state (unreduced oxide), because the translational and the
rotational entropies of gaseous O2 are large.273 As a result, the
entropy Sv of the reaction forming oxygen vacancies is
positive. Because the Gibbs free energy of the reaction is Gv =
Hv TSv, the free energy of the reaction that makes oxygen
vacancies is smaller than Ev. A thermodynamic calculation
therefore makes vacancy formation less forbidding than a
calculation of the total energy.
It is likely that stable oxides such as CaO, MgO, La2O3, or
Sm2O3 do not have oxygen vacancies on their surface as long as
sucient oxygen is available during their preparation and no
reductants are present. The large values of Ev for these oxides
explain why they are so hard to reduce. It also explains why
they are so popular as catalysts for the oxidative methane
coupling reaction (2CH4 + O2 C2H4 + 2H2O), which takes
place above 600 C (it is often carried out at 700800
C).81,82,274 They are the oxides that interact with methane
without combusting it. In this case, their ability to hold tightly
to the oxygen atoms at their surface is an asset.
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The situation is more confusing for oxides for which Ev is
not as large. Quite a bit of information regarding oxygen
vacancies is available for TiO2(110), for which one can perform
high-quality STM measurements in
UHV.147,160162,164,240,275290 These measurements nd that
there are always oxygen vacancies on the surface. Their
concentration can be as high as 16% (a vacancy concentration
of 8% is more common), but achieving this requires heating
at high temperature in UHV. One creates vacancies by heating
TiO2 to high temperature, and one annihilates them by
exposure to oxygen. These results seem inconsistent with the
high values of the energy of vacancy formation.
It is very dicult to compare these numerical values of Ev
to experimental values for real catalysts for a number of reasons.
The precursors used to make oxide catalysts have a purity of
99.99%. The 0.01% impurities may segregate at the surface and
change dramatically Ev. For example,291293 STM experi-
ments found that Ca segregates on the surface of TiO2.
Leerts115 used low-energy ion scattering experiments and
showed that F, Na, Al, or Si (the mass dierence is too small to
decide which one), K or Ca, and Cr or Mn, from unknown
sources, were present on the surface of some commercial
yttrium-stabilized zirconia, while X-ray uorescence detected
the presence of Hf and Ti in the bulk. All calculations show that
if these dopants are LVDs, the energy of vacancy formation will
be diminished substantially. Any acidic adsorbate, such as H (in
the form of hydroxyls), will also lower the energy of vacancy
formation.221 Calculations show that the value of Ev on
dierent crystal faces can vary substantially. Because the grains
of the catalysts are amorphous or have many facets, we can at
best measure an average value of Ev. All of these make it
dicult to compare the experimental values to those provided
by calculations. The situation is complicated by the fact that
experiments with the same oxide prepared by dierent
methods give very dierent results. The temperature at which
O2 starts to desorb from ceria, in temperature programmed
desorption experiments, depends strongly on the dispersion of
the oxide: the ner is the powder, the smaller is Ev.294298
Information about the energy of forming oxygen vacancies on
ceria can also be obtained from temperature programmed
reduction with H2 or CO. TPR with hydrogen gives a
widespread of the light-o temperature, hence a spread in the
stability of surface oxygen.299308 Temperature programmed
reduction with CO leads to similar conclusions.309311 As a
result, we cannot tell which measurement of Ev should be
compared to the calculated values.
We repeat here that we are interested in the energy of oxygen
vacancy formation Ev because it is a descriptor of the ability of
an oxide to function as an oxidant. We show below that the Ev
is strongly aected by substitutional cationic dopants.
9. OXIDE CATALYSTS DOPED WITH LOW-VALENCE
DOPANTS (LVDS)
9.1. Introduction
We accept the majority view224,225 that most oxidation
reactions catalyzed by undoped oxides take place by a Mars
van Krevelen (MvK) mechanism. This means that any oxide
modication that facilitates the removal of surface oxygen will
increase the eciency of the MvK process. Because oxygen is
electrophilic, we can remove it easier from the surface layer if
we create an electron decit at the surface. We propose to
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create this decit by replacing some of the cations of the host
oxide with cations having a lower valence.
The same strategy is suggested from another point of view.
An oxygen vacancy is a Lewis base. If we make a chemical
modication that creates a Lewis acid on the surface, the
subsequent formation of an oxygen vacancy will benet by a
strong acidbase interaction and the energy to make a vacancy
will lowered by this interaction.221 Doping with an LVD creates
a Lewis acid on the surface and therefore facilitates oxygen
vacancy formation and increases the binding energy of Lewis
bases to the surface.
Because the presence of an LVD in the surface layer makes it
easier to make oxygen vacancies, the oxygen atoms that are
easier to remove are also more reactive; an oxide doped with an
LVD is a better oxidant than the undoped oxide. However, it is
important to keep in mind that a better oxidant is not
necessarily a better oxidation catalyst.
In addition, because a surface doped with an LVD is a Lewis
acid, it will bind strongly Lewis bases, such as H or CH3.221,312
It follows that doping with an LVD will increase the energy of
the dissociative adsorption of an alkane because the fragments
produced by dissociation are Lewis bases and they interact
strongly with the Lewis acid surface. This makes such surfaces
promising candidates for breaking the CH bond in alkanes. If
the BrnstedEvansPolanyi rule313326 holds for alkane
activation on doped oxides, increasing the binding energy of
the fragments to the surface leads to lower activation energy for
dissociation.
9.2. The Eect of LVDs on the Energy of Oxygen-Vacancy
Formation
A large number of calculations studied the chemical eects of
doping an oxide surface with an
LVD.141,142,145,190,228,234,238,243,258,260,261,271,272,327339 We enu-
merate below the conclusions of these calculations and propose
that these are general and valid for any oxide doped with any
LVD.
(a) The energy Ev to make an oxygen vacancy near the
location of an LVD is much smaller than Ev for the
undoped oxide. Doped oxides are better oxidants than
the undoped host.
(b) The presence of an LVD aects oxygen atoms several
sites away from the dopant, making them easier to
remove than those of the undoped oxide. The oxygen
atom easiest to remove is adjacent to the dopant.258
(c) The presence of an LVD makes the doped oxide a strong
Lewis acid.221 As a result, the bond of any Lewis base
(e.g., H, CH3, NH3, CO) with the oxygen atoms in the
surface layer of the doped oxide is much stronger than
the same bond with the undoped oxide.
(d) The adsorption of a Lewis base on the surface of an oxide
doped with an LVD will tend to cancel the properties
conferred by the dopant, as if the base neutralizes the
acidity caused by the LVD. We have called this a
chemical compensation eect.145 The compensation
eect may play an important role in alkane activation.
When the CH bond is broken by dissociative
adsorption on an oxide surface doped with an LVD,
the fragments (H and CH3) are Lewis bases. They
neutralize the eect of the dopant (whose presence
makes the surface an acid) making the activity of the
doped oxide comparable to that of the undoped oxide.
The activity of the doped oxide is restored only after H
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and CH3 are removed from the surface by subsequent
chemistry. This raises the possibility that in some cases
the limiting step will be the rate of this removal. Otsuka
et al.340 and Sokolovskii et al.341 suggested that their
experiments support this idea.
In what follows, we present some of the computational
results that were extrapolated to formulate these rules.
Early examples of low-valence dopants dealt with very stable
oxides (e.g., alkali-earth oxides, La2O3, Sm2O3) doped with
alkali atoms, which catalyze oxidative coupling of methane to
ethane and ethylene. We do not discuss this system here
because excellent recent reviews are available.81,82 In addition, it
is doubtful that the doped oxides catalyzing this reaction are
stable under the reaction conditions used for oxidative methane
coupling (very high temperature).
In our earliest work,141 we have shown that the energy of
oxygen vacancy formation in the surface layer of rutile
TiO2(110) is substantially diminished by substitutional doping
with, Au, Cu, Ag, Ni, Pd, or Pt. Similar results were obtained for
CeO2 doped with Au,142,243,261,329,338 Ag,142 Cu,142,228,334,335,339
La,145,331,332 Y,190,258 Fe,329,333 Al,190 Sc,190 Mn,342 and In.190
This behavior is not conned to ceria. The same conclusion
was reached in studies of ZnO271 doped with Li, Na, K, Rb, Cs,
Cu, Ag, Au; of La2O3(100) and La2O3(011) doped with Cu,
Zn, Mg;260,272 of CaO doped with Li, Na, or K;145 of NiO
doped with alkali (Sun and Metiu, in preparation); and of TiO2
doped with Fe,234 Au, Ag, Cu, Ni.141 We are not aware of any
exception to this rule. For this reason, we postulated that the
rule is valid for any oxide doped with any LVD.
In all cases, the lowering of Ev by the presence of an LVD is
substantial. We give below a few examples.
(i) The computed energy Ev of oxygen-vacancy formation
at the surfaces of very stable oxides, such as CaO, MgO,
or La2O3, is very large. For example, the surface of
La2O3(001) has six-coordinated and four-coordinated
oxygen atoms exposed to the vacuum. The energy to
make a vacancy on this surface is260 6.44 eV (for the
four-coordinated O) and 5.77 eV (for the six-coordinated
O). Doping La2O3(001) with an LVD lowers the energy
needed for removing a four-coordinated O atom to
0.58 eV for a Cu dopant, to 2.38 eV for a Zn dopant,
and to 2.57 eV for a Mg dopant. A collapse in Ev of
the same order of magnitude was obtained for the energy
of removing a six-coordinated O atom from the doped
surface. The same behavior was observed for
La2O3(001)260 and other very stable, irreducible oxides
such as MgO258 and CaO. It is likely that the same
results will be observed for other stable oxides such as
Sm2O3, alkali earth oxides, Al2O3, SiO2.
(ii) The decrease of Ev by low-valence dopants, in less
stable oxides (e.g., CeO2, TiO2, NiO, ZnO), is also large
but not as dramatic as at (i). For example, the energy of
vacancy formation on CeO2(111) is 3.00 eV.258 For
CeO2(111) doped with La, Ev 1.36 eV;145 with Y,
Ev 1.06 eV;258 with Fe, Ev 2.73 eV.234,333 This
behavior is not caused by the fact that CeO2 is a
reducible oxide. Calculations in our group have shown
that doping NiO(011), which is not reducible, with Li
reduces Ev from 3.28 to 2.65 eV. The lowering of Ev
is a consistent trend. However, there is no qualitative
explanation for the dierences in Ev between samples
having the same host oxide and dierent dopants that
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have the same valence (e.g., CeO2 doped with In, Ga,
Al). Some correlations have been found between the
magnitude of Ev and other properties (e.g., the energy
of formation of the oxide of the dopant, or the cation
oxygen bond length of the oxide of the dopant).
However, most of them have been tested only on a
small number of systems.
(iii) The ability of a dopant to aect Ev may vary with the
crystalline face of the guest oxide. In the case of La2O3,
we found relatively small dierences between the Ev on
the (011) and the (001) face. Large dierences have
been observed for ceria doped with Au.261,338 The
manner in which the eect of an LVD varies from one
crystal face to another has not been suciently explored,
and no qualitative explanation for these dierences has
been proposed.
(iv) In the literature on materials chemistry, it is often stated
that doping with an LVD will generate spontaneously an
oxygen vacancy for charge compensation. This view is
reinforced by measurements that show that an oxide
doped with an LVD (in the bulk) has more oxygen
vacancies and higher oxygen mobility than the undoped
oxide. The calculations show that for the majority of
oxides whose surface is doped with an LVD, the
formation of an oxygen vacancy in the surface layer is
endoergic. Often the magnitude of Ev ranges between 1
and 2.5 eV, which means that doping with an LVD
facilitates the formation of an oxygen vacancy, but
oxygen vacancies are not made spontaneously. However,
for some crystalline faces of some oxides, with some
LVDs in the surface layer, Ev is positive (the oxygen
vacancy formation is exoergic). This happens, for
example, for ceria doped with Au.142,261 This sponta-
neous vacancy formation is more likely to be observed
when the valence of the dopant is lower by 2 or 3 than
the valence of the cation it replaces.
The number of oxygen vacancies at a surface (or in the bulk)
of an oxide doped with an LVD depends on the partial pressure
of the oxygen gas and the temperature of the surface used
during the preparation of the oxide. For this reason, some
workers use thermodynamic equilibrium calculations,335,343 in
computations that examine oxygen-vacancy formation. This is
useful for characterizing the as-prepared catalyst, which is
likely to be in thermodynamic equilibrium with the oxygen gas
present during calcination. However, catalytic reactions are run
under steady-state conditions, not at equilibrium. The surface is
exposed simultaneously to an oxidant (e.g., O2, CO2, N2O,
H2O2) and a reductant (e.g., an alkane, CO, H2). The reductant
makes vacancies, and the oxidant annihilates them. The steady-
state concentration of vacancies is controlled by the interplay
between the rate of vacancy formation and that of vacancy
annihilation and can be very dierent from the concentration at
equilibrium between oxygen gas and the oxide surface. For
example, in alkane oxidation, the surface is reduced by the
alkane and oxidized by the gas-phase oxygen (or whatever
oxidant is used). At high alkane partial pressure and low oxidant
pressure, the catalyst surface is likely to be reduced (a surface
with many oxygen vacancies). In the opposite limit, the surface
is close to being fully oxidized. If we use CO2 as an oxidant, the
surface has substantially more oxygen vacancies than in the case
when the oxidant is O2. In all cases, the oxygen leaving the
surface, to make a vacancy, comes o as H2O, or CO, or CO2,
etc. Forming oxygen vacancies by using a reductant is much
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Figure 3. The location of CH3 and H formed by the dissociative adsorption of CH4 on Zn-doped La2O3(001) (see Table 2). Top and side views of
(a) the structure with the lowest energy, and (b) the structure with the next-lowest energy, in which CH3 binds to the Zn dopant.
more favorable energetically than desorbing surface oxygen
atom as O2. The fact that Ev is 2 eV or higher does not mean
that there are no vacancies on the surface because much energy
is gained if the surface oxygen is removed by formation of water
(rather than 1/2O2) or by formation of CO2 (in a reaction with
CO).
9.3. The Presence of an LVD Makes the Surface More
Reactive
9.3.1. General Comments. One of the guiding rules in
working with doped oxide catalysts is that the easier it is to
remove a surface oxygen atom, the more reactive is that atom. If
this is true, a surface doped with LVDs ought to be more
reactive than the undoped surfaces. We show below that this is
the case.
Because doping with an LVD turns the oxide surface into a
Lewis acid, the oxygen on the surface of such oxide will bind
strongly Lewis bases. This means that the presence of the LVD
will activate the oxygen to bind more strongly CO, H, or an
alkyl (which are Lewis bases). In particular, the doped surface
will break a CH in an alkane because the fragments formed by
dissociation are Lewis bases.
Calculations conrm these qualitative rules. For example,
rutile TiO2(110) doped with Au is a much better CO oxidant
than the undoped rutile.141 This early work made a number of
observations about CO oxidation catalyzed by oxides doped
with LVDs that are likely to be general.333,334,338,339,342 It
showed that CO reacts with a surface oxygen atom located near
the dopant to form a OsCO group (Os is an oxygen atom in
the surface layer) whose CO bond lengths are close to those
of CO2. CO binds most strongly to the oxygen atom that is
easiest to remove. The CO2 molecule formed in this way
desorbs easily from the surface, leaving behind an oxygen
vacancy. Because the vacancy is a Lewis base and gaseous O2 is
a Lewis acid, our rules suggest that the vacancy adsorbs O2
readily. Moreover, the vacancy donates electrons to the
adsorbed O2, weakening the OO bond. The calculations
show that this is true: O2 adsorbed at the vacancy site reacts
readily with CO and forms a carbonate, which is easily
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decomposed to form CO2 and heal the oxygen vacancy. The
last step closes the catalytic cycle. This is a typical Marsvan
Krevelen mechanism. The role of the LVD is to make the
surface oxygen atom more reactive; it is not the ionic dopant
that is the active site. Therefore, these calculations provide no
support for the old idea that one should think of doping with an
LVD as a way of tuning the activity of the dopant (e.g., that a
Ni dopant will do catalytic chemistry similar to that of metallic
Ni but modied by being imbedded in the surface of the oxide).
9.3.2. Methane Activation: Does the Brnsted
EvansPolanyi Rule Work For It? A more interesting
reaction is the activation of alkanes for conversion to syngas,
alkenes, or valuable oxygenates. An appealing feature of such
reactions, as far as computational screening is concerned, is that
the rate-limiting step is the breaking of the CH bond.
Therefore, one can screen the ability of a catalyst for activating
methane by calculating the activation energy for this step. Such
calculations can help us nd active catalysts but tell us nothing
about selectivity because this would require computing the
activation energies for all possible steps in alkane oxidation.
Because such calculations would be extremely time-consuming,
our strategy has been to use computations to nd catalysts that
break the CH easily and then perform experiments to
determine what products are formed.
Aside from the early work on oxidative methane coupling by
doped oxides, Mayernik and Janik229,344 seem to be the rst to
have used computations to calculate the activation energy for
methane activation by a doped oxide. They showed that CeO2
doped with Pd or Zr is a better methane activation catalyst than
ceria. Subsequent work showed that the same is true for La2O3
doped with Cu, Mg, or Zn272 and for ceria doped with Pt.337
We propose that, in general, oxides doped with low-valence
atoms are better alkane activation catalysts than the undoped
oxides. We need however to qualify this statement. In most
cases, alkane activation takes place with a useful conversion at
temperatures above 400 C. If the dopant makes the surface
oxygen too easy to remove, then the doped oxide in contact
with a reductant (CO, H2, an alkane) may lose the activated
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oxygen at a temperature that is lower than that of CH bond
activation. This is more likely to happen when the oxidant is
CO2 than when it is O2. In this case, the oxide is reduced at the
reaction temperature, and this reduced oxide might or might
not be a good oxidation catalyst. Experiments underway in our
group show that this is the case for dry reforming of methane
by Ru-doped ceria: the catalyst is the reduced oxide. We believe
that this is the case because pulsing O2 through the system
under steady-state reaction conditions reduces the methane
conversion.
An interesting example of alkane activation by oxides doped
with an LVD is provided by Zn-doped La2O3(001). The
undoped oxide reacts with methane at very high temperatures,
close to those at which CH4 dissociates into H and CH3 in the
gas phase. The DFT calculations show that dissociative
adsorption of CH4 is extremely exothermic (4.45 eV).145 The
dissociative chemisorption of methane on Zn-doped
La2O3(001) is slightly exoergic. In Figure 3, we show the two
lowest energy states of the dissociated methane on this system
(all other binding schemes we have studied have higher
energies). In Figure 3a, the H and CH3 fragments bind to
surface oxygen atoms neighboring the Zn dopant. In Figure 3b,
CH3 binds to the dopant and H to an oxygen atom nearby. In
what follows, we call these states 3a and 3b. In Table 2, we give
Table 2. Information Regarding the Dissociative Adsorption
of CH4 on Zn-Doped La2O3(001)a
Er, eV Ea, eV dCH,
Figure 3a 0.45 1.3 3.74
Figure 3b 0.12 0.54 3.12
a
Er is the reaction energy, Ea is the activation energy, and dCH is the
distance between the C atom in the chemisorbed CH3 and the H atom
in the hydroxyl formed by disociation.
the dissociation energies and the activation energies (calculated
with the NEB method) for reaching 3a and 3b. Clearly the
presence of the dopant has a dramatic eect on the reaction
energy and on the activation energy for CH4 dissociation. The
table also shows the distance dCH between the carbon atom in
the adsorbed CH3 radical and the hydrogen atom forming the
hydroxyl. This is relevant because of a very simple rule that we
use for a preliminary screening of the activation energy for
reaching various possible product state. The activation energy
of a bond-breaking reaction is lowered when the fragments are
able to start making bonds with the surface before one stretches
too much the bond to be ruptured. This allows us to eliminate a
priori nal states in which the distance between the
chemisorbed fragments is substantially larger than the length
of the bond to be ruptured. Table 2 indicates that the distance
dCH between the fragments in 3b is smaller than that in 3a.
According to the rule just stated, the activation energy for
reaching 3b should be smaller than that for reaching 3a, and it
is. This runs counter to the BrnstedEvansPolanyi rule,
which states that the activation energy is controlled by the
binding energy of the nal state. In the present example, the
state 3a is bound more strongly to the surface than 3b, but the
activation energy to reach 3a is higher.
9.4. The Electronic Structure of an Oxide Doped with an
LVD
Chemists often use orbital energies and shapes to explain
qualitatively the properties of chemical bonds. While there is no
rigorous theoretical justication for such analysis, extensive
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experience shows that it often provides a useful rationalization
of the experimental or computational results.
The most relevant change, when an oxide is doped with an
LVD, is the appearance of an empty orbital (hole) in the
valence band; the LVD is a p-type dopant. This hole is
responsible for the acidity of the doped oxide: when a Lewis
base binds to the doped oxide, it donates an electron, which lls
the hole. The energy gained in this hole-lling process
contributes to the increase in the binding energy of the base.
A much-debated question is whether the empty orbital is
located around one oxygen atom (the hole is localized) or it is
spread over many oxygen atoms neighboring the dopant (the
hole is delocalized) or over the whole solid (the hole is
completely delocalized). The answer to this question may be
important: a localized hole converts (formally) an O2 into an
O, and a chemist will think, rightfully, that O is more reactive
than O2.
We have detailed information on this issue for Al-doped -
SiO2 (smoky quartz). Al atoms are a common impurity in silica,
and they are low-valence dopants. In what follows, we denote
Al and the four atoms bound to it by the symbol [AlO4h]0,
where h signies the presence of a hole caused by the
replacement of a tetravalent Si atom with a trivalent Al atom.
The superscript 0 indicates that the AlO4 group is electrically
neutral. GGA-DFT calculations on this system found that the
hole is delocalized over the four oxygen atoms neighboring
Al.327,345347 Calculations on SiO2 clusters doped with Al and
capped with H atoms,348350 which allow the use of more
reliable methods of computation, show that the hole is localized
on one oxygen atom. This localization breaks the tetrahedral
symmetry: one of the oxygen atoms is closer to Al than the
other three. This is the oxygen atom on which the hole is
localized. In particular, Pacchioni et al.350 have calculated the
coupling parameters in the EPR Hamiltonian and obtained
results that are close to the experimental ones.351353
Prompted by this situation, Nolan and Watson328 proposed
that whenever hole formation is suspected (e.g., when an LVD
is present), one should use DFT+UO where UO is a U
parameter for oxygen (in addition to the more common U
parameter for the cations). They varied the value of UO to
obtain a distorted geometry for [AlO4h]0 and localize the hole
on one of the oxygen atom. They found that UO = 7 eV gives
the desired result and smaller values of UO do not.
Subsequently, they recommended that UO = 7 eV should be
used by all studies of oxides containing low-valence
dopants.190,328,330,332 One would infer that if U for oxygen is
needed when an LVD is present, it should also be used in
calculations on undoped oxides. We are not aware of any work
in which such a procedure was used.
To better understand what is involved, we summarize some
of the facts about the [AlO4h] system, presented in several
review articles.351353 [AlO4h] is not normally present in
smoky quartz; instead, one has either AlO4H or AlO4Li. This is
not a surprise because Al-doped siliceous zeolites are well-
known to always come with a charge compensating ion. This
is in keeping with the chemical compensation concept145 that
proposes that whenever a surface is a Lewis acid, like the
surface of an oxide doped with an LVD, energy is gained if a
Lewis base binds to it. H and Li are the Lewis bases available
when the quartz is synthesized, and, as a result, AlO4H or
AlO4Li is present in the material. One has to resort to extreme
measures to prepare [AlO4h]0: irradiate Al-doped silica351353
for a long time with X-rays, or electrons, or -rays, or neutrons,
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or heat the silica sample for 10 h at 1400 C, and a pressure of
103 Torr.354 After one of these procedures is used, EPR
measurements conrm that the oxygen geometry around Al is
distorted and a localized hole (an O) is present. Schnadt and
Schneider, 352 however, found that the EPR spectrum
disappears at a temperature above 170 K because the hole
moves rapidly from one oxygen atom to another. It was
estimated that the barrier preventing this motion is 0.03 eV.
This means that at the temperatures at which catalysis takes
place, the hole is very mobile and the total energy dierence
between a system with a localized hole and one with a
delocalized hole is very small. At the temperatures used in
catalysis, the localization or the delocalization of the hole is an
irrelevant issue. We are therefore of the opinion that one
should not use a UO parameter for oxygen if the reason is to
localize the hole, because this will alter all other results of the
computation.
The question is whether the same small localization energy is
observed in other systems. Chretien has performed calculations
on La-doped ceria and found that one can obtain a hole
localized on oxygen by performing PBE-GGA as follows.
Perform the electronic-energy optimization with a geometry in
which one O atom is slightly shifted toward the La dopant to
break the symmetry. After the electronic energy is optimized,
release the constraint on O positions and optimize both the
electronic energy and the geometry. The nal state obtained by
this procedure maintains the distorted structure, and the hole in
this state is localized on two oxygen atoms (forming a polaron).
A PBE-GGA starting with symmetric oxygen positions will
maintain symmetry and will produce a delocalized hole. The
energy dierence between the two states is 0.03 eV; within the
accuracy of DFT these states are equally probable. Chretien has
also performed calculations of the binding energy of hydrogen
to various O atoms on the La-doped Ce(111) surface. The
binding energies when using for oxygen UO = 7 eV
(recommended by Nolan and Watson) dier from those
obtained by using UO = 0 eV. This dierence is of 0.7 eV,
which is much larger than the localization energy. By using UO
for oxygen, we are correcting an unimportant (i.e., small)
energy error (that of localization) and causing large energy
changes in a quantity (H-binding energy) that is important to
chemistry. We do not know whether the binding energy
obtained when UO is used is more accurate than the one
obtained when UO = 0. Given this situation, we think that one
should not use U for oxygen. However, this is an open
question, and it will surely be taken up again in the future.
9.5. Comparison with Experiments
We have already pointed out many of the diculties related to
comparing these calculations with experiments: we do not
know to what extent the materials we prepare are similar to the
models used by the calculation. The qualitative conclusion from
calculations is that doping with an LVD in the surface layer will
make the doped oxide a better oxidant than the undoped oxide.
This means that we expect that temperature programmed
desorption of oxygen, temperature programmed reduction by
CO or H2, and the light-o temperature for alkane activation
will occur at lower temperature for an oxide doped with an
LVD than for the undoped host oxide. We give here a few
examples to emphasize the diculties we encounter. Qiao et
al.355 prepared FexCe1xO2 and showed that, as long as x is less
than 0.2, CO oxidation and CH4 oxidation start (in TPR
experiments) at lower temperature than on either CeO2 or
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Fe2O3. At a given temperature, the conversion by the doped
oxide catalyst is higher than on either one of the undoped
oxides. This is what one expects from calculations. Wilkes et
al.356 studied methane oxidation by ceria doped with trivalent
La, Pr, and Gd and found that all of these dopants facilitate
methane oxidation. This is another success for the calculations.
However, Wilkes et al.357 tested the same doped ceria catalysts
for CO oxidation and found that doping inhibits the reaction:
the doped oxide is less reactive than the undoped one. This is
not what calculations suggest. These two reactions are carried
out at dierent temperatures, and CO and CH4 have dierent
reducing power so it is likely that the surface of the doped
oxide catalyst under reaction conditions is not the same for the
two reactions.
Zhao and Gorte have presented results on alkane combustion
on doped and undoped ceria, which seem to be at odds with
what is inferred from computations on other doped-oxide
systems as well as with other measurements on doped ceria. In
a study of n-butane combustion catalyzed by ceria and by
Me0.2Ce0.8O2 with Me = Yb, Y, Sm, Gd, La, Nb, Ta, or Pr, Zhao
and Gorte96 found that all doped-ceria oxides are less ecient
than the undoped ceria, except for Zr0.2Ce0.8O2 whose activity is
comparable to that of ceria. The dierence in rate (measured in
a dierential reactor and given in units of molecules/(s m2)) is
a factor of 100, and it is well outside the margin of error of the
experiments. The amount of oxygen that can be removed by
reacting with CO is larger on the undoped ceria than in the
doped one, contrary to what the rules on LVDs eects would
suggest. Another anomaly is that all doped-ceria samples had
a smaller area per gram than ceria, contrary to what is
frequently observed on other doped oxide systems. Note that
some of the dopants are LVDs, some are HVDs, and one is an
FVD; nevertheless, they all lower the rate of the combustion
reaction. This is not what one would expect from theory. Zhao
and Gorte358 focused next on the combustion of methane,
ethane, propane, and n-butane on Sm0.2Ce0.8O2. They found
that doping with Sm does not aect the rate of combustion of
methane and ethane but lowers the rate of combustion of
propane and n-butane. This is not what one would expect if one
extrapolates what is known from calculations on other systems.
It is however unwise to conclude that calculations are
misleading without performing detailed calculations on these
specic systems. We note that all dopants used in these studies
form very stable and unreactive oxides, and therefore it is
possible that they formed (during calcination) small unreactive
oxide clusters at the surface, blocking ceria reactive sites. It is
also conceivable that the LVDs used as dopants facilitate the
removal of the oxygen from ceria: the catalyst is then the
reduced oxide, and this may be less active than ceria.
10. THE EFFECT OF HIGH-VALENCE DOPANTS (HVDS)
10.1. Introduction
The eect of high-valence dopants on the chemistry of the host
oxide is more complex than that of LVDs because it depends on
whether the host is reducible or not. It is easiest to understand
why this is so in terms of Lewis acidbase interactions.221 In an
irreducible oxide (e.g., ZnO), a high-valence dopant, such as Al,
has one excess electron (two out of the three valence electrons
of Al are used to replace Zn2+). This formal electron counting
is not rigorous, but it is very helpful in understanding the
behavior of an oxide doped with an HVD. If the host oxide is
irreducible, this additional electron is localized on the
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dopant.260,272 This means that the dopant is a Lewis base, and

this controls some of its chemistry. A high-valence dopant in a
reducible oxide (e.g., Ta dopant in CeO2) behaves dier-
ently.258 Because Ce4+ cations are easily reduced to Ce3+ (Ce4+
is a Lewis acid), an HVD can donate its excess electrons to
reduce Ce ions in the host oxide. For example,258 hexavalent W
or Mo dopants donate two electrons and reduce two Ce4+ ions;
pentavalent Ta or Nb dopants donate one electron and reduce
one Ce4+ ion. Thus, these high-valence dopants are formally
tetravalent, and as a result they do not aect reducible oxides in
the same way they would aect the irreducible ones.
Because of this situation, we treat high-valence dopants in
irreducible oxides separately from those in which the host oxide
is reducible. We generalize the results of a small number of
calculations to propose some qualitative rules that need to be
tested by further calculations on similar systems.
10.2. HVDs in Irreducible Oxides Figure 4. Top and side views of the structure of a Zr-doped
271 La2O3(001) surface exposed to gaseous O2. The oxygen molecule
Pala et al. examined the eect of all substitutional dopants on
the energy of oxygen-vacancy formation on the surface of ZnO. shown in dark blue adsorbs on the dopant. The light-blue spheres are
La atoms, and the red spheres are surface oxygen atoms. The dopant is
They showed that all HVDs increased the energy needed for
dark gray.
removing a surface oxygen atom located near the dopant. This
suggests that the HVDs can be used to hinder oxidation by the adsorbs dissociatively in this system. In Figure 5, we show one
Marsvan Krevelen mechanism. However, this does not nal state for dissociative adsorption, in which H and CH3 bind
necessarily mean that their presence converts the host oxide
into a poor oxidation catalyst. If an oxidation reaction is
performed with O2 (as opposed to other oxidants such as
CO2), the oxygen, which is a strong Lewis acid, will bind to the
high-valence dopant, which is a Lewis base. At this point, we
need to distinguish two limiting cases. If the valence of the
dopant exceeds that of the cation it substitutes by 1 (we call this
an HVD1), then the adsorbed oxygen molecules gain one
electron (formally) in an antibonding orbital. As a result, the
bond length of the adsorbed species is substantially longer than
that of gaseous O2, and the adsorbed species gains electron
charge and closely resembles O2. This is a reactive species, and
when exposed to CO it makes a carbonate that decomposes to
release CO2. This leads to what Pala et al.359 called a non-
Marsvan Krevelen mechanism: the oxygen atom from the
oxidized product originates from the gas, not from the surface
of the oxide. Experiments on CO oxidation by Al- or Ti-doped
ZnO359 conrmed this prediction: when the oxidation was
performed with short pulses of gaseous 18O2, the CO2 produced
in the reaction contained 18O.
Figure 5. The dissociative adsorption of CH4 on a surface consisting
A limited number of calculations on other systems suggest
of Zr-doped La2O3(001) on which an O2 molecule was preadsorbed
that the activation of the oxygen adsorbed on an HVD1 is likely on the dopant. The system consists of a methoxide and hydroxyl, both
to be general. For example, Zr-doped La2O3(001) binds an bound to the Zr dopant. The oxygen atoms originating from the gas
oxygen molecule (see Figure 4) with an energy release of 2.63 are blue, and the oxygen atoms connected to the gray Zr dopant are
eV. The O2 molecule is not dissociated, but its bond length is red. The La atoms are located at the blue corners and the rest of the
1.35 , which is longer than the bond length of gas-phase O2 surface oxygen atoms at the red corners. Carbon is the smaller gray
and comparable to that of the gas-phase O2 ion. The adsorbed sphere, and the H atoms are white. The lower gure is the side view of
O2 makes use of the extra electrons on Zr; therefore, the ZrO2 the upper gure.
group no longer has three electrons to form bonds with the
oxide. Thus, ZrO2 creates an electron decit in the system, to the oxygen atoms adsorbed from the gas phase (which, in
which means that it acts as a low-valence dopant and turns the turn, are bonded to the Zr dopant). This reaction is exoergic by
surface into a Lewis acid. If this qualitative model is correct, 1.20 eV. A second nal state is shown in Figure 6, where the
then the presence of ZrO2 should facilitate the formation of methyl radical binds to one of the oxygen atoms previously
oxygen vacancies. Calculations show that indeed it does: it adsorbed from the gas (to form a methoxide bound to Ru) and
takes only 0.96 eV to remove an oxygen atom next to the ZrO2 the other binds to one of the oxygen atoms in the surface layer,
group and form 1/2O2 in the gas. There are now two kinds of near to Ru, to form a hydroxyl. This reaction is exoergic by 1.04
active oxygen atoms in the system: the adsorbed O2 and any eV. Similar results are obtained for La2O3 doped with Ti, and
one of the three surface oxygen atoms neighboring the ZrO2 we propose that this kind of behavior is general for HVD1
group. This is reected in the manner in which methane dopants in irreducible host oxides. However, more calculations
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Figure 6. The dissociative adsorption of CH4 on a surface consisting
of Zr-doped La2O3(001) on which an O2 molecule was preadsorbed
on the dopant. The system consists of a methoxide bound to the Zr
dopant and a hydroxyl formed with a surface oxygen atom near the
dopant. The oxygen atoms originating from the gas are blue, and the
oxygen atoms connected to the gray Zr dopant are red. The La atoms
are located at the blue corners and the rest of the surface oxygen atoms
at the red ones. Carbon is the smaller gray sphere, and the H atoms are
white. The lower gure is the side view of the upper one.
and more experiments are needed for establishing this
statement rmly.
The situation is dierent in the limiting case of HVD2. An
example is provide by Ta-doped La2O3(001) exposed to
oxygen. The O2 molecule dissociates: one atom binds to Ta,
and the other binds to a surface oxygen atom forming a sort of
O2 molecule (dark yellow in Figure 7). The binding energy of
O2 is 4.58 eV. Similar results were obtained for Nb-doped
La2O3. Although not many studies of this kind are available, we
Figure 7. The interaction of Ta-doped La2O3(001) with gas-phase
oxygen. The Ta dopant is bright yellow. The four purple spheres are
oxygen atoms bound to Ta; three are surface oxygen atoms, and one
(sticking into the vacuum) comes from the gas phase. The dark yellow
spheres are oxygen atoms. One is a surface oxygen atom, and the other
came from the gas phase. The rest of the oxygen atoms are red or
magenta, and La is gray.
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believe that this very strong bond with oxygen is typical for
HVD2 or HVD3. This means that these dopants bind oxygen
too strongly and the complex formed in this way is too low in
energy to participate in redox reactions. More studies are
needed to conrm these qualitative statements.
10.3. HVDs in Reducible Oxides
Very few calculations have examined this kind of system. They
allow us to make some guesses and extrapolations, but they
need to be reinforced (or modied) by further work. By
denition, the cation in a reducible oxide (e.g., CeO2, TiO2)
can easily change its formal charge while interacting with
electron-donating species (Lewis bases). The few existing
calculations suggest that Lewis bases adsorbed on the surface
are able to reduce Ce4+ to Ce3+ (or Ti4+ to Ti3+). For example,
H (a Lewis base) reduces a Ce ion when it is adsorbed on
CeO2360 and so does a Cu atom adsorbed on ceria.335 Nolan331
has examined oxygen-vacancy formation at the surface of CeO2
doped with La. Because La is an LVD, its presence creates a
hole located on an oxygen atom, which acts as an acid site.
When an oxygen vacancy is formed, two unpaired electrons are
created: one lls the hole and the other reduces Ce4+ to Ce3+.
In all calculations, the reducibility of Ce4+ is present only in
DFT+U (with suciently large U) or when hybrid functionals
are used. These statements are consistent with experiments,
which show that the adsorption of H (a Lewis base) or the
formation of an oxygen vacancy (a Lewis base) is accompanied
by the appearance of Ce3+ or Ti3+ in the XPS or in the EPR
spectra.
On the basis of these observations, we accept the suggestion
that Ce4+ and Ti4+ can act as Lewis acids. It is also reasonable to
assume that in the presence of oxygen in the gas, the high-
valence dopant will adsorb oxygen and form either an MeO2
group or an MeO group.262 This should happen because
oxygen is a much stronger acid than Ti4+ or Ce4+. We are not
aware of the existence of calculations that have examined
whether such behavior extends to other reducible oxides (V2O5,
Nb2O5, SnO2, MoO3, etc.). We hope that the conjectures made
here will stimulate more calculations on HVDs in reducible
oxides.
10.4. The Stability of High-Valence Dopants
This is a question that has received little attention so far even
though it is on the mind of anyone performing experiments
with doped oxides. Consider a high-valence dopant that forms a
very stable oxide (e.g., Ta, Nb, La) with a high coordination to
oxygen. Imagine that such a cation is used to dope an oxide
(e.g., NiO, PbO2, CuO) that is less stable than the dopants
oxide. One would suspect that such a dopant in contact with
gas-phase oxygen might prefer to leave the cationic site, move
on top of the surface, and adsorb oxygen from the gas phase to
form an oxide cluster. If this structure has lower energy it is
likely that it will become prevalent during calcination (when the
doped oxide is prepared). The intended doped oxide ends up
being a submonolayer (or a layer) of small dopantoxide
clusters covering a surface with cationic defects. A few
exploratory calculations in our group show that this is the
case for Cr-doped CeO2 and for Nb-doped NiO. As we have
discussed earlier, it is very dicult to determine by experiments
whether this segregation of the dopant takes place.
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11. SAME-VALENCE DOPANTS (SVDS) AND
FLEXIBLE-VALENCE DOPANTS (FVDS)
Quite a bit of work has been devoted to the situation when the
dopant and the cation being substituted have the same valence.
Calculations have been performed to study the properties of
TiO2 doped with Ce,361 Zr,361 and Pt141 and of CeO2 doped
with Zr,229,235,255,258,334,361,362 or with Ti,362 or Hf,362 or Pd,229
or Pt,258 or Si, Ge, Sn, and Pb.363 We note in particular a study
by Mayernick and Janik229 on methane activation by Zr-doped
ceria. All of these calculations show that the dopant aects
favorably the properties of the host oxide. We mention a few
experimental papers, many of which investigated the
modication of the oxygen release in CeO2 doped with same-
valence dopants, such as Zr,364367 Ti,365,368374 Sn,375 or
Sn.376 Other studies investigated the redox properties of CeO2
doped with Ti,377 CO oxidation by CeO2 doped with Pt,378
watergas shift by Pt-doped CeO2,379 and methane oxidation
by ZrCeO2.380 In all cases, doping with an SVD improves
performance. However, we were unable to formulate any
simple rules regarding the SVDs in catalysis other than to say
that they should be tried, especially if one tunes the properties
of an oxide that is already an ecient catalyst.
Because we dene the valence of a dopant by examining the
stoichiometry of its stable oxides, we cannot assign a unique
valence to dopants that have several stable oxides. For example,
V2O5 and V2O3 are stable oxides, VO2 and VO are also stable
but less so, and compounds with formulas VnO2n+1 and VnO2n1
have also been prepared. Obviously vanadium is a very versatile
atom capable of taking a variety of valences when binding to
oxygen. If we dope an oxide whose cations are tetravalent (e.g.,
SnO2) with vanadium, should we assume that vanadium is an
HVD (because V2O5 is stable) or an LVD (because V2O3 is
stable)? There is no a priori answer to this question. More
complications arise if one considers that tetravalent and
divalent vanadium are also possible. This is why we classify a
V-dopant in a MeO2 host oxide as being a exible-valence
dopant (FVD). Not much is known about the general behavior
of such systems.
Nb is an FVD (Nb2O5 is the most stable Nb oxide but NbO2
and NbO are also stable), and if it dopes CeO2 it will donate an
electron and reduce a cerium ion.258,330 Therefore, the formal
valence of Nb is IV. It is interesting that if NO2 is adsorbed on
the Nb-doped ceria surface an NO2 ion is formed.330 NO2 is
apparently a stronger acid than Ce4+, and it manages to capture
the electron that Nb (a Lewis base) makes available. The
conclusions drawn from these calculations are supported by
experiments on V-doped SnO2 catalysts, which consist, when
the concentration of V is low, of a solid solution in which
vanadium is V4+.
Another interesting example of exible-valence dopant is
provided by Cr-doped ceria. Experiments in Hegdes
group381,382 indicated that this doped oxide contains Ce3+
and Ce4+ as well as Cr4+ and Cr6+. Cr-doped ceria is a very
good oxygen storage material (when heated it releases O2 at
350 C). The as-prepared compound has an excess of oxygen
(the proposed formula is Ce0.67Cr0.33O2.11). While the amount
of Cr in Hegdes study is uncomfortably high (most solid
solutions are not stable at such high concentrations of dopant),
the XRD measurements show that no Cr oxide is present and
the system has the uorite structure of CeO2. Calculations in
our group found that this system has very peculiar behavior. In
general, doping CeO2(111) with a high-valence dopant distorts
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slightly the position of the oxygen atoms surrounding the
dopant. Cr makes three stable oxides, CrO3, CrO2, and Cr2O3,
so it is therefore capable of being hexa-, tetra-, or trivalent,
which makes it a exible-valence dopant. Calculations in which
one Ce ion in the CeO2(111) surface is replaced with a Cr
atom show that this system has six dierent geometries whose
energy diers by at most 0.26 eV from the lowest energy one.
Two of the structures are practically degenerate and have the
lowest energy. In one of these Cr binds to ve oxygen atoms,
one of which is pulled out of its lattice site by 1 . We call this
the CrO5 structure. When the oxygen atom is pulled out of its
lattice site, a vacant oxygen-lattice site is created, and we call
this a pseudo oxygen vacancy (pseudo because the O atom
has been removed from its lattice site but not from the surface).
In addition to having a pseudo vacancy, the system also has a
reduced Ce atom. In another structure, with practically the
same energy as CrO5, the Cr dopant binds to four oxygen
atoms, makes one pseudo oxygen vacancy, and reduces two Ce
ions to Ce3+. A dopant causing such large distortions of oxygen
positions is unusual. Both the CrO4 and the CrO5 structures
adsorb oxygen from the gas phase, and the reaction
Crdoped ceria + 1/2 O2 (g)
Crdoped ceria with an additional O atom
is exoergic by 1 eV for CrO4 and 0.7 eV for CrO5. This means
that excess oxygen is present in the system, and this might
explain why Hegde et al. found that the stoichiometric formula
of the compound is Ce0.67Cr0.33O2.11. The calculations show
that the compound formed by oxygen adsorption on Cr-doped
ceria is a strong oxidant.
The examples presented here suggest that it may be dicult
to nd simple rules for the eects of exible-valence dopants,
especially if the host oxide is a reducible. More computational
and experimental work is needed for clarifying the behavior of
these systems.
12. TWO CASE STUDIES: OXIDATIVE
DEHYDROGENATION OF ETHYLBENZENE AND
ETHANE
12.1. Introduction
While the literature on catalysis by doped oxide is extensive,
there are very few cases in which such catalysts were studied
systematically, by preparing one host oxide with a variety of
dopants, by a variety of methods, and by using them for the
same reaction under a variety of conditions. For this reason, we
thought that it would be useful to concentrate on two examples
for which substantial information exists. Both examples are
oxidative dehydrogenation reactions: one converts ethyl
benzene to styrene, and the other converts ethane to ethylene.
12.2. Oxidative Dehydrogenation: Generalities
The dehydrogenation reactions examined here are both
described by the formula
RCH 2CH3 RCHCH 2 + H 2
In one case R is a hydrogen atom, and in the other it is a phenyl
group C6H5. Both reactions are endothermic, equilibrium
limited, and take place at suciently high temperatures to
require expensive technology. It is therefore tempting to
perform the dehydrogenation reaction in the presence of a
compound that reacts with H2, thereby shifting favorably the
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thermodynamic equilibrium and diminishing the amount of
heat necessary for the reaction.
A much-pursued variant of this scheme is oxidative
dehydrogenation (ODH) using oxygen to form water:
RCH 2CH3 + 1/2 O2 RCHCH 2 + H 2O
An alternative is to use CO2, to react with H2 and make CO
and water (the reverse watergas shift reaction, RWGS):
RCH 2CH3 + CO2 RCHCH 2 + CO + H 2O
To our knowledge, the rst coupling of a dehydrogenation
reaction with a hydrogen consuming reaction is the Deacon
process,383,384 which can be viewed as a oxidative dehydrogen-
ation of HCl (2HCl + 1/2O2 Cl2 + H2O).
A detailed comparison between ODH with O2 and with CO2
is best made separately, for each compound being dehydro-
genated. There are however several aspects that are common to
all dehydrogenation reactions. The use of CO2 has the
advantage of producing CO and thus recovering some of the
fuel capacity of the disappearing hydrogen; ODH with O2
produces water and no fuel. One can think of the ODH with
CO2 as using CO2 as an oxidant, instead of O2. CO2 is less
aggressive than oxygen, and it is less likely to react with the
alkene produced by dehydrogenation. The amount of oxygen in
the ODH feed with O2 is limited by the danger of explosion.
This is not a problem in ODH with CO2. Unfortunately, ODH
with CO2 is an endothermic reaction and requires net heat
addition.
While the idea of coupling dehydrogenation with a hydrogen
consuming reaction is appealing, the performance of the
catalysts studied so far is not good enough for commercial use.
13. THE OXIDATIVE DEHYDROGENATION OF
ETHYLBENZENE TO STYRENE
Styrene, C6H5CHCH2, is an important alkene used to make
a variety of polymers.385 It is prepared industrially by
dehydrogenating ethylbenzene:
C6H5CH 2CH3 C6H5CHCH 2 + H 2
H 0 = 123.6 kJ/mol (1)
a reaction catalyzed by a mixture of Fe2O3 (4090%) and K2O
(530%) promoted with Cr, Ce, Mo, Ca, and Mg oxides.385
There are many catalyst preparations that are variations on this
theme, and Lloyd2 mentions that 1215 dierent iron oxide
catalysts for this reaction are provided by various suppliers. The
promoters are added in small amounts, and we do not know if
they are dopants or small oxide clusters supported on the
surface of the main oxides. The role of these promoters is
explained in a review by Cavani and Triro.386 The
dehydrogenation reaction is endothermic, equilibrium-limited,
and thermodynamically favored by high temperature and low
pressure. Because the temperature used in industry ranges
between 550 and 680 C, one cannot use molten salts as a heat
transfer agent, and the reactants are heated by injecting hot
steam in the feed. Besides serving as a heat-transfer medium,
the steam reduces coking, acts as a diluent (which favors
product formation according to the Le Chatelier principle), and
prevents the reduction of the iron oxide catalyst. The need to
use at least 68 mol of steam per mole of ethylbenzene387 is a
major expense in styrene manufacturing. The conversion is 60
70%, and molar selectivity is 9095%.387 High conversion is
particularly important for this system because the boiling point
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of ethylbenzene (136.2 C) is very close to that of styrene
(145.2 C), and separation is dicult.
This is a demanding process that could stand improvement,
and much work has been devoted to nding good catalysts for
oxidative dehydrogenation (ODH) of ethylbenzene to styrene.
As discussed in section 12.2, this can be done by using either
O2 or CO2. In what follows, we discuss the use of doped oxides
to perform these reactions.
14. OXIDATIVE DEHYDROGENATION OF
ETHYLBENZENE TO STYRENE USING CO2 AS AN
OXIDANT
14.1. Introduction
In 1968, Olson was granted a patent388 suggesting that the
conversion of ethylbenzene by dehydrogenation can be
improved by coupling it with the reverse watergas shift
(RWGS) reaction. Towler and Lynn387 have calculated that at
600 C and a CO2-to-ethylbenzene ratio of 5:1, the equilibrium
conversion of ethylbenzene is 95%. If the dehydrogenation is
performed under the same conditions, but in the absence of
CO2, the equilibrium conversion is 67%. These calculations
were made by assuming that no other reactions, besides eq 1
and RWGS, take place in the system, which is true only if the
catalyst is very selective. Because of this assumption, the
equilibrium yield of styrene calculated in this way is an upper
limit.
The reverse watergas shift reaction is endothermic, so heat
must be provided externally, but the cost of heating CO2 is
smaller than that of heating steam, which is a signicant
advantage. Producing CO recovers to some extent the fuel lost
by consuming the hydrogen, which is not the case when O2 is
used as oxidant.
A large number of papers have used oxides389416 or mixed
oxides390392,394,395,399401,403,407411,413,415,417427 as catalysts
for the conversion of ethylbenzene to styrene. Many of the
papers using mixed oxides did not intend to make substitu-
tionally doped oxides. In most cases, their goal was to create
two phases of two oxides, one basic (to adsorb and perhaps
activate CO2) and one acidic (to activate the dehydrogenation
of the ethylbenzene). Many examples are oered by the work in
Parks group390392,394,403,424426 that studied ZrO2 mixed with
TiO2, or with MnO2,391 with SnO2,392 or with vanadium
oxide394 or with TiO2 or with K2O,390 and vanadia supported
on Al2O3 mixed with MgO, P2O5, Cr2O3, MoO3, Sb2O3.426
Reviews of this work are available.424,425 As a rule, the mixed
oxides (two phase system) performed better than the
individual, unmixed oxides. It is possible that these catalysts
contained some amounts of doped oxides, but this has not been
documented or suggested.
We will not discuss work on mixed oxides further and
concentrate on papers that intended to prepare doped oxide
catalysts or are likely to have done so. Given the fact that so
many oxides have fairly good activity for styrene preparation by
ODH, it is natural to ask whether doping them might increase
their activity.
14.2. Ethylbenzene Dehydrogenation in the Presence of
CO2, Catalyzed by Doped Oxides
14.2.1. Experimental Results. There is little work that
attempted deliberately to prepare doped oxides and test them
for ethylbenzene ODH with CO2. Ren et al.415 studied TiO2
and TiO2 doped with Fe, V, Zr, and Mg, and Gao et al.420 used
ZrO2 and Ga-doped ZrO2. We examine Fe-doped TiO2 and
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Ga-doped ZrO2 together because in both cases the dopants are
LVDs. TiO2 is reducible and ZrO2 is not, but this should not
play an essential role in the chemical eects caused by the low-
valence dopants.
Doping with Fe increases substantially the area per gram
even though the doped and the undoped oxide were prepared
by the same solgel method, under identical conditions (except
for the presence of the precursor for the dopant). For example,
the surface of TiO2 is 21.7 m2/g, that of Fe1Ti is 98.0 m2/g, and
that of Fe3Ti is 61.1 m2/g. Here, we use the notation of Ren et
al.,415 and Fe3Ti means that 3% of the Ti atoms were replaced
with Fe. The XRD measurements detected no crystalline iron
oxide. The undoped TiO2 made by the solgel method has an
anatase structure. The presence of Fe results in a compound
whose structure is a mixture of anatase and rutile; Fe7Ti is
almost entirely rutile. This suggests that some of the Fe is
atomically dispersed inside the TiO2 grains because it is
unlikely that Fe will induce this phase transformation if all Fe
atoms introduced in the system form small iron oxide clusters
on the surface (which are not detectable in XRD).
The reactivity of these catalysts, for ethylbenzene ODH with
CO2 as oxidant, was measured at a temperature of 550 C, a
pressure of 0.1 MPa, W/F = 40 gcat h/mol, a CO2/ethylbenzene
ratio of 1:1, and a ow rate of 50 mL/min. The best
ethylbenzene conversion, obtained with Fe3Ti, was 19.3% with
a styrene yield of 18.6%. The undoped TiO2 converted 5.4% of
the ethylbenzene, with a styrene yield of 5.4%. If we do not take
into account the change of surface area caused by doping, it
would seem that Fe3Ti is more eective in converting
ethylbenzene than TiO2. However, the area per gram of
Fe3Ti is 98 m2/g, while that of TiO2 is 21.7 m2/g. If we
calculate the ethylbenzene conversion per unit area then, by
this measure, TiO2 is about as active as Fe3Ti; the main eect of
the dopant on conversion is to increase the area per gram.
However, the dopant improves selectivity, at the same
conversion per area, which is 83.0% for TiO2 and 96.4% for
Fe3Ti. The styrene yield is independent of area, and the better
styrene yield on Fe3Ti indicates that selectivity benets from
doping.
Aside from low conversion, a further disappointment is the
low stability of the catalyst: the conversion drops from 19.4% to
8.6% after 2 h on stream. TGA experiments on the catalyst after
the reaction show that the catalyst coked. However, reoxidizing
the catalyst did not restore the ethylbenzene conversion fully,
which suggests that additional factors are involved in
deactivation.
Gao et al.420 prepared Ga-doped ZrO2 by coprecipitation.
We follow below their notation, in which 10GZ means ZrO2
doped with Ga and having 10% Ga2O3 by weight. The
properties of ZrO2 and those of 5GZ, 10GZ, 15GZ, and 20GZ
were studied. XRD, Raman, and UVvis measurements
support the assumption that Ga-doped zirconia has been
prepared even though one has not ruled out the possibility that
Ga is present in the form of very small GaOx clusters on the
surface. Reactivity tests were performed with a gas mixture with
the molar ration of N2/CO2/ethylbenzene = 361/19/1, at a
temperature of 600 C, with a ow rate of 60 mL/min. All
catalysts tested were heated for 2 h at 600 C in N2 ow before
performing the ODH reaction.
The conversion of ethylbenzene catalyzed by ZrO2 is 16.8%,
and the selectivity is 100%, which gives a styrene yield of 16.8%.
The ethylbenzene conversion increases by adding Ga, and the
selectivity decreases slightly (it is in the nineties for all GZ
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catalysts). The best styrene yield is 34.3%, catalyzed by 15GZ.
The yield increases with increased amount of Ga up to 15GZ
and then decreases for 20GZ. This is common with many
doped oxides: when too much dopant is added, the activity is
lost. Doping with Ga increases the conversion, however, as the
area per gram of 15GZ is 53.9 m2/g, while that of ZrO2 is 19.0
m2/g. The conversion per area of catalysts is higher for ZrO2
(0.88) than for 15GZ (0.63). The selectivity on ZrO is slightly
better. We conclude therefore that ZrO2 doped with Ga is a
worse catalyst than ZrO2, and both have very low performance.
It is unfortunate that the ethylbenzene conversion decreases
with the time on stream, and after 4 h it is 15%.
Ren et al.415 prepared TiO2 doped with Fe, V, Zr, and Mg.
Among these, Fe3Ti is most active. The measurements on V3Ti,
Zr3Ti, and Mg3Ti show that all of them have higher conversion
and better selectivity than TiO2. When compared to each other,
they have similar performance. In light of the computational
results in other systems, this is surprising, given the fact that the
V is a high-valence dopant, Mg is a low-valence dopant, and Zr
has the same valence as Ti.
We caution that the experiments described here were very
limited in scope and look only at a narrow range of parameters
(dopant concentration, method of preparation, gas composi-
tion, temperature, etc.). The conclusions we draw are
temporary, and further experiments may change the situation.
14.2.2. Are These Results Consistent with What We
Know from Calculations? Unfortunately, we have no
systematic calculations for the systems discussed in this section.
From calculations on other systems, we know that low-valence
dopants lower the energy of vacancy formation and will make
the oxide a better oxidant. Corma et al.234,329,428 have shown
that this is also true for anatase doped with Fe, which is close to
one of the systems we discuss here. We also know that the
easier it is to remove an oxygen atom from the surface layer, the
more reactive is that atom. In particular, the oxide doped with a
low-valence dopant (LVD) should break a CH bond more
eciently than the undoped one. This should be the case for
Ga-doped zirconia and Fe-doped TiO2. This prediction would
be best tested by doing TPR experiments with ethylbenzene to
determine the temperature of the onset of reaction with the
doped oxide and the undoped one. Such measurements are not
available for the systems reviewed in this section. The situation
is more complicated for steady-state experiments. The oxide
catalyst is reduced by ethylbenzene, and it is oxidized by CO2.
Because CO2 is a poor oxidant, the rate of reduction is likely to
be faster than the rate of reoxidation of the surface, and the
catalyst under working condition is likely to be the reduced
doped oxide. Doping with an LVD makes the reduction of the
oxide more facile. This qualitative prediction could be tested by
running the reaction at steady state and then suddenly stopping
the feed, sending oxygen pulses through the catalyst bed, and
measuring the oxygen consumption. As far as we know, such
experiments have not yet been performed on these systems.
The next question is why Mg-, Zr-, and V-doped titania are
less active than the Fe-doped sample. By analogy with
calculations performed on other systems, we expect that
doping with Zr will have a small eect on catalytic chemistry
because its oxide is very similar to TiO2 (same valence, same
structure). Calculations on CeO2 doped with a high-valence
dopant have shown that the dopant loses electrons, which
reduce a Ce atom from a formal charge of 4+ to 3+. If this
happens for TiO2, which is a reducible oxide similar to CeO2,
the V dopant will be tetravalent, and this means that the
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chemistry of the V-doped TiO2 surface is similar to that of
TiO2. The formal charge of Mg is 2+, and a few calculations on
other systems of this type showed that when the valence of the
dopant is lower by 2 than the valence of the cation it
substitutes, the energy for making an oxygen vacancy near the
dopant is either very small or exothermic. Therefore, the doped
oxide may have lost the active oxygen by the time the system
reaches the temperature at which ethylbenzene is activated.
These speculations may explain why Zr, V, and Mg dopants are
less ecient than Fe.
Coupling the dehydrogenation of ethylbenzene with the
reverse watergas shift reaction is worth exploring further.
Doping oxide catalysts, to improve their performance for this
reaction, has received little attention. Very few oxidedopant
pairs have been examined, and no attempt was made to
optimize the performance of those studied so far. No
computations have been performed specically for this reaction
system, and the analysis performed here is based on analogy
with other systems.
15. OXIDATIVE DEHYDROGENATION OF
ETHYLBENZENE TO STYRENE BY USING OXYGEN
AND DOPED OXIDE CATALYSTS
As we have emphasized, the use of oxygen to react with the H2
shifts the equilibrium of the dehydrogenation reaction
favorably. An obvious disadvantage is that an aggressive
molecule such as oxygen might react with styrene, reducing
selectivity. Danger of explosion and re limits the oxygen/
hydrocarbon ratios that can be used. Burning hydrogen, which
is a valuable product, may also diminish the economic appeal of
the process.
Sivarajani et al.412 prepared vanadium-doped titania,
Ti1xVxO2, by the combustion method. The values of x in
the above formula were 0.05, 0.10, and 0.15, but these are
calculated on the basis of the amount of V present in the
precursors. The authors caution that some V may have been
lost by evaporation during calcination. In their preparation
method, they used urea as a fuel to avoid carbon contamination.
No vanadium oxide peaks were observed in XRD, and the
material is a mixture of rutile and anatase structures. Neither
Raman nor IR measurements nd evidence for the formation of
VOx clusters supported on TiO2. The electron binding energies
of Ti2p3/2, V2p, and O1s were measured by XPS. The Ti peaks
were assigned to Ti4+, and there is no mention of the presence
of Ti3+, which would be expected if the V dopant donates
electrons to Ti. The XPS measurements were interpreted to
mean that V dopants have a formal charge of 5+.
Calculations262 have shown that a V atom substituting a Ti
atom in the surface layer will bind oxygen from the gas phase,
and the dopant is the VO group formed during calcination.
In this compound, V is 5+ and it is possible that the surface-
sensitive XPS measurements detect this group. This is
consistent with the fact that no Ti3+ was detected. Another
way of saying the same thing is to note that a V atom
substituting a Ti atom is a Lewis base; given the chance to
transfer an electron to Ti4+ or to oxygen, it will chose the
oxygen, which is the stronger Lewis acid.221
Doping with V causes an increase in area per gram, as
compared to that of TiO2 prepared by the same method.
The styrene yield on all doped oxides is higher than that of
undoped TiO2, but unfortunately the performance deteriorates
rapidly with the time on stream. Sivarajani et al. performed a
careful analysis of the catalyst after the reaction. They found
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that the structure of the working catalyst is converted entirely
to the rutile, which does not aect performance. No V2O5 was
detected in the XRD spectra of the spent catalyst, and the XPS
measurements detected coke on the surface. Calcination in air
for 20 min at 500 C restores activity, which suggests that the
main reason for deactivation is coking.
These experiments show that doping TiO2 with V improves
performance, but the lack of stability is a serious limitation. If
process economics justies the added cost, the catalyst can be
moved continuously out of the reactor, decoked, and moved
back into the reactor. Such a procedure is used for several
industrial catalytic processes.
Fans group413 studied ODH of ethylbenzene to styrene with
oxygen, catalyzed by CeO2 doped with Al, Sn, Zr, Mn, and Ni.
All doped oxides had a 10% molar ratio of dopant to cerium.
They were prepared by a template-assisted method,429,430
which makes a disordered mesoscopic solid. The Ni-doped
ceria catalyst was also prepared by oxalate-gel coprecipitation to
determine how the preparation method aects catalytic
performance.
The best catalyst in this group is Ni0.1Ce0.9O2, which gives an
ethylbenzene conversion of 70% and a selectivity to styrene of
75%, at a temperature of 450 C, O2/ethylbenzene ratio = 0.8,
and space velocity = 250 mL/gcat/min. Changing the space
velocity to 418 mL/gcat/min lowers the conversion to 64%, but
increases the selectivity to 86%. Increasing the temperature
increases the conversion but decreases selectivity. The
performance of the catalyst decreases if the Ni content is
lower or higher than 10% molar. It is likely that the
performance can be improved by a more thorough optimization
of the catalyst and of the reaction conditions.
The performance of all other materials tested by Fan et al. is
worse than that of Ni0.1Ce0.9O2. The selectivity is roughly the
same, but the conversion is lower. The order of catalysts by
their conversion at 450 C is
Ce0.9Ni 0.1O2 > Ce0.9Mn 0.1O2 > Ce0.9Sn 0.1O2 > CeO2
> Ce0.9Zr0.1O2 > Ce0.9Al 0.1O
However, this scale was made without normalizing the
conversion to surface area. If we perform that normalization
(we divide the conversion by the specic area), Zr-doped and
Al-doped ceria are slightly more active than CeO2, because
CeO2 has the highest area per gram of all of the materials
studied here. It is interesting to note that for other methods of
preparation, doping increases, almost always, the specic area of
the catalyst; the method of preparation used by Fan et al. is an
exception from this rule.
The method of preparation makes a dierence. Ce0.9Ni0.1O2
made by oxalate-gel coprecipitation has a conversion of 40.8%,
which is much lower than that of the same composition
prepared by the template-assisted method. However, the BET
area of the material made by coprecipitation is 71 m2/g, and
that of the material made by the template method is 134 m2/g.
If one scales the conversion by the area, the solgel material
has better performance.
All Ni-doped catalysts are stable for 12 h on stream: neither
the conversion nor the selectivity change, and the meso-
structure of the catalyst is maintained. It is interesting that the
activity of the mesoscopic undoped CeO2 decreases due to
structural deterioration414 and doping with Ni suppresses or at
least slows this process.
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XRD measurements on Ni-doped ceria show no peaks
corresponding to NiO. The structure is that of the CeO2 with a
smaller lattice spacing (the ionic radius of Ni is smaller than
that of Ce).
H2-TPR measurements show a dramatic change upon doping
with Ni. For CeO2, the TPR signal (hydrogen consumption) is
very broad, while that for Ni-doped CeO2 has a sharp peak at a
much lower temperature. While we are not aware of any
calculations of Ni-doped ceria surfaces, all calculations in which
the dopant has a lower valence than the cation it replaces show
that the dopant makes the oxygen atoms in the surface more
reactive. This means that the dissociative adsorption of H2 and
the removal of water (with the creation of an oxygen vacancy)
are facilitated by the presence of the LVD. This is consistent
with the H2-TPR results.
The temperature programmed reaction of oxygen with the
Ni-doped ceria catalyst that spent 12 h on stream was
accompanied by TGA measurements. These show that no
carbon deposits were present on the catalyst. The reaction is
not catalyzed by carbon deposits, as has been sometimes
suggested.
Both Ce3+ and Ce4+ are observed in the XPS spectrum, and
this is consistent with a Marsvan Krevelen mechanism. The
hydrogen released by the hydrocarbon reacts with a surface
oxygen atom desorbing as water and leaving behind an oxygen
vacancy. Calculations show188,268 that an oxygen vacancy
formation is accompanied by the reduction of two Ce4+ ions
to Ce3+, and this will account for the presence of both ions in
the catalyst (after use).
As a rule, we expect that replacing Ce with a tetravalent
dopant does not have a dramatic eect on the energy of oxygen
vacancy formation or on the reactivity of the oxide. Calculations
on Zr-doped ceria229,255,334,362 show that the presence of Zr
makes it easier to make oxygen vacancies and make the oxygen
atoms near the dopant more reactive. If the rate-limiting step in
ODH is the breaking of a CH bond in ethylbenzene, then the
presence of Zr should improve the catalytic activity. This is not
what the experiments nd. However, if we normalize for
dierences in surface area, then Zr-doped ceria has roughly the
same activity as CeO2.
In general, the presence of an LVD, like Al, is expected to
make the surface a better oxidant. This is true, but Al overdoes
it: calculations by Nolan190 show that the formation of an
oxygen vacancy on the surface of Al-doped ceria is exothermic.
This means that the catalyst loses one oxygen atom next to the
dopant when it is heated. We are not aware of any calculations
that examine whether the oxygen atoms remaining on the
surface (after on O-vacancy has been made) are still activated
by the presence of Al. The acidbase rules proposed by us221
suggest that this will not be the case.
16. OXIDATIVE DEHYDROGENATION OF ETHANE TO
ETHYLENE
Ethylene is produced by steam cracking of naphtha, or light
petroleum products or natural gas rich in ethane.431 Early
contributions to steam cracking were made by Dubbs father
and son. In a moment of excessive enthusiasm for industrial
organic chemistry, Dubbs father named his son Carbon. One
would think that upon reaching maturity, the son might want to
change his name: he did and became Carbon Petroleum Dubbs.
His daughters were named Methyl and Ethyl.
More ethylene is produced in the world than any other
organic compound. The value of the product compensates for
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numerous shortcomings of the process: it is performed at high
temperature (850 C), it is endothermic and requires
prodigious amounts of heat, it produces signicant amounts
of CO2, it is economical only if the units are of enormous size,
the technology is complicated by a residence time of
milliseconds (the gas velocity exceeds the speed of sound),
and the composition of the products cannot always be adjusted
to track changes in the demand. These diculties stimulate the
need for new processes for ethylene production, such as
oxidative dehydrogenation with oxygen or CO2. Several reviews
of alkane ODH are available.7,432434
To be competitive with steam cracking, the oxidative
dehydrogenation of ethane to ethylene ought to have433 high
selectivity and productivity higher than 1.0 kg C2H4/gcat/h. The
best catalyst found so far is MoVTeNb oxide,435,436 which
achieves 87% conversion and 89% selectivity. We are not aware
of a commercial application of this catalyst.
We dedicate substantial space to ethane ODH on NiO or
doped NiO catalysts because they are the most extensively
studied doped-oxide catalysts for this reaction.126,127,437441
These articles provide information on ethane ODH catalysis by
undoped NiO and NiO doped with Li, Mg, Al, Ga, Ti, Zr, Ta,
and Nb. We have thus an opportunity to study, for one reaction
and one host oxide, how catalytic performance changes with the
dopant and the method of preparation of the catalyst. We do
not review here work442445 on undoped NiO supported on
other oxides; we are interested in undoped and unsupported
NiO for comparing it to unsupported, doped NiO.
17. BACKGROUND INFORMATION ON NiO
Nickel forms446 one stable oxide, NiO, which has the sodium
chloride structure. Ni2O3 exists, is a strong oxidant, and is much
less stable than NiO. The heat of formation of NiO is small,
and it should be a good oxidant as compared to most other
oxides. NiO prepared at 700 C is green and is stoichiometric;
we have not found any work that uses this oxide as a catalyst.
NiO prepared at 450 C is black, has Ni vacancies, and is a p-
conductor.58,447 The presence of a Ni vacancy creates
(formally) a decit of two electrons, which is equivalent to
two holes and is believed to be responsible for the p-
conductivity of the material.58,447 The two holes may be
localized on either two oxygen atoms or on two Ni
atoms.448,449 In a chemists language, the presence of a Ni
vacancy will create either O or Ni3+ ions. Density functional
theory has been used to examine Ni vacancies in the surface of
NiO. The diculties encountered by DFT in describing NiO
correctly have been discussed by Pacchioni and Illas.450,451 The
calculations on NiO (doped or undoped) that we report here
used PBE+U with the U recommended by Rohrbach et
al.452,453 Because of these uncertainties in the accuracy of DFT,
we only emphasize here the trends suggested by the
calculations.
Pacchionis calculations454 show that if a Ni vacancy is
present on the (100) surface of NiO, two holes are localized on
the oxygen atoms. However, NiO is particularly easy to
cleave159 along the (100) surface, and this suggests that this is
not a reactive face. For this reason, we have examined Ni
vacancies on the Ni(011) face. When a Ni vacancy is present on
the surface of NiO(011), the Fermi level shifts toward the top
of the valence band, which indicates that the vacancy is a p-
dopant, as expected. The empty orbitals at the top of the
valence band are localized on the oxygen atoms next to the Ni
vacancy. Therefore, formally the formation of a Ni vacancy at
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the surface results in the creation of two O ions. We note that
by creating two holes localized on the oxygen atoms, a Ni
vacancy is equivalent to an LVD. This means that the surface
having a Ni vacancy is a strong Lewis acid and is a better
oxidant than NiO that has no Ni vacancies. As in the case of all
LVDs, it is possible that the presence of a Lewis base (e.g., H or
C2H5) on the surface will compensate the eect of the Ni
vacancy.145,221 In particular, it is reasonable to expect that H
binds to the two O atoms near the Ni vacancy to form two
hydroxyls. We know no experimental evidence for or against
this possibility.
18. ETHANE OXIDATIVE DEHYDROGENATION WITH
OXYGEN CATALYZED BY Zr-DOPED NiO
Wu et al.126 have prepared Zr-doped NiO and undoped NiO by
a solgel method. Citric acid was added slowly to an aqueous
solution of Ni(NO3)26H2O and Zr(NO3)45H2O. The solvent
was evaporated at 70 C until a gel was formed. This was dried
at 120 C for 24 h and then calcined in air at 450 C for 6 h.
Pure ZrO2 was not tested, but it is unlikely that it will catalyze
ethane ODH at the temperature used in this work (T 400
C). The amount of precursors was chosen so that the molar
ratio 100 Zr/(Zr+Ni) was equal to 5, 10, 20, 40, and 75.
The XRD measurements found that 5Zr and 10Zr have the
structure of NiO. The notation 5Zr indicates Zr-doped NiO
with the molar ratio 100 Zr/(Zr + Ni) = 5. The lattice
parameter of NiO increased with the addition of Zr, whose
ionic radius (0.72 ) is larger than that of Ni (0.69 ). No
ZrO2 diraction pattern was observed for Zr molar fractions
less or equal to 10%. These results suggest that a Zr-doped NiO
has been prepared when the dopant concentration is less or
equal to 10%. In the XRD of 20Zr, one can see ZrO2 diraction
peaks. Because the catalytic activity of 20Zr is essentially the
same as that of 10Zr, we suggest that 20Zr consists of a Zr-
doped NiO phase (rather than an undoped NiO phase) and a
ZrO2 phase.
The NiO prepared by the solgel method mentioned above
has a high specic area of 90 m2/g. Doping with Zr increases
the specic area to 122 m2/g (for 5ZrNiO) and 170 m2/g (for
10ZrNiO). Later in this section, we show that the catalytic
activity of undoped NiO depends strongly on the method of
preparation.126,438,440,441
Reactivity experiments were performed126 at temperatures
between 250 and 450 C. The feed was a mixture of ethane,
oxygen, and nitrogen (C2H6/O2/N2 = 1/1/8) with a space
velocity of 30 000 mL/hgcat. NiO starts converting ethane126 at
275 C, and between 270 and 350 C, it converts more
ethane than any of the Zr-doped catalysts. The ethylene yield
on NiO at 350 C is 23% with ethylene selectivity of 47%; CO2
and ethylene were the only products. Unfortunately, at
temperatures above 350 C, the selectivity for ethylene is
rapidly and completely lost. One suspects that the oxide also
deactivates at lower temperatures, but it does so more slowly.
The performance of the NiO and ZrNiO catalysts can be
best judged from a plot (Figure 8) of selectivity to C2H4 versus
ethane conversion.126 A point in the graph gives the conversion
and the selectivity at a given temperature. Dierent points
correspond to dierent temperatures. The conversion increases
with temperature (up to 400 C). At any given conversion, the
ethylene selectivities of 5ZrNiO, 10ZrNiO, and 20ZrNiO are
close to each other and substantially higher than that of NiO.
For example, at a 50% ethane conversion the ethylene
selectivity of NiO is 47%, while that of 10ZrNiO is 66%.
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Figure 8. Ethylene selectivity as a function of ethane conversion for
dierent concentrations of the Zr dopant in NiO. Reprinted with
permission from ref 126. Copyright 2012 Elsevier.
It is clear that doping improves the selectivity and therefore the
overall performance for ethane ODH. The best performance
was obtained for 10ZrNiO at 430 C with an ethylene yield of
40% and an ethylene selectivity of 66%.
While 5ZrNiO and 10ZrNiO consist of one phase with the
NiO structure, 20ZrNiO consists of a phase with NiO structure
and a second phase which is ZrO2. It appears that the phase
with NiO structure, in this two-phase 20ZrNiO system, is a
doped nickel oxide because the activity of 20ZrNiO is very
close to that of 10ZrNiO (which consists of one phase with
NiO structure) and because a mixture of NiO and ZrO2 has the
same activity126 as NiO, which indicates a lack of synergy
between NiO and ZrO2.
Zr-doped NiO behaves as calculations lead us to expect from
an irreducible oxide doped with a high-valence dopant. Doping
with Zr improves the selectivity to ethylene substantially, makes
the oxide less reducible, and binds surface oxygen more
strongly to the oxide, just as the calculations predict. We are
not aware of any calculations on Zr-doped NiO. However, on
the basis of calculations on similar systems (e.g., high-valence
dopants (HVDs) in irreducible oxides), we expect the
following. Because the only stable oxide of zirconium is
ZrO2, Zr is a high-valence dopant (in NiO) and will act as a
strong Lewis base. This can aect the system in several ways.
Because NiO has a tendency to have Ni vacancies, they may be
present even though we doped the oxide. In the absence of Zr,
these Ni vacancies make NiO a better oxidant, and some
authors assume that this is why NiO is an eective alkane
combustion catalyst. A Zr dopant, which is a strong Lewis base,
is very likely to transfer electrons to the electronholes
associated with the Ni vacancies. Put in another way, Zr will
transfer electrons to the O centers created when the Ni
vacancy was formed, converting it to O2. Thus, the presence of
Zr is likely to decrease ethane oxidation.
In addition to diminishing the reactivity caused by the Ni
vacancies, Zr will increase the binding energy of the
neighboring oxygen atoms to the oxide surface. This is
equivalent to making these oxygen atoms less reactive.
Temperature programmed hydrogen reduction126 experiments
support this suggestion. Doping with even a small amount of Zr
increases substantially the temperature at which hydrogen
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Chemical Reviews
consumption by the oxide begins. Therefore, if the rate-limiting
step in ethane ODH is the dissociative adsorption of ethane, to
make a hydroxyl and an ethoxide with the oxygen atoms on the
surface (Mars-van Krevelen mechanism), the presence of Zr
should make this reaction more dicult. This is not necessarily
bad, because Zr will also limit the reactivity of the doped oxide
with ethylene: a loss in conversion may be a gain in selectivity.
Our ability to anticipate the mechanism without detailed
calculations on this specic system is diminished by the fact
that the Marsvan Krevelen mechanism is not the only
possibility. As we have already explained, high-valence dopant
adsorbs O2 from the gas phase. If the binding energy of the O2
to the dopant is not very large, the adsorbed O2 is reactive and
can break the CH bond in an alkane. We are not aware of any
calculation in which this possibility has been examined for Zr-
doped NiO. Experiments with 18O2 are sometimes able to
distinguish which of these two mechanisms is operative (i.e.,
reaction with O2 adsorbed on Zr or reaction with surface O),
but they have not been performed for this system. Experiments
on hydrogen TPR and oxygen desorption from NiO and Zr-
doped NiO are of help. They show that doping with Zr makes
the oxide less able to consume hydrogen or to release oxygen.
This suggests that Zr acts as a typical high-valence dopant
(without O2 adsorbed on it).
19. ETHANE OXIDATIVE DEHYDROGENATION TO
ETHYLENE CATALYZED BY Nb-DOPED NiO
19.1. Background Information about Nb and Its Oxides
We are interested in the oxides formed by Nb because they may
allow us to guess some of the chemical properties of the Nb
dopant. Niobium is a exible atom when it combines with
oxygen. It makes three stable oxides, Nb2O5, NbO2, and NbO,
as well as compounds with the stoichiometry Nb3n+1O8n2 with
5 n 8. Among these oxides, Nb2O5 has the highest energy
of formation, and it is very unreactive. NbO has the lowest heat
of formation (406 kJ/mol) and is a stable oxide. It has a
sodium chloride structure, just like NiO, except that 25% of the
NaCl lattice sites are unoccupied; occasionally the formula
Ni0.75O0.75 is used to draw attention to this fact. In binding to
oxygen Nb prefers the oxidation state +5 if enough oxygen is
available. However, when Nb is a substitutional dopant in
another oxide, its oxidation state is likely to depend on its
immediate environment. It is therefore dicult to guess a priori
the oxidation state of a Nb atom that substitutes a Ni atom in
the surface layer.
19.2. Computational Results on Nb-Doped NiO
Among all rocksalt oxides, NiO is most easily cleaved along the
(100) plane.159 This suggests that the (100) plane is likely to be
the least reactive face of the oxide, and this is what the
calculations nd. Therefore, we report here only results for the
Nb-doped NiO(011). The Nb dopant has ve valence electrons
and when it substitutes a divalent cation (such as Ni in NiO)
three of its electrons that are not tied up in chemical bonds.
These unused electrons make the dopant a strong Lewis base.
According to the rules we proposed, as a result of calculations
on a variety of systems,141,142,145,221,262,271 a high-valence
dopant in an irreducible oxide will increase the binding of
neighboring surface oxygen atoms to the oxide, and this will
hinder oxidation by a Marsvan Krevelen mechanism.
However, in the presence of oxygen in the gas phase, which
is always the case in an ODH reaction, the behavior of the
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system is complex. Calculations on a variety of systems show
three possible scenarios.
(a) A high-valence dopant may adsorb O2 from the gas phase
and it may activate it.359 Ethane may react dissociatively
with the adsorbed O2 to make an ethoxide and a
hydroxyl. We rule out this mechanism for Nb-doped
NiO(011) because our calculations nd that the
adsorption energy of O2 on top of the Nb dopant is
8.40 eV. The distance between the two oxygen atoms is
much longer than any reasonable O2 bond length, and
therefore the NbO2 group contains two O atoms (not a
weakened O2 molecule). The adsorbed oxygen atoms
are so strongly bound to Nb they cannot possibly be
involved in the ODH reaction (Sabatier principle).
(b) Because O2 binds so strongly to Nb and the O atoms are
unreactive, it seems reasonable to consider that the
dopant is NbO2. This changes the formal electron
counting. If we assume that the formal charge on each O
adsorbed on Nb is 2, then binding two oxygen atoms
from the gas phase uses four of the Nb electrons and
only one is left for making bonds with the oxide.
Therefore, NbO2 should be viewed as a low-valence
dopant similar to an alkali or a Ag atom. We have used
calculations to test this hypothesis: if NbO2 is an LVD,
then its presence will lower the energy of oxygen-vacancy
formation at a neighboring oxygen site. DFT calculations
in our group show that the presence of the NbO2 dopant
lowers the energy of oxygen-vacancy formation in the top
layer of the doped NiO(011): this energy is 3.28 eV for
the undoped Ni(011), and it is 2.31 or 2.67 eV for the
NiO(011) doped with NbO2 (depending on the position
of the removed oxygen with respect to the Nb site). This
is comparable to the value of 2.65 eV we obtained when
the dopant is Li, and it is typical behavior for a low-
valence dopant. We also know that the presence of an
LVD in the surface of an oxide lowers the energy of
dissociative adsorption of an alkane (see section 9.3).
Our calculations nd that this is the case for ethane
dissociative adsorption on NiO(011) doped with NbO2.
The activation energy for breaking the CH bond is low
enough to explain why this system activates ethane. We
would have suggested this mechanism for breaking of the
CH bond (the rate-limiting step in ODH), except for
the next possible scenario.
(c) Nb has a high anity for oxygen and a propensity to
make compounds in which it is pentavalent. Because of
this, we investigated whether in contact with a gas-phase
oxygen the dopant may come out of the Ni lattice site
and form an oxide cluster on top of the surface. Our
calculations show that when the doped surface is exposed
to oxygen, the NbO2 cluster gains energy by reacting
with 1/2O2 and forming the NbO3 cluster shown in
Figure 9. In this nal state, there is a NbO3 cluster on the
surface (bound to the oxygen atoms on the surface of
NiO) and a Ni vacancy in the surface layer. This is likely
to happen with other high-valence dopants whose oxides
are very stable, when they substitute lower valence
cations in a less stable host oxide. When doped oxides are
prepared, it is common to calcine them at temperatures
around 450 C for 4 or 5 h in the presence of oxygen. It
is possible that Nb atoms are mobile at these
temperatures and have enough time to reach the surface,
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Chemical Reviews
Figure 9. In the presence of oxygen, the Nb dopant (light purple) is
pulled out of the Ni lattice site (the circle) to form a NbO3 cluster,
where the three oxygen atoms (blue) are from the gas phase. The Ni
atoms in the top layer are green, and the ones in the second layer are
cyan. The oxygen atoms in the top surface layer are red, and the ones
in the second layer are yellow.
react with the gas-phase oxygen, and form Nb oxide
clusters or perhaps a Ni niobate (our calculations have
not explored the latter possibility). The properties of the
structure shown in Figure 9 have not been adequately
explored.
It is well-known8,9 that submonolayers of an oxide A (a
generic name) supported on an oxide B (another generic
name) are often better catalysts than the bulk oxide A or bulk
oxide B. In an important experiment, Millet et al.441 have
prepared, by an impregnation method (see below), submono-
layers of NbOx supported on NiO. The activity of this catalyst
is less than that of the samples that were prepared with the
intention of making doped oxides. One infers that small NbOx
clusters supported on NiO are not as active as Nb-doped NiO.
However, this does not rule out the presence of a Nb-rich phase
in Nb-doped NiO. While attempting to prepare doped oxides,
Heracleous and Lemonidou439 found that besides a phase with
NiO structure, a second phase is present that is amorphous and
has an excess of Nb (determined by EDS microscopy). They
believe that this phase is a precursor to the formation of
NiNb2O6. Millet et al.441 found that some Nb0.15Ni0.85O seems
to be embedded in Nb2O5. Caps440 saw regions with high Nb
concentration in EDS and showed that NiNb2O6 is present.
These ndings agree qualitatively with the suggestion made by
calculations that in the presence of oxygen some of the Nb
substitutional dopant will segregate to the surface and be
oxidized. The kinetics of this segregation is likely to be slow and
might explain why some of the Nb-doped catalysts lose activity
in time.
19.3. The Preparation of NiO and Nb-Doped NiO
Experiments have found that the catalytic activity of NiO and
Nb-doped NiO depends substantially on the method of
preparation. It is not clear whether such dierences persist
for a long time: one might think that under steady-state
reaction conditions catalysts prepared dierently, but having
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Review
the same elemental content, are likely to evolve and end up
having the same structure and surface composition.
Wu et al.455 prepared NiO by a solgel method, a
precipitation method, a microemulsion method, and by solid-
state milling.
Heracleous and Lemonidou438 dissolved Ni(NO3)26H2O
and ammonium niobium oxalate in water by stirring and
heating at 70 C for 1 h. The solvent was then evaporated and
the solid dried and calcined in synthetic air at 450 C for 5 h.
The pure NiO was obtained by the same procedure, in the
absence of the Nb precursor.
Caps and co-workers440 prepared NiO by three methods and
showed that their solgel method provides the best NiO
catalyst for ethane ODH, which is consistent with the results of
Wu et al.455 Therefore, they prepared the Nb-doped NiO by
the same solgel method. In this procedure, NbCl5 was added
to water, which caused the formation of a Nb2O5nH2O
precipitate. This was washed to remove the chloride. After that,
the precipitate was dissolved in a warm citric acid solution, and
Ni(NO3)26H2O was added to it. The gel was slowly dried in
several steps440 and then calcined at 450 C for 4 h in air.
Millet et al.441 prepared Nb-doped NiO by using the oxalate-
based method developed in Lemonidous group (see above).456
Three other preparations used various amounts of oxalic acid
(because the precursor for Nb is an oxalate) to test whether the
amount of oxalate matters. The preparation having the most
oxalic acid had the highest catalytic activity, and, in what
follows, we discuss only the activity of this NiO sample from
Millets group.
19.4. Catalytic Performance of NiO for ODH of Ethane to
Ethylene
There are no widely accepted methods for ranking catalysts
even when we disregard some of the practical factors such as
heat management, equipment cost, and separation cost.
Because conversion and selectivity are very important, we
compare the ODH catalysts based on the conversion of C2H6
and the yield of ethene (the percent of the converted ethane
that produces ethene). Physical chemists may prefer to use
conversion per unit area (which we use here occasionally) or
even the elusive turnover frequency.
A comparison between the results of Millet441 and Caps440 is
made in Table 3. In addition, we note the results of Wu et al.455
who give only the ethylene yield but not the conversion. They
found that the ethylene yield is highest for the NiO prepared by
a solgel method (15%), decreases to 8% for the one
prepared by the precipitation method, and decreases further for
the one prepared by a microemulsion method (3%). The
specic area of the solgel sample, which had the highest
Table 3. A Comparison of Results Obtained for Ethane
ODH Catalyzed by NiO and Nb-Doped NiOa
% yield % conversion
441 440
catalyst Millet Caps Millet441 Caps440
NiO 3.7 24 12 42
Nb0.03 15 25 22 41
Nb0.15 26 14 33 19
Nb0.20 8
a
The temperature is 350 C, the ethane to oxygen ratio is 1:1, and W/
F = 0.6 g s/mL for Caps and 0.54 g/s mL for Millet. The subscript x
in Nbx indicates the atomic fraction of Nb in the Nb-doped NiO
catalyst.
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ethylene yield, was much smaller than the area of the other
samples.
The NiO prepared by Caps gives a substantially higher
ethane conversion and ethylene yield than that prepared by
Millet or Wu. The NiO prepared by Lemonidou has 80% CO2
selectivity439 (the ethylene yield on NiO is not reported in their
paper but it is likely to be the same as in Millets work who used
the same method of preparation), so one should think of it as
more of a combustion catalyst than an ODH catalyst.
This comparison shows that both conversion and selectivity
in the catalytic oxidation of ethane on a NiO catalyst depend on
the way in which the catalyst was prepared. The dierence is
both qualitative and quantitative: in one preparation, NiO is a
fair catalyst for ethylene production, while in another, it
combusts ethane.
19.5. Catalytic Performance of Nb-Doped NiO for Ethane
ODH
In Millets experiments, adding a very small amount of Nb (to
make Nb0.03Ni0.97O) improves dramatically both the ethane
conversion and the ethylene yield as compared to the
performance of NiO (see Table 3). However, such a small
amount of Nb makes no dierence in the experiments reported
by Caps. Increasing the amount of Nb to make Nb0.15Ni0.85O
increases ethane conversion and ethylene yield in the case of
Millet and decreases them for the catalyst made by Caps. These
are qualitative dierences: in Millets experiments, doping with
Nb improves the performance, while in Capss experiment it
decreases it; the method of catalyst preparation is clearly
important.
Lemonidous experiments438 for Nb0.15Ni0.85O at T = 350 C,
C2H6/O2 = 1/1, and W/F = 0.54 g s/cm3 (the W/F is the same
as Millets and slightly dierent from Capss 0.6 g/s cm3) give
an ethylene selectivity of 81% and an ethane conversion of 35%,
which corresponds to a yield of 28%. This is close to Millets
results but dierent from those of Caps. Because Millet used
the same method of synthesis as Lemonidou, we expect their
results to be very similar.
There are some data at 400 C that show dierences between
Nb0.15Ni0.85O prepared by Caps440and that prepared by
Lemonidou.127,437439 Millet did not publish data at this
temperature. The conversions are 25% (Caps) and 65%
(Lemonidou), and the selectivities are 74% (Caps) and 66%
(Lemonidou).
19.6. NbOx Clusters Supported on NiO
Millet et al.441 performed an important experiment, which
should become standard in research on catalysis by doped
oxides. Our calculations suggest that, in the presence of oxygen
in the gas phase, Nb is likely to segregate and make niobium
oxide clusters on the NiO surface. The binding energy in the
XPS spectrum of Nb atom in the material will be dierent from
that of Nb in Nb2O5 for any of the following: for NbOx
supported on NiO, for the substitutional Nb dopant in the
surface of NiO, or for NbO2 that substitutes a Ni atom in the
surface. Therefore, the shift in the XPS spectrum cannot be
used to distinguish between these three possibilities. When
physical methods give ambiguous results, it is often useful to
appeal to chemistry. Millet et al.441 prepared NbOx clusters
supported on NiO and tested the catalytic activity of this
material for ethane ODH.
The supported NbOx clusters were prepared by impregna-
tion of a NiO powder prepared by the oxalate method. This
NiO sample (with no Nb) is active for ODH and gives 23%
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conversion and 39% selectivity (9% yield). A suspension of this
NiO oxide powder in a solution of ammonium niobium oxalate
was stirred at room temperature for an hour, then the water was
evaporated at 70 C and the powder left behind was calcined in
air, for 5 h, at 450 C. We denote the resulting compound by
NbOx/NiO. This catalyzes ethylene formation with an ethane
conversion of 32% and a selectivity of 40%. NbOx/NiO is more
active than the NiO support, but it is less active than
Nb0.15Ni0.85O, or Nb0.07Ni0.93O, which are believed to be
doped oxides. This does not rule out that when doped oxides
are made some NbOx is formed on the surface, but indicates
that it is unlikely that all or most of the Nb is in this form.
19.7. Long-Term Stability of the Nb-Doped NiO Catalyst
Lemonidou438 found that Nb0.15Ni0.85O is stable on stream for
20 h at 350 C. The conversion of the doped catalyst prepared
by Caps440 drops slowly and steadily for 70 h, while selectivity
increases. The change is most rapid in the rst 5 h. Millet441
performed more extensive stability studies and found that at a
temperature of 380 C the conversion of ethane on
Nb0.15Ni0.85O drops from 58% to 35% after 325 h on stream,
while selectivity increases from 67% to 78%. The degradation
of the catalyst is not due to coking because heating the
degraded catalyst to 450 C in air, for 30 min, and then using it
again as a catalyst at 380 C, did not restore its performance.
Nor is the degradation caused by coarsening becauase the area
did not change substantially. One possible explanation439 for
deactivation is the formation of NiNb2O6.
19.8. The Inuence of Doping and of the Method of
Preparation on Surface Area per Gram
We have compared the performance of NiO and the Nb-doped
NiO catalysts prepared by various methods without taking into
account their specic area. It is often preferable to know the
conversion per unit area rather than the conversion per gram of
catalyst. The specic area of the NiO is 9.4 m2/g for
Lemonidou catalyst and 90 m2/g for that of Wu. The specic
areas of the other NiO preparations mentioned here are
between these values. Because of this, it is important to note
that the area depends strongly on the method of preparation.
As we have already pointed out, these preparations have very
dierent catalytic activity. A possible reason for this is that the
smaller particles are likely to have more defects (steps, kinks,
etc.), and these are chemically active.
NiO doped with Nb or Zr has a much larger specic area
than undoped NiO. The specic area increases with the amount
of Nb, as long as Nb concentration does not exceed 20%. For
example, the area in m2/g is 16.7 for NiO, 55.9 for
Ni0.9Nb0.01O, and 85.1 for Ni0.85Nb0.15O. This is often the
case: a doped oxide has a substantially larger specic area than
the host oxide prepared by the same method. There are
however exceptions to this rule.96
19.9. Chemical Characterization of Nb-Doped NiO
Temperature programmed reduction with H2 shows that
doping with Nb reduces the hydrogen uptake.438,440,441
Temperature programmed desorption shows that less oxygen
is released from the Nb-doped NiO than from the undoped
NiO. These observations are consistent with the fact that Nb is
a high-valence dopant that reduces the reactivity of surface
oxygen and increases the energy of oxygen-vacancy formation.
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Chemical Reviews
19.10. Ethane ODH by NiO Doped with Li, Mg, Al, Ga, Ti, Ta,
or Nb
Heracelous and Lemonidou127 prepared NiO doped with Li,
Mg, Al, Ga, Ti, and Nb. These dopants were chosen because
their ionic radius is similar to that of Ni and their valence in
their stable oxides varies from one to ve. All doped oxides
were prepared under identical conditions, and all had the same
nominal dopant to Ni ratio of 0.176 (the stoichiometry is
Me0.15Ni0.85O, where Me stands for the dopant). The
precursors for the dopants were nitrates, and the preparation
was the same as in the early work of Lemonidou.438
The ODH of ethane was investigated in the temperature
range from 300 to 425 C, with a W/F ratio of 0.54 g s/cm3
and a feed containing 9.1% ethane, 9.1% O2, and 81.8% He.
Ethane conversion, per gram of catalyst, decreased in the order:
NbNi MgNi > LiNi > GaNi = NiO AlNi
TiNi TaNi
Here, the symbol MeNi (where Me is the dopant) stands for
Me0.15Ni0.85O. According to this metric, NiO doped with Nb is
the most ecient catalyst for breaking the CH bond in
ethane. Of course, it is dicult to judge the quality of a catalyst
by using one simple metric. Selectivity is also of paramount
importance, and we will examine this later. It seems reasonable,
however, to examine ethane conversion per unit area because
there are large dierences in the surface areas per gram between
various doped NiO catalysts. The BET measurements of the
specic area give (in units of m2/g) 16.7 for NiO, 85.1 for
NbNi, 7.6 for LiNi, 19.2 for MgNi, 67.8 for AlNi, 45.3 for
GaNi, 18.6 for TiNi, and 78.9 for TaNi. With the exception of
Li-doped NiO, all doped oxides have larger specic area than
NiO. If we normalize the conversion to surface area per gram,
the order of the eciency of the catalysts for ethane activation
(conversion per area) changes to
LiNi (0.139) MgNi (0.055) NiO (0.049)
> NbNi (0.028) > GaNi (0.018) = TiNi (0.017)
AlNi (0.011) TaNi (0.0004)
The numbers in parentheses are g of C2H6 consumed per m2
per second.On the basis of these results, Li-doped NiO is by far
the catalyst most able to break the CH bond.
To assess the reactivity of the oxygen atoms in the surface of
doped and undoped NiO, we have calculated the energy of
oxygen vacancy formation in the surface layer. For NiO(011),
we obtained 3.28 eV. The energies to make an oxygen vacancy
in the surface layer of a doped oxide, near the dopant, are 2.65
eV for Li, 2.74 eV for Mg, 4.6 eV for Al, 4.25 eV for Ti, and
4.13 for Nb. The reliability of these numerical values is not
certain, and therefore we concentrate on trends. In general, a
low-valence dopant will decrease the energy of vacancy
formation, and this is what we see for Li-doped NiO. Mg has
the same valence as Ni, and its ionic radius is comparable to
that of Ni, and we expect it to have a small eect on Ev, which
is the case. Al, Ti, and Nb are high-valence dopants, and they
increase the energy of vacancy formation. The values of these
energies of oxygen-vacancy formation suggest that doping with
Li and Mg will activate the oxide and it will convert more
ethane than NiO. This is what the experiments found. The
calculations suggest that the high-valence dopants Al, Ti, and
Nb will make the doped surface less active than NiO, for the
4419
Review
Marsvan Krevelen mechanism. However, we are left with the
possibility that O2 adsorbs on the dopant and ethane reacts
with it. There are no calculations regarding this possibility.
The amount of desorbed oxygen from various samples is also
qualitatively consistent with the calculations. Li-doped NiO
releases the largest amount of oxygen (per gram of catalyst),
while the catalysts containing Al, Ga, Ti, Ta, or Nb release less
(as predicted by calculations).
The XRD measurements nd that all samples contain a phase
with the NiO structure with slightly shifted lattice constant.
This is taken to signify that all samples consist of doped NiO.
However, this is not always the only phase present. Anatase is
observed in Ti-doped NiO, a phase tentatively assigned to
NiTa2O6 is seen in the Ta-doped NiO, and either a Nb-rich
phase or a NiNb2O6 phase is seen in the Nb-doped NiO
sample. It is not clear how these phases aect catalytic
performance. This presents us with additional complications
when we compare the behavior of the doped NiO with the
results of exploratory calculations.
19.11. Ethane ODH on Doped NiO: Conclusions
This detailed examination of ethane ODH by doped NiO
illustrates the diculties encountered by both theory and
experiments when studying catalysis by doped oxides. It is
impossible at this time to construct realistic models of the
catalytic surface, and we are limited, in both computations and
experiments, to making educated guesses. However, several
broad conclusions can be reached. The trends predicted by
computations compare fairly well with the experimental
observations. The distinction between the eect of high- and
low-valence dopants, so prevalent in calculations, is observed in
experiments. The computed trends in the ability of a doped
oxide to break the CH bond are in agreement with the
observations and so are the trends in reducibility (whether
measured by H2-TPR or oxygen thermal desorption). The
strong dependence on the method of preparation is a surprise.
It might appear that this provides an additional parameter in
the optimization of the catalyst. However, it is not clear
whether this dependence on the method of preparation is of
practical importance: after several days on stream, various
morphologies, generated by dierent methods of preparation,
may evolve into the same steady-state morphology. It is
therefore important, for this and other reasons, to perform long
time experiments. The dependence on the method of
preparation points to a shortcoming of the computations:
there is practically no computational work in which surface
morphology is systematically varied and its inuence on the
ability to break the CH bond is studied. Such calculations are
possible and should be performed.
20. BRIEF CONCLUDING REMARKS
Catalysis by doped oxides is an emerging eld, which is still
awaiting consolidation and rationalization. The number of
possible oxidedopant pairs is large, and none has been studied
exhaustively by a combination of computations and experi-
ments. Much more work is needed before we can form a clear
picture of the eects of doping and of its utility.
The characterization methods are unable to prove beyond
doubt that the method of synthesis has produced a substitu-
tionally doped oxide with the dopant imbedded in the surface
layer. At this time, and for some time in the future, we have to
rely on circumstantial evidence. We have no experimental
methods that will tell us the morphology and the composition
dx.doi.org/10.1021/cr300418s | Chem. Rev. 2013, 113, 43914427
Chemical Reviews Review

of the surface at an atomic level, under reaction conditions. Biographies

Because of this, the models used in computations are
approximate. To bridge this model gap, we need to perform
calculations of catalysis on surfaces having a variety of defects
to obtain an estimate of their importance. Experiments on
model systems that resemble more closely the models used in
the calculations, such as those developed by Freund,1014,249
for example, will also be very helpful. Furthermore, it is
necessary to perform experiments specically designed to test
the predicted trends, which has not been done so far.
Because of these uncertainties, one should use computations,
at this time, mainly to obtain qualitative trends and design rules.
The most important question is: does doping improve the
catalytic activity of an oxide? With a few exceptions, both
computations and experiments answer yes. In most cases, Eric McFarland studied Nuclear Engineering at the University of
doping improved the catalytic performance, as compared to the California, Berkeley. After obtaining a Ph.D. from MIT and an M.D.
from Harvard Medical School, McFarland joined the MIT Nuclear
undoped host oxide, by increasing the conversion, or the
Engineering faculty. In 1991, he moved to the University of California,
selectivity, or the area per gram of catalyst. Despite such Santa Barbara where he is a Professor of Chemical Engineering.
improvements, we are not aware of any example where a McFarland works closely with industry on problems related to fuel
deliberate doping of an oxide leads to a commercial catalyst. A production. His recent research interests focus on heterogeneous and
second question is: Are computations helpful in our search for photoelectrochemical catalytic processes and production of fuels and
better doped-oxide catalysts? So far they helped us divide chemicals from light alkanes.
oxidedopant pairs into classes based on commonality in the
calculated chemical behavior. They have explained some
aspects of surface chemistry on the basis of strong interaction
between Lewis acids and bases. They are likely to be useful in
prospecting for promising dopantoxide pair catalysts, if it is
understood that they provide probable behavior rather than
absolute answers. The best we can hope, at this time, is to
derive qualitative design rules that will allow us to guess a priori
which doped-oxide systems are most promising catalysts for
each specic reaction. The work performed so far is incomplete,
fragmented, and exploratory, but the results obtained are
promising and much remains to be done. There is also no
reason to conne doping to the binary oxides examined here.
Horia Metiu graduated from the Chemical Engineering Department of
Doped perovskites have shown interesting catalytic proper- the Polytechnic Institute in Bucharest in 1961, received his Ph.D. in
ties.108,135,457490 MoS2 doped with Co or Ni is an industrial theoretical chemistry from MIT, in 1974 working with John Ross and
catalyst for oil hydrotreating.6,491,492 One can also imagine Robert Silbey, and then was a postdoctoral fellow at the University of
doping halide catalysts used, for example, in oxichlorination Chicago with Karl Freed. He has been a professor in the Department
reactions,3 or any other inorganic material that has catalytic of Chemistry at the University of California, Santa Barbara since 1976.
activity (e.g., vanadates, molybdates, nitrides, carbides). Finally, In the past, he performed theoretical work on surface-enhanced
spectroscopy, nonadiabatic processes at surfaces, correlation-function
one can imagine using anion doping such as replacing some theory of rate constants, quantum dynamics with Gaussian wave-
oxygen in an oxide with a halogen, or sulfur, etc. Finally, we packets, spectroscopy in time domain, femtochemistry, genetic
note that doping is starting to be used in electrochemistry programming, crystal growth, thermoelectric materials, and polymeric
where doped oxides and doped suldes have been explored as membranes for fuel cells. He has also performed experimental work on
electrocatalysts493495 and in surface photochemistry where Penning spectroscopy of adsorbates, polymeric membranes for fuel
doping can change the absorption spectrum and the catalytic cells, and mass selected clusters on surfaces. He is currently involved in
experimental and computational investigations of catalysis and
properties.54
electrocatalysis.

AUTHOR INFORMATION ACKNOWLEDGMENTS

Corresponding Author We are grateful to numerous students and postdocs with whom
*E-mail: metiu@chem.ucsb.edu. we have collaborated while working on doped oxide catalysts:
Steeve Chretien, Alan Derk, Zhenpeng Hu, Bo Li, Lauren
Notes
Misch, Raj Pala, Vladimir Shapovalov, Sudhanshu Sharma,
The authors declare no competing nancial interest. XiaoYing Sun, and Wei Tang, and to Professors Galen Stucky
4420 dx.doi.org/10.1021/cr300418s | Chem. Rev. 2013, 113, 43914427
Chemical Reviews
and Ram Seshadri. We are grateful for numerous and useful
discussions with Matthias Scheer and Jens Nrskov. Funding
was provided by the Air Force Oce of Scientic Research
(FA9550-09-1-0333), the U.S. Department of Energy (DE-
FG02-89ER140048), the University of California Lab Fees
Program (09-LR-08-116809), and by the National Science
Foundation through TeraGrid resources provided by Ranger@
TACC under grant number TG-ASC090080. We acknowledge
support from the Center for Scientic Computing at the
California NanoSystems Institute and the UCSB Materials
Research Laboratory: an NSF MRSEC (DMR-1121053) and
NSF CNS-0960316 and Hewlett-Packard. Use of the Center
for Nanoscale Materials was supported by the U.S. Department
of Energy, Oce of Science, Oce of Basic Energy Sciences,
under Contract No. DE-AC02-06CH11357.
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