DOI: 10.1002/ente.

201500343

Recent Advances in the Synthesis of Layered, Double-

Hydroxide-Based Materials and Their Applications in
Hydrogen and Oxygen Evolution
Kai Yan,*[a] Guosheng Wu,[b] and Wei Jin[c]

Layered double hydroxides (LDHs) consist of brucite-like
layers containing hydroxides of two or more different kinds
of metal cations. These positively charged layers are neutral-
ized by exchangeable anions in the interlayer galleries. LDH-
based materials have substantial potential in efficient energy
(e.g., H2, O2) generation. Over the last few decades, tremen-
dous progress has been made toward developing LDH-based
materials for H2 and O2 evolution, for which the per-
formance of LDH-based materials is closely related to the
synthesis method. This minireview initially outlines the
recent advances in the synthesis of LDH-based materials.
The advantages and challenges of the protocols in tuning the
properties of the material are also discussed and highlighted.
The application section concentrates on the most recent
progress in photocatalytic H2 generation and photocatalytic
and electrocatalytic O2 evolution. By taking advantage of the
flexible tunability and uniform distribution of metal cations
in the brucite-like layers or the intercalated anions in the in-
terlayer space, LDH-based materials exhibit attractive prop-
erties in the generation of H2 and O2 with advantages such as
improved light absorption, enhanced charge separation,
better electron transfer, promoted electrode reaction kinet-
ics, and high durability.

1. Introduction

With the rapid depletion of fossil fuels and environmental Table 1. Some naturally occurring hydrotalcite-like compounds.[8, 9]
issues, the development of renewable energies based on suffi-
cient energy sources with sustainable supply for the long Name Cation Anion
term in large quantity is in high demand.[1–7] The conversion hydrotalcite 2+
Mg , Al 3+
CO32¢
of solar energy through water-splitting processes into chemi- manasseite Mg2 + , Al3 + CO32¢
cal energy (e.g., H2 and O2) is considered a promising strat- meixnerite Mg2 + , Al3 + OH¢
motukoreaite Mg2 + , Al3 + SO42¢
egy to solve the energy and environmental problems in the pyroaurite Mg2 + , Fe3 + CO32¢
near future.[6, 7] Owing to their unique and attractive proper- sjogrenite Mg2 + , Fe3 + CO32¢
ties, layered double hydroxide (LDH)-based materials have igelstromite Mg2 + , Fe3 + OH¢
garnered much attention for the clean and efficient genera- stichtite Mg2 + , Cr3 + CO32¢
barbertonite Mg2 + , Cr3 + CO32¢
tion of H2 and O2. During the past several decades, a number takovite Ni2 + , Al3 + CO32¢
of research activities centered on developing robust LDH- carboydite Ni2 + , Al3 + SO42¢
based materials for the purpose of trying to improve their reevessite Ni2 + , Fe3 + CO32¢
performances in water splitting have been envisioned. honessite Ni2 + , Fe3 + SO42¢
wermlandite Mg2 + , Fe3 + , Al3 + SO42¢, CO32¢
LDHs (also named hydrotalcite-like compounds) are coalingite Mg2 + , Fe3 + CO32¢
a family of 2 D clay materials having special structural and
compositional features with the general formula
{(MII)1¢x(MIII)x(OH)2}x + {(An¢)x/n·y H2O} (Table 1).[8] They are [a] Dr. K. Yan
rare examples of layered solid materials with positively School of Engineering
charged layers balanced by exchangeable anions.[9] The basic Brown University
182 Hope Street
layer structure of LDHs is based on that of brucite
Providence, RI 02912 (USA)
{Mg(OH)2} composed of edge-sharing Mg(OH)6 octahedra E-mail: kai_yan@brown.edu
units that form infinite layers.[10–12] As shown in Figure 1, MII [b] Dr. G. Wu
and MIII are the divalent and trivalent metal cations, respec- Department of Chemistry
tively, for which the ratio of MII/MIII crucially influences the Lakehead University
955 Oliver Road
charge density on the layers of the LDHs.[13, 14] The value of
Thunder Bay, Ontario P7B 5E1 (Canada)
x is the cation concentration of the trivalent metal, and it has
[c] Dr. W. Jin
a profound influence on the composition as well as the struc- Institute of Process Engineering
ture of the resulting LDHs. The range of the x value is re- Chinese Academy of Sciences, 100190 Beijing (PR China)

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 354

Figure 1. The typical structure of a LDH.[13, 24]
Kai Yan is currently working in the School
of Engineering at Brown University. He
started his PhD degree at the Max Planck
Institute for Coal Research in 2008 in
Germany with the support of a Max
Planck Society Scholarship. He obtained
his PhD degree from RWTH Aachen Uni-
versity in 2011. He obtained an Ontario
Postdoctoral Fellowship in 2012. His re-
search interests concentrate on the devel-
opment of robust nanomaterials for cata-
lytic conversion of biomass, solar fuel,
and electrocatalysis in energy generation. He is the author and coauthor
of 30 journal papers and a book chapter, publishing mainly in the area
of sustainable energy generation.
Guosheng Wu completed his PhD degree
at the Institute of Solid State Physics,
Chinese Academy of Sciences in 2004.
After obtaining his PhD degree in 2004,
he was an Assistant Professor at Anhui
University, China, and then he moved to
Lakehead University (Canada) as a Post-
doctoral Fellow. He is now a Materials
Scientist in the Department of Chemistry
and Instrumentation Laboratory, Lake-
head University. His main research inter-
ests are the design of earth-abundant,
highly efficient photocatalysts for environmental purification and solar
to fuel conversion. He is the author and coauthor of more than 50
peer-reviewed papers and a book chapter.
Wei Jin obtained his PhD degree at the
Institute of Process Engineering, Chinese
Academy of Sciences (CAS) in 2012.
During his PhD studies, he was selected
as a visiting researcher to the University
of Utah from 2010 to 2011 under the
support of a China Scholarship Council.
After postdoctoral training at Lakehead
University (Canada) and Missouri Univer-
sity of Science and Technology (USA)
from 2013 to 2015, he will start a faculty
career as an Associate Professor at the
CAS. His research focuses on novel design processes for electrowinning
and metal recovery, electrochemical monitoring and conversion of
heavy-metal contaminants, and thermodynamics of phase behavior.
Energy Technol. 2016, 4, 354 – 368
ported to be 0.2 < x < 0.4, which could achieve high
purity and good crystallization of the LDHs.[13, 15, 16]
Anion and water often comprise the interlayer
space in the structure of LDHs and compensate the
positive charge of the brucite-like layer.[17–19] The
type of anion (An¢) also has an important effect on
the purity and crystallinity of the LDHs.[20, 21] The
amount y of water can exist in the interlayer or be
adsorbed on the surface of the fabricated
LDHs.[9, 22–24] By benefitting from the tunability of
the metal cations in the brucite-like layers and the nature of
the coordinated anions in the interlayer galleries, a large
number of host–guest assemblies and nanoarchitectures with
attractive physical and chemical properties have been ration-
ally created. As a result of their unique properties, LDHs
represent an inexpensive and versatile source for a variety of
catalyst supports, catalyst precursors, and actual cata-
lysts.[8, 9, 13]
Owing to the unique properties of LDHs, which include
adsorption capacity, cation-exchange ability of the brucite
layer, and anion-exchange ability of the interlayer space,
LDH-based materials can provide spatially separate reduc-
tion and oxidation reaction sites for the active generation of
H2 and O2 from water splitting. The unique properties of the
matrix of LDHs offer the benefits of better charge separa-
tion in the photocatalytic process, excellent electronic and
optical properties, better electron transfer at the interface of
the LDHs and the electrolyte, improved electrode reaction
kinetics, and reduced electrolyte ohmic drop.[8, 9, 13] The crystal
size, shape, and morphology and the types of anions and cat-
ions in the layered structure exhibit a strong influence on
charge separation, electron transport, and overall energy-
conversion efficiency. These crucial parameters are closely
related to the synthetic methodologies.[25–29] Over the last
several decades, tremendous progress has been made in the
design and synthesis of LDH-based materials to fulfil the
specific requirement of water splitting. There are many ad-
vanced reviews on methods for the synthesis of
LDHs,[8, 12–15, 18, 19, 30] and herein we will not systematically
detail this aspect. In this minireview, we initially outline
recent advances in the synthesis of LDHs by several crucial
routes (i.e., urea hydrolysis, sol–gel, coprecipitation, and
anion exchange). We further focus on recent progress of
LDHs in photocatalytic H2 generation and photocatalytic
and electrocatalytic O2 evolution through tuning their optical
and electronic properties. To our limited knowledge, this is
the first minireview on recent advances in the synthesis of
LDHs for the efficient production of H2 and O2. The advan-
tages and challenges of LDH-based materials are also high-
lighted. The structure–properties correlations are addressed
and future potentials are also discussed. In general, this mini-
review may provide useful insight into ways to develop
robust and promising catalysts based on LDH materials for
energy applications.
Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 355
2. Recent Advances in the Synthesis of Layered cipitate together under the basic conditions to produce MgAl
Double Hydroxides LDHs [Eq. (6)].

There are a number of techniques that can be applied to syn- H2 N¢CO¢NH2 ! NH4 þ þ NCO¢ ð1Þ
thesize LDHs, depending on the specific requirements for
catalytic applications.[8, 13] LDHs are constituted by two NCO¢ þ 2 H2 O ! NH4 þ þ CO3 2¢ ð2Þ
metals typically having 2 + (MII) and 3 + (MIII) or 4 + (MIV)
NCO¢ þ 2 Hþ þ 2 H2 O ! NH4 þ þ H2 CO3 ð3Þ
oxidation states, octahedrally surrounded by oxo bridges and
hydroxyl groups.[8] During the last few decades, it has been
MgðH2 OÞn 2þ þ H2 O ! MgðOHÞðH2 OÞn¢1 þ þ H3 Oþ ð4Þ
demonstrated that layered LDHs materials containing Ti4 +
or Cr3 + are good for photocatalytic water splitting and that AlðH2 OÞn 3þ þ H2 O ! AlðOHÞðH2 OÞn¢1 2þ þ H3 Oþ ð5Þ
those importing Ni2 + are good for electrocatalytic O2 evolu-
tion.[7, 9, 12, 13] Through rational choice of proper synthesis MgðOHÞðH2 OÞn¢1 þ þ AlðOHÞðH2 OÞn¢1 2þ þ OH¢ þ CO3 2¢
methods and control of reaction parameters, different robust
! MgAlðOHÞ3 ðCO3 ÞH2 O
MIITi, MIICr, and NiMIII LDH based photocatalysts and elec-
ð6Þ
trocatalysts can be successfully synthesized. Different diva-
lent and trivalent metal cations in the brucite-like layer and
Different parameters in the synthesis of MII/Al-carbonate
variable anions in the interlayer gallery offer spatially sepa-
LDHs (MII = Mg, Zn, and Ni) by using urea hydrolysis have
rate reduction and oxidation reaction sites. Alternatively, the
been studied by Costantino et al.[24] They have investigated
optical and dielectric properties, which determine the
the effects of varying the temperature, total metal-cation
energy-conversion efficiency, can be tuned. Considering cur-
concentration, molar fraction ratio of Al/Al + MII, and the
rent advances in their application for energy generation, four
molar fraction ratio of urea/MII + Al on the final composition
advanced methods (i.e., urea hydrolysis, sol–gel, coprecipita-
and crystallinity of the resulting samples. According to their
tion, and anion exchange) are outlined. The physicochemical
findings, the optimum conditions to prepare LDHs with
properties (e.g., phase purity, crystallinity, porosity, morphol-
good crystallinity in a relatively short time are suggested to
ogy, and electronic and optical nature) of the LDH materials
involve dissolving solid urea in a 0.5 m solution of the chosen
as influenced by the synthesis method will also be highlight-
metal chloride to give a urea/metal ion molar ratio of 3.3.
ed.
The clear solution is aged at 100 8C for 36 h. Well-crystallized
LDHs with a relatively large size (microns in diameter) and
2.1. Urea hydrolysis a well-defined hexagonal shape are fabricated. Besides, this
work demonstrates that the urea-hydrolysis method is not
Owing to two NH2 groups joined by a carbonyl (C = O) func-
only suitable for the preparation of MgAl LDHs with low
tional group, urea has been utilized as an attractive agent for
charge density but also allows the preparation of compounds
the precipitation of several metal ions into metal hydroxides
with high charge density.
from mixed solution.[31, 32] Urea has a few unique properties
such as weak Brønsted base (pKb = 13.8) characteristics, high
Fe3þ þ 3 OH¢ Ð FeðOHÞ3 ð7Þ
solubility in water, and controllable hydrolysis rate.[33] For
urea, the hydrolysis reaction progresses slowly, which leads
2 FeðOHÞ3 þ 6 Ni2þ þ 10 OH¢ þ CO3 ¢ þ 5 H2 O
to a low degree of supersaturation and better precipitation. ð8Þ
By altering the reaction temperature, the hydrolysis rate of Ð ½Ni6 Fe2 ðOHÞ16 ¤ðCO3 Þ ¡ 5 H2 O
urea can be varied and the particle size of the LDHs can be
FeðOHÞ3 þ 2 C6 H5 O7 3¢ Ð ½FeðC6 H5 O7 Þ2 ¤6¢ þ OH¢ þ H2 O
controlled.
By using a retardant urea as the precipitating agent in the ð9Þ
synthesis of LDHs, the nucleation step can be separated
2 ½FeðC6 H5 O7 Þ2 ¤5¢ þ 6 Ni2þ þ CO3 2¢ þ 6 OH¢ þ 7 H2 O
from particle growth, and ageing is prevented from the be-
ginning. Different advanced technologies (e.g., in situ spec- Ð ½Ni6 Fe2 ðOHÞ16 ¤ðCO3 Þ ¡ 5 H2 O þ 2 C6 H5 O7 3¢
troscopic characterizations) have been applied, and support- ð10Þ
ing evidence seeking to explore the formation of MgAl
LDHs by urea hydrolysis has been obtained.[9, 13] The hydrol- Introduction of a surfactant or chelating agent in the urea-
ysis of urea generally proceeds over two steps: the formation hydrolysis process is a promising strategy to increase the sur-
of ammonium cyanate (NH4CNO) is considered as the rate- face area and pore volume of the resulting LDH-based mate-
determining step [Eqs. (1) and (2)] with subsequent fast hy- rials. It has been reported that a surfactant or chelating agent
drolysis of the cyanate to ammonium carbonate [Eqs. (2) and mainly influences the formation of LDHs in the last two
(3)].[31] Two key intermediates, Mg(OH)(H2O)n¢1 + [Eq. (4)] steps [Eq. (4) and (5)]. Han et al.[35] have introduced trisodi-
and Al(OH)(H2O)n¢12 + [Eq. (5)], are formed in weak alka- um citrate (C6H5Na3O7·H2O, TSC) as a chelating agent and
line media. Owing to the low solubility of Mg(OH)(H2O)n¢1 + have successfully fabricated NiFe LDHs with high crystallini-
[Eq. (4)] and Al(OH)(H2O)n¢12 + [Eq. (5)], they tend to pre- ty and a relatively large surface area. As the pH value in-

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 356
creases, amorphous Fe(OH)3 is initially formed [Eq. (7)]. In
the absence of a TSC chelating agent, further addition of the
base results in the conversion of Fe(OH)3 into NiFe LDHs
[Eq. (8)].
The very low solubility of Fe(OH)3 possibly makes trans-
formation of the pH value from Fe(OH)3 to NiFe LDHs
close to that of Ni2 + ion deposition, which causes the forma-
tion of impure b-Ni(OH)2 in the final LDHs sample. The ad-
dition of the TSC chelating agent increases the pH value of
the deposition range of Fe(OH)3, because Fe3 + ions are che-
lated by TSC [Eqs. (9) and (10)]. Besides, the TSC chelating
agent mainly exists as C6H5O73¢ ions, which in solution indu-
ces the Fe3 + ions to form the metal–ligand complex
[Fe(C6H4O7)2]5¢. At favorable concentrations of Ni2 + and
OH¢ , the NiFe LDH material is formed with high crystallini-
ty and controllable size.
Silva et al.[40] have synthesized a series of ZnTi, ZnCe, and
ZnCr LDHs at different Zn/metal atomic ratios and have
found that the resulting LDH materials have vast potential
as visible-light photocatalysts. All the prepared materials ex-
hibit quite remarkable photocatalytic activity, and the one
containing Zn and Cr is the most active. The concentration
of Cr plays a beneficial role in the photocatalytic activity.
The most active material is the ZnCr LDH with an atomic
Zn2 + /Cr3 + ratio of 4:2; it exhibits two absorption bands in
the visible region at lmax = 410 and 570 nm. More typical and
successful work on the synthesis of various LDH-based mate-
rials by using the urea-hydrolysis method are shown in
Table 2. Although some studies have shown that this method
is not suitable for preparing LDHs containing CuII or CrIII[17]
and that the prepared LDHs may have carbonate ion impuri-
ties because of their high affinity for LDHs, the LDH materi-
als prepared by using the urea-hydrolysis method offer many
attractive advantages that cannot be obtained by any other
method. The resulting LDH-based materials often display
good crystallinity, relatively large surface area, controllable
morphology, homogeneous sizes, and platelet-like primary
particles with well-defined hexagonal shapes. These proper-
ties strongly influence their surface defects, which affect light
absorbance, charge separation, and charge-carrier recombi-
nation. Besides, the resulting LDH materials obtained by the
urea-hydrolysis method often present nanosize 2 D spaces
that are beneficial for improving electron–hole separation
and electron transportation and the overall energy-conver-
sion efficiency.
2.2. Sol–gel method
The sol–gel method is a wet-chemical technique that has
been recently widely employed in the fields of materials sci-
ence and membrane engineering.[41–43] This methodology is
initially used for the fabrication of metal oxides starting from
a chemical solution acting as the precursor for an integrated
network (or gel) of either discrete particles or network poly-
mers.[44] During the sol–gel processing, the desired metal pre-
cursors (e.g., organic metal compounds) are hydrolyzed in
water or ethanol, aqueous solution, or a liquid–organic sol-
vent under ambient conditions to produce a polymeric or
particulate sol. An appropriate amount of acid (e.g., HCl or
HNO3, as shown in Table 3) can be added into the sol mix-
ture during hydrolysis to facilitate precipitation.
Prince et al.[45] have reported the synthesis of multimetallic
LDHs (MgAl, NiAl, and NiCoAl) with different morpholo-
gies by using the sol–gel method, as shown in Figure 2. They

Table 2. Typical works of LDH synthesis by using the urea-hydrolysis method.

No. Cations Anion Synthesis conditions Phase composition/formula Ref.

2+ 3+
1 Ni , Fe
2 Ni2 + , Fe3 +
3 Ni2 + , Fe3 +
4 Ni2 + , Fe3 +
5 Ni2 + , Fe3 +
6 Zn2 + , Al3 +
7 Mg2 + , Al3 +
8 Zn2 + , Al3 +
9 Ni2 + , Fe3 +
10 Co2 + , Ni2 + , Fe3 +
¢ ¢
NO3 NO3 /urea molar ratio of 0.25; NiFe–CO3 LDHs [34]
hydrothermal treatment at 110 8C for 24 h
NO3¢ NO3¢/urea molar ratio of 2.0; NiFe–NO3 LDHs, Ni(HCO3)2, NiFe–CO3 LDHs [34]
hydrothermal treatment at 110 8C for 24 h
NO3¢ NO3¢/urea molar ratio of 3.0; NiFe–NO3 LDHs [34]
hydrothermal treatment at 110 8C for 24 h
NO3¢ trisodium citrate additive, urea precipitant; [Ni0.75Fe0.25(OH)2] (CO3)0.13·0.5 H2O [35]
hydrothermal treatment at 150 8C for 2 days
NO3¢ trisodium citrate additive, urea precipitant; [Ni0.8Fe0.2(OH)2](CO3)0.1·0.54 H2O [35]
hydrothermal treatment at 150 8C for 2 days
Cl¢ initially reflux at 105 8C under stirring for 1 h; ZnAl–Cl LDHs [36]
then hydrothermal treatment at 95 8C for 24 h
Cl¢ 120 8C for 1 day, the pH of the solution changed [Mg0.65Al0.35(OH)2]·0.13 CO3·n H2O [33]
from 3.4 at the beginning to 8.4 at the end
Cl¢ initial stirring of 1000 rpm at 90 8C, pH 7.6, ZnAl–Cl LDHs [37]
separated from solution by pressure filtration
NO3¢ trisodium citrate as chelating reagent; [Ni0.75Fe0.25(OH)2]·[(CO3)0.125·0.5 H2O] [38]
hydrothermally treated at 150 8C for 2 days;
solid product was filtered, washed with deionized water
and anhydrous ethanol, and dried at RT in air
Cl¢ trisodium citrate as chelating reagent; [Co0.11Ni0.663Fe0.225(OH)2]·[(CO32¢)0.113·0.85 H2O [39]
hydrothermally treated at 150 8C for 2 days;
solid product was filtered, washed with deionized water
and anhydrous ethanol, and dried at RT in air

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 357
 Table 3. Typical works of LDH synthesis by using the sol–gel method.

No. Precursors Conditions LDH phase Refs.

1 Mg(OMe)2, Al(Os-Bu)3, Ni(OAc)2·4 H2O HNO3 to hydrolyze the precursor and acetic acid as chelating agent; NiMgAl LDHs [46]
ethanol as solvent; MgAl LDH is formed first,
then Ni2 + partially replaces Mg2 + to form NiMgAl LDH
2 Al(Os-Bu)3, Mg(NO3)2·6 H2O Al alkoxide in ethanol solution, heated at 90 8C for 1 h MgAl LDHs [47]
3 Mg(OEt)2, Al(acac)3[a] HCl as hydrolysis acid, synthesis pH 10, initial Mg2 + /Al3 + ratio of 3 MgAl2.85 LDHs + brucite [44]
4 Mg(OEt)2, Al(acac)3[a] HCl as hydrolysis acid, synthesis pH 10, initial Mg2 + /Al3 + ratio of 5 MgAl4.29 LDHs [44]
5 Mg(OEt)2, Al(acac)3[a] HNO3 as hydrolysis acid, synthesis pH 10, initial Mg2 + /Al3 + ratio of 3 MgAl2.53 LDHs [44]
6 Ni(acac)2, Al(acac)3[a] HCl as hydrolysis acid, synthesis pH 6, initial Ni2 + /Al3 + ratio of 3 NiAl3.39 LDHs + others [44]
7 Ni(acac)2, Al(acac)3[a] HNO3 as hydrolysis acid, synthesis pH 6, initial Ni2 + /Al3 + ratio of 3 LDHs + others [44]
8 Mg(OEt)2, Al(acac)3[a] HCl as hydrolysis acid, synthesis pH 10 by adding NH4OH, MgAl LDHs [48]
initial Mg2 + /Al3 + ratio of 13
9 Mg(OEt)2, Al(Os-Bu)3 HNO3 as hydrolysis acid, temperature of 0 8C, ethanol as solvent, MgAl LDHs [45]
dried at 70 8C for 24 h
10 Ni(OAc)2, Al(Os-Bu)3 HNO3 as hydrolysis acid, temperature of 0 8C, ethanol as solvent, NiAl LDHs [45]
dried at 70 8C for 24 h
11 Co(OAc)2, Ni(OAc)2, Al(Os-Bu)3 HNO3 as hydrolysis acid, temperature of 0 8C, ethanol as solvent, NiCoAl LDHs [45]
dried at 70 8C for 24 h
12 Al(Oi-Pr)3, Zn(NO3)2·6 H2O HNO3 as hydrolysis acid, water as solvent, at 85 8C for 2 h to form ZnAl LDHs [49]
boehmite, zinc nitrate and NH4NO3 were precipitated at pH 6.5

[a] acac: acetylacetonate.

Figure 2. TEM images of sol–gel LDHs: a) MgAl, b) NiAl-A, c) NiCoAl, and

d) NiAl-N. Reprinted with permission from Ref. [45].

ascribe the successful synthesis to accurate control of crucial

synthesis parameters and the complexation rate of the metal-
lic precursors, for which the complexation of metallic precur-
sors is to equalize their hydrolysis and condensation rates to
produce transparent gels. The fabricated MgAl LDH has
been successfully casted as thin films over glass substrates.
Upon depositing the sols on monoliths followed by calcina-
Figure 3. SEM images of thin films: a) CoNiAl, b) CoNiAl-2d, c) NiAl-A, and
tion, the catalytic membrane (Figure 3) is obtained with d) NiAl-A-5d; e) SEM image and corresponding elemental map of the MgAl
a uniform distribution of catalytically active particles with film [scale bars correspond to 20 (a, b), 2 (c), and 1 mm (d)]. Aged sols are
high thermal stability, which is highly promising for solid named (M)Al-Xd, for which X indicates the aging time of the sol in days. Re-
printed with permission from Ref. [45].
oxide fuel cells for energy generation.
More representative work on the synthesis of LDHs by
using the sol–gel method are depicted in Table 3. Overall, advantages over traditional methods: one, low-temperature
the sol–gel method is beneficial in terms of its cost effective- processing and consolidation is possible; two, smaller particle
ness and the high purity of the resulting LDHs. It has several size and morphological control in powder synthesis; three,

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 358
the homogeneity and structural properties of the resulting
solids are controllable at the synthesis level by simply vary-
ing the composition of the precursors, temperature, aging
time, and removal/addition of reactant species. These fabri-
cated LDHs allow higher and homogeneous dispersion of
the catalytically active phase, which results in better photoca-
talytic and electrocatalytic activity. Another feature that
makes these sol–gel LDHs distinguishable from those pro-
duced from other synthetic methods is their high specific sur-
face area of approximately 150 m2 g¢1 or higher. These ad-
vantages may provide the resulting LDHs with better elec-
tron transport and a greater electrochemically active surface
area.
2.3. Coprecipitation method
This is the most common method used to prepare LDHs. Co-
precipitation is often coupled with hydrothermal treatment
(together called the coprecipitation method) to increase
yields, to form crystalline LDHs, and to control crystal size.
It is based on the slow addition of a mixed solution of diva-
lent (M2 + ) and trivalent (M3 + ) metal salts in adequate pro-
portions into a reactor containing water. The second solution
(i.e., alkaline solution) is added in the reactor at a selected
pH value, which leads to coprecipitation of the two metallic
salts; this is followed by hydrothermal treatment, filtering,
washing, and drying. This method yields fairly substantial
amounts of products within a reasonable period of
time.[6, 50–52]
The mechanism of coprecipitation is ideally based on the
condensation of hexaaqua complexes in solution, which leads
to a buildup of brucite-like layers with evenly dispersed met-
allic cations and with solvated interlamellar anions. The co-
precipitation method offers a high degree of control for pro-
cess parameters such as pH, temperature, aging time, mixing
rate, ratio of cations, and solution concentration. Depending
on the control of the precipitation parameters, well-crystal-
lized LDH phases can generally be obtained, and control of
the properties of the LDH particles, including crystallinity,
particle size, size distribution, purity, and stability, is also pos-
sible.[31] To obtain well-defined phases, the operating condi-
tions have to be optimized for each system. Ahmed et al.[51]
have prepared ZnAl–NO3 LDHs with different Zn2 + /Al3 +
molar ratios at pH 7.5. The authors have determined the op-
tical band-gap energies of the LDH samples by using absorb-
ance data from UV/Vis–near-IR diffuse reflectance spectros-
copy. They have found that the band gaps are affected by
variation of the Zn2 + /Al3 + molar ratio, which is due to the
formation of phases with low crystallinity (i.e., ZnO and
ZnAl2O4). Besides, the water molecules and NO3¢ anions in
the LDH interlayer have been reported to be responsible for
the generation of the dielectric response. This response has
been described by an anomalous low-frequency dispersion by
using the second type of the universal power law. The domi-
nance of ZnO dipoles and charge carriers (NO3¢ ions) in the
dielectric relaxation increases with an increase in the molar
ratio.
It is important to identify the effects of various precipita-
tion parameters influencing the characteristics of the result-
ing LDHs. On the basis of literature reviews, the general ef-
fects of the coprecipitation parameters on the formation of
LDHs are presented in Table 4. Depending on the precipita-
tion conditions, it is possible to obtain well-crystallized LDH
phases or quasiamorphous materials. Some of the influencing
experimental parameters are clear, such as pH of the reac-
tion medium. The pH value must be chosen carefully, be-
cause if it is too low, not all the different metal ions will pre-
cipitate together, and if it is too high, the dissolution of one
or more metal ions may occur. The pH value needed for pre-
cipitation of LDHs is not necessarily equal to the pH value
for precipitation of the most soluble metal hydroxide. For in-
stance, pure Al(OH)3 precipitates at pH 4.5, Ni(OH)2 precip-
itates at pH 7, and Mg(OH)2 precipitates at pH 9.5,[6, 30, 53]
whereas NiAl LDHs precipitate at pH 4.0–4.5 and MgAl
LDHs precipitate at pH 7.7–8.5, as determined by potentio-
metric titrations.[6, 30, 53] In general, LDH materials are often
synthesized at pH 7–10.[15, 16, 54] According to the addition of
resources, this method can be briefly divided into precipita-
tion at low and high supersaturation. Important parameters
influencing the coprecipitation method and typical reports in
the synthesis of LDHs are depicted in Tables 4 and 5, respec-
tively.
2.3.1. Precipitation at low supersaturation
Precipitation at low supersaturation is often performed by
the slow addition of an aqueous solution containing the pre-
calculated ratios of both divalent and trivalent metal salts
into a reaction vessel. The second basic solution is simultane-
ously added, either manually or by an automatic titration
device, to the reaction vessel to maintain the desired pH
value. After precipitation, hydrothermal treatment at an op-

Table 4. Important parameters influencing LDH synthesis.

Parameter name Influence

precipitation pH formation of pure LDHs phase, crystallinity
temperature related to phase transformation
mixing controls uniformity of reaction, impacts size distribution
aging time increases size and crystallinity
ratio of cations formation of pure LDH phase, controls charge of brucite layer
intercalated anion propensity to undergo anion exchange, may contribute to stability of LDHs depending on cations
solution concentration degree of supersaturation, crystal size and size distribution

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 359
 Table 5. Typical works of LDH synthesis by using the coprecipitation method.

No. Precursors Synthesis conditions Phase/formula Ref.

1[a] Cu2 + , Co2 + , Cr3 + NaOH and Na2CO3 as precipitates, constant pH 9.5, RT for 6 h CuCoCr LDHs [61]
2 Mg(NO3)2·6 H2O, K2CO3 and NaOH as precipitates, pH 10, filtered and washed, dried in oven for 24 h at MgAl–CO3 LDHs [47]
Al(NO3)3·9 H2O 100 8C
3 Mg(NO3)2·6 H2O, synthesis at pH 9, initial Mg2 + /Al3 + ratio of 3 MgAl2.69–NO3 LDHs [44]
Al(NO3)3·9 H2O
4 Ni(NO3)2·6 H2O, synthesis at pH 9, initial Ni2 + /Al3 + ratio of 3 NiAl2.98–NO3 LDHs [44]
Al(NO3)3·9 H2O
5 CaO, Al(NO3)3·9 H2O ultrasonic oscillation of mixed solution at 55 8C; washed, vacuum filtered, dried at 80 8C CaAl–NO3 LDHs [62]
6 Co(NO3)2·6 H2O, solution 1 of Co2 + , Al3 + salt; solution 2 of (NH4)2CO3 and NH4OH; solution 2 was added CoAl–CO3 LDHs [63]
Al(NO3)3·9 H2O dropwise to solution 1 with constant stirring at 40 8C for 1 h, with pH 8.5; washed, filtered,
and dried at 80 8C overnight
7 Mg(NO3)2·6 H2O, NaOH solution was continuously dropped into the mixed salt solution until pH 7.8; stirred MgCoAl–NO3 LDHs [55]
Co(NO3)2·6 H2O, for 30 min; hydrothermally treated at 110 8C for 3 h; filtered, washed, and then dried at
Al(NO3)3·9 H2O 80 8C for 12 h
8 Cu(NO3)2·6 H2O, NaOH solution and mixed salt solution were continuously dropped into the beaker with CuFe–NO3 LDHs [64]
Fe(NO3)3·9 H2O constant pH 4.6; stirred for 30 min; hydrothermally treated at 110 8C for 0.5 h; filtered,
washed, and dried at 80 8C for 12 h
9 Cu(NO3)2·6 H2O, NaOH solution and mixed salt solution were continuously dropped into the beaker with CuCr–NO3 LDHs/ [65]
Cr(NO3)3·9 H2O, constant pH 4.6; stirred for 30 min; hydrothermally treated at 110 8C for 0.5 h; filtered, CuAl–NO3 LDHs
/Al(NO3)3·9 H2O washed, and dried at 80 8C for 12 h
10 Ni(NO3)2·6 H2O, NaOH solution and the mixed salt solution were continuously dropped into the beaker NiAlCe–NO3 LDHs [56, 66]
Al(NO3)3·9 H2O, with constant pH 6.5; stirred for 30 min; hydrothermally treated at 120 8C for 3 h; filtered,
Ce(NO3)3·6 H2O washed, and dried at 80 8C for 12 h
11 Mg(NO3)2·6 H2O, solution 1 of NaOH and Na2CO3, and solution 2 of mixed salt were continuously dropped MgAl–CO3 LDHs [67]
Al(NO3)3·9 H2O into a beaker with constant pH 9.5; aged at 100 8C for 13 h; filtered, washed, and dried at
100 8C for 24 h

[a] CuCoCr–CO32¢ : Cu–Co–Cr ternary LDH containing CO32¢ in the interlayer.

timal temperature and aging time is utilized to increase the
size and crystallinity of the LDHs. The anion in the reaction
vessel should typically have a high affinity for the LDHs and
should easily enter into the interlayer space to expel the for-
eign anions (e.g., carbonate). On the basis of this consider-
ation, metal salts containing chloride or nitrate are typically
chosen. The primary advantage of this method is the precipi-
tation of well-crystallized, large particles. A series of MgAl,
MgCoAl, CuZnAl, NiAl, CoAl, CuCr, and CuFe LDHs have
been synthesized in our laboratory, and they have been em-
ployed in various catalytic transformations with good per-
formance.[55–59] Owing to the high affinity of carbonate anions
for LDHs materials, the coprecipitation reaction is often per-
formed under an atmosphere of nitrogen or argon to mini-
mize the adsorption of atmospheric carbonate during precipi-
tation.
2.3.2. Precipitation at high supersaturation
This preparation method often involves the fast addition of
a mixed divalent and trivalent metal salt solution to an aque-
ous basic solution. Constantino and Pinnavaia[60] have suc-
cessfully prepared MgAl LDHs containing OH¢ , Cl¢ , and
SO42¢ anions. However, preparation at high supersaturation
often produces LDHs with poor crystallinity and small parti-
cle sizes, which is due to the relatively large number of crys-
tallization nuclei. Additionally, LDH materials prepared by
using this method may contain impure phases. This is due to
the easy formation of M(OH)2 and M(OH)3 hydroxides.
These hydroxide impurities often exist in the resulting
LDHs, and it is also difficult to control the final M2 + /M3 +
ratio.
Despite many advantages, the coprecipitation method still
suffers from several disadvantages: one, this method is not
suitable for the preparation of accurate stoichiometric
phases; two, it does not work well if the reactants have large-
ly different solubilities. However, as shown in Table 5, the co-
precipitation process often presents a more homogeneous
mixing of the reactant precipitates, precipitation occurs at
low reaction temperatures, and it presents a simple and
direct process for the synthesis of multimetallic LDH materi-
als with high crystallinity and controllable crystal sizes. These
structural features increase the light-harvesting capabilities
of these materials, because they enhance light use by allow-
ing as much light as possible to access the interior, which re-
duces the recombination of electrons and holes. These prop-
erties also offer the benefits of better charge separation in
the photocatalytic process, better electron transfer at the in-
terface of the LDH and electrolyte, and improved electrode
reaction kinetics.
2.4. Anion exchange
Anion exchange is a very important method to significantly
modify the structure and functionality of LDH-based materi-
als.[11, 68] It is based on the exchange properties of the inter-
layer anions, and this method is very useful if the coprecipi-
tation method is inapplicable, for example, the involved

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 360
anions are unstable in alkaline solution. Anion exchange in
LDHs depends mainly on the electrostatic interactions be-
tween the host layers and the exchanging anions; thus, ex-
change is favored for in-going anions with a high charge den-
sity. By exchanging the desired anion, the fabricated LDHs
can have a narrower band gap and enhanced light-harvesting
capabilities, because they enhance light use by allowing as
much light as possible to access the interspace, which reduces
the recombination of electrons and holes. Their light-harvest-
ing capabilities make them good candidates for use in photo-
catalysis with the advantages of high photocatalytic activity
and good durability.
The anion-exchange method is a synthesis process in
which an ion or molecule is inserted in between the layers of
the crystal lattice, leaving the basic structure unchanged.[69]
Owing to the fact that the process is reversible, LDHs can be
incorporated into polymers after intercalation to improve the
chemical and physical properties of the materials, that is, the
thermal stability and optical and magnetic properties, and
also to change the surface properties of the host from hydro-
phobic to hydrophilic.[14, 70] Layered host lattices may adjust
their interlayer separation to adapt to the packing geometry
of the inserted species.[71, 72] Intercalation reactions involve an
electrostatic interaction between the guest anionic charge
and the cationic sites in the LDHs layers.[71] The higher the
layer charge density, the higher the content of intercalated
anions and water molecules. This results in a strong interac-
tion between the layers, which leads to a tight stacking of the
sheet.[73] One example of LDHs intercalated with CO32¢ ions
is shown in Figure 4. Considering the selectivity scale for the
most common counterions,[2, 15] CO32¢ > SO42¢ > OH¢ > F¢ >
Cl¢ > Br¢ > NO3¢ > ClO4¢ , LDHs containing nitrate anions
are the most suitable precursors for the intercalation of cata-
lytically active species.
During the past two decades, increasing interest has been
devoted to the use of these layered inorganic solids as host
materials to create host–guest supramolecular intercalation
structures with desirable physical and chemical properties.[14]
As shown in Table 6, the exchange ability of incoming anions
increases with increasing charge and decreasing ionic radius.
The intercalation of catalytically active species (e.g., simple
inorganic anions, complex anions) in the interlayer galleries
of LDHs is an effective confinement strategy that greatly en-
larges the family of available LDHs materials. This method
has been proven to improve catalytic stability and recyclabili-
ty relative to that of homogeneous catalysts.

Figure 4. a) Schematic representation of the LDH structure; b) detailed schematic view of some physisorbed water molecules within layers. Bonds represented
as discontinuous try to depict the hydrogen-bonding interactions. Reprinted with permission from Ref. [74].

Table 6. Typical research works on the synthesis of LDHs using the anion exchange method.

No. M2 + M3 + Anions Phase/Formula Refs.

1 Mg Al CO3, NO3 Mg0.80Al0.20(OH)1.98(NO3)0.19(CO3)0.015 0.9H2O [75]
2 Mg Al C8H17SO3 Mg2Al(OH)6(C8H17SO3-)·H2O [76]
3 Mg Al Cl [Mg0.66Al0.33(OH)2]Cl0.33·nH2O [77]
4 Mg Al Fe(CN)6 [Mg0.74Al0.26(OH)2][Fe(CN)6]0.067(CO3)0.002·1.05H2O [78]
5 Mg Al, Fe CO3 [Mg0.74Fe0.11Al0.15(OH)2](CO3)0.13·0.70H2O [79]
6 Ca Al OH [Ca0.66Al0.33(OH)2](OH)0.33·nH2O [80]
7 Ca Al CO3 [Ca0.66Al0.33(OH)2](CO3)0.17·nH2O [80]
8 Ca Al NO3 [Ca0.66Al0.33(OH)2](NO3)0.33·0.66H2O [81]
9 Mg Cr Fe(CN)6 [Mg0.56Cr0.44(OH)2][Fe(CN)6]0.15·0.7H2O [82]
10 Ni Al Cl [Ni0.75Al0.25(OH)2]Cl0.25·nH2O [83]
11 Ni Al NO3 [Ni0.67Al0.33(OH)2](NO3)0.20(CO3)0.066·0.7H2O [84]
12 Mg Al CO3, NO3 Mg0.66Al0.34(OH)2(NO3)0.31(CO3)0.01·0.3H2O [75]
13 Zn Cr ClO4 [Zn0.66Cr0.33(OH)2](ClO4)0.33·0.66H2O [85]
14 Zn Cr HPO4 [Zn0.66Cr0.33(OH)2](HPO4)0.17·0.66H2O [85]
15 Zn Cr SO4 [Zn0.66Cr0.33(OH)2](SO4)0.17·0.66H2O [85]

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 361
 Owing to the electronic and magnetic properties and the
acidic nature of LDH intercalates, the design of such materi-
als pillared with robust polyoxometalates (POMs) has at-
tracted much attention, and intercalated LDHs have been
used for materials applications in shape-selective adsorption
and catalysis.[12, 18, 21, 86, 87] Pristine LDHs are seemingly weak
bases, and intercalation of acidic anions (e.g., POM anions)
makes them simultaneously possess acidity. One example of
pillaring that has been achieved by ion exchange of NO3¢ in
the LDH interlayer with [NH4]6[V10O28]·6 H2O at pH 4.5
and 25 8C is shown in Figure 5. Besides, LDHs pillared with
Figure 5. Schematic representation of POM/LDH nanocomposites through ion-exchange
synthetic route (H2O, POM, CO32¢, and NO3¢ molecules in the interlayer in polyhedral
representation, and the anions are schematized). Reproduced with permission from
Ref. [18].
the paratungstate A ion, Mg12Al6(OH)36(W7O24)·4 H2O; lacu-
nary Keggin [SiW11O39Mn(H2O)]6¢, [SiW11O39Ni(H2O)]6¢,
and [SiW11O39]8¢ ions; the monosubstituted Dawson
[P2W17O61Mn(H2O)]8¢ ion; and the Preyssler
[NaP5W30O110]14¢ ion have also been successfully reported
and have been found to present efficient performances in
photocatalysis.[16, 30, 33] These POM-intercalated LDHs have
large gallery height, a unique interlamellar chemical environ-
ment, and high dispersion of catalytically active species.
Under irradiation of UV or visible light, POM-intercalated
LDH nanosheets can accept photoexcited electrons from the
conduction band of the hybridized LDH lattice, which leads
to the formation of reduced POM* species that can work as
electron-transfer mediators.[88] Beside, the porous structure is
also beneficial for photocatalyst performance.
3. Advances on Layered Double Hydroxide Based
Materials for H2 and O2 Evolution
3.1. Photocatalytic H2 generation
Hydrogen (H2) is an excellent energy carrier for the develop-
ment of a low-carbon-emission economy.[1, 6, 7] Although it has
issues of easy exploration and transportation, it has several
overwhelming advantages:[89, 90]
Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1) No harmful emissions exists. The biggest advantage of
using H2 energy is that almost no harmful byproducts are
left if it is burned.
2) H2 is also nontoxic, which makes it a rarity among fuel
sources. This makes hydrogen ideal for use in a number
of ways other fuel sources cannot compete against.
3) H2 energy is a more efficient fuel source than traditional
sources of energy and produces more energy per pound
of fuel.
4) H2 is the most abundant element that can be obtained
from a broad range of substances.
5) H2 is also an important chemical reagent in the
chemical industry.
Among the various hydrogen-production routes,
photocatalytic H2 evolution is a promising strategy
owing to its low cost, environmental benignity, and
high efficiency. Over the last several decades, it has
been shown that layered materials containing Ti4 +
and Cr3 + are good for photocatalytic water split-
ting.[9, 13] However, the biggest disadvantages of
these materials are the easy aggregation of the pho-
toactive species as well as the relatively low energy-
conversion efficiency. Recently, it has been found
that confining the active photocatalyst in the LDH
matrix through intercalation or another synthetic
route enhances the dispersion of the active sites
and then improves the energy-conversion efficiency.
One diagram for the process of photocatalytic hy-
drogen production on LDH-derived materials is
shown in Figure 6. If the irradiation of light with
Figure 6. Photocatalytic H2 evolution based on LDH-derived photocatalysts.[94]
energy is greater than the bandgap of the LDH-derived ma-
terial, by separating the vacant conduction band (CB) and
filling the valence band (VB), an electron is excited in the
VB and jumps into the CB to result in the formation of an
electron (e¢)–hole (h + ) pair in the first stage.[91–93] In the
second stage, the photoexcited electron–hole pairs can either
recombine or migrate to different surface reaction sites and
drive a chemical reaction. If the excited electrons and pro-
duced holes recombine quickly, the energy is transferred to
heat or re-emitted as photons, a process through which the
absorbed energy is lost; as such, the efficiency of the energy-
conversion process is decreased.
362
 A carbonate-intercalated ZnCr LDH synthesized by the
coprecipitation method has been reported to be active for
photocatalytic H2 production,[94] and the ligand-to-metal
charge-transfer (LMCT) transitions of CrO6 octahedra visi-
ble in the UV/Vis spectra are thought to be the origin of its
ability for water splitting to generate hydrogen,[61] because
the carbonate radicals originating from the oxidation of in-
tercalated carbonate anions by photogenerated holes im-
prove the light-induced electron–hole separation. Further-
more, replacing part of the Zn2 + ions with Ni2 + ions also re-
sults in the transitions of ZnII/NiII¢O¢CrIII to ZnI/NiI¢O¢
CrIV,[95] which accounts for the enhanced photocatalytic activ-
ity for hydrogen evolution. In addition, the high dispersion
of TiO6 octahedra confined in a 2 D matrix of a series of MTi
LDHs (M = Ni, Zn, Mg) can suppress carrier recombination
under visible-light excitation by taking advantage of the
large number of surface Ti3 +¢O defects serving as trapping
sites to improve electron–hole separation.[96] The modified
band gap of approximately 2.1 eV obtained by the formation
of the M2 +¢O¢Ti network greatly facilitates water splitting,
which accounts for the 1.23 eV thermodynamic overpotential
and other kinetic overpotentials for both hydrogen and
oxygen evolution. The resulting Ti-containing LDHs
show a high photocatalytic H2-production rate of
0.314 mmol g¢1 h¢1, which is 18 times higher than that of the
K2Ti4O9 photocatalyst.
The use of LDHs on conducting materials allows a higher
and homogeneous dispersion of the active phase, which re-
sults in better photocatalytic activity. Cho et al.[97] have re-
ported a facile synthesis of ZnCr LDHs on the conducting
substrate fluorine-doped tin oxide (FTO) glass. The resulting
calcined photocatalyst displays a high photoresponse under
visible-light irradiation (l > 420 nm). Besides, the catalyst is
stable and exhibits activity for photoelectrochemical water
splitting that is one order of magnitude higher than that of
a zinc–chromium mixed-metal-oxide-nanoparticle film fabri-
cated ex situ by electrophoretic deposition.
The addition of electron donors (hole scavengers) can en-
hance hydrogen production through irreversible reaction
with VB holes to prohibit charge recombination. Carja
et al.[98] have reported the self-assembly of Au nanoparticles/
mesoporous matrices of LDHs (Au/ZnAl LDHs and Au/
ZnCeAl LDHs) and the derived mixed oxides as novel plas-
monic photocatalysts for H2 production from water/methanol
mixtures (80:20) by using solar irradiation at room tempera-
ture. The fabrication of the Au/LDH composite is based on
the formation of Au nanoparticles on the surface of the
anionic clay during manifestation of the clay structural
“memory effect” in an aqueous solution of AuCl3. An almost
linear correlation is observed between the amount of evolved
hydrogen and the irradiation time. The order of the catalytic
activity is: Au/ZnCeAl LDHs > Au/ZnAl LDHs > Au/
ZnCeAl LDHs750 > Au/ZnAl LDHs750 (calcined at 750 8C),
which suggests that the presence of Ce in the LDHs pro-
motes the catalytic activity of the material though calcina-
tion.
Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3.2. Photocatalytic O2 production
The formation of oxygen from water is challenging, as it
needs four positive holes and the formation of O¢O
bonds.[40, 99] Over the last decades, Ti- and Zn-containing
LDH materials have been tested for their photocatalytic abil-
ities in water oxidation. Silva et al.[40] have reported a series
of ZnTi, ZnCe, and ZnCr LDHs by using coprecipitation
and the urea-hydrolysis method at different Zn/metal atomic
ratios for visible-light photocatalytic oxygen generation, as
shown in Figure 7. The most active material in the series is
Figure 7. Photocatalytic O2 evolution on Ag supported on ZnCr LDHs. Repro-
duced with permission from Ref. [40].
the ZnCr LDH with an atomic Zn2 + /Cr3 + ratio of 4:2; it ex-
hibits two absorption bands in the visible region at lmax =
410, 570 nm. The efficiency of these chromium LDHs for
oxygen generation increases asymptotically with the Cr con-
tent. The apparent quantum yields for oxygen generation are
60.9 and 12.2 % at 410 and 570 nm, respectively. The overall
efficiency of the ZnCr LDHs for visible-light oxygen genera-
tion is 1.6 times higher than that of WO3 under the same
conditions. The good crystallinity and light-induced charge-
transfer transition (between CrIII¢O¢ZnII and CrIV¢O¢ZnII)
of the ZnCr LDHs enhances light absorbance and low
charge carrier recombination, which play crucial roles in
photocatalytic oxygen generation.[40]
Gunjakar et al.[92] have recently reported the synthesis of
mesoporous layer-by-layer ordered nanohybrids by self-as-
sembly of oppositely charged 2 D nanosheets of ZnCr LDHs
(Figure 8 a, b) and layered titanium oxide for visible-light-in-
duced O2 generation from water (Figure 8). The obtained
heterolayered nanohybrids show a strong absorption of visi-
ble light and a remarkably depressed photoluminescence
signal, which is indicative of effective electronic coupling be-
tween the two component nanosheets. The resultant nanohy-
brids are fairly active for visible-light-induced O2 generation
with a rate of approximately 1.18 mmol g¢1 h¢1. Furthermore,
the chemical stability can be significantly improved as
a result of the protection of the LDH lattice by a highly
stable titanate layer, which is superior to the pristine ZnCr
LDH material under the same experimental conditions.
Recently, some attempts have been made to combine
LDHs with graphene to enhance the photocatalytic per-
363
 LDHs help to prevent the recombination of holes
with electrons. In particular, a Fe-rich LDH catalyst
displays the highest photocatalytic efficiency for
water oxidation ( … 0.3 mmol g¢1 h¢1 of O2) under
visible light, and this has been attributed to its good
crystallinity, enhanced light absorbance, and low
charge carrier recombination originating from an
increase in the number of oxo bridges. Such LDH
materials can be expected to act as a useful step-
ping stone for the exploration of new photocatalysts
for water oxidation.

3.3. Electrocatalytic O2 evolution

Figure 8. The as-synthesized mesoporous layer-by-layer ordered nanohybrids by self-as-
sembly between oppositely charged 2 D nanosheets of ZnCr LDHs and their high activity
for visible-light-induced O2 generation from water. Reproduced with permission from
Ref. [92].
Owing to expensive noble metal catalysts that are
available with limited supply, LDH-based materials
containing inexpensive and abundant metal cations,
particularly Ni- and Co-containing LDHs, have
been widely used in various chemical processes re-
lated to renewable energy and electrocatalytic reac-
tions.[102–108] Oxygen can be recombined with hydro-
gen to produce water and electricity. The LDH
structure is attractive for use in electrochemical re-
actions, as it is highly accessible to electrolytes by

formance because of the excellent carrier transportation ca-

pability of graphene and its ability to induce visible-light re-
sponsive activity. The nanohybrids of LDHs and graphene
are supposed to create a strong physical contact, which acts
as a good acceptor for photoinduced electrons and thus re-
duces the electron–hole recombination. Li et al.[100] have re-
ported the fabrication of NiTi LDHs/reduced graphene oxide
(RGO) composite materials (Figure 9 a). The resulting NiTi
LDHs/RGO composite displays enhanced photocatalytic ac-
tivity toward water splitting into oxygen with a rate of
1.968 mmol g¢1 h¢1 and a quantum efficiency as high as
61.2 % at l = 500 nm (Figure 9 b), which thus places it among
the most effective visible-light photocatalysts. Electron spin
resonance (ESR) and Raman scattering spectroscopy have
confirmed electron transfer from the NiTi LDH nanosheets
to RGO with a good separation of electron–hole pairs indi-
cated by the photoluminescence measurements. The X-ray
diffraction (XRD) patterns and scanning electron microscopy
(SEM) images indicate that the NiTi LDH nanosheets (diam-
eter: 100–200 nm) are highly dispersed on the surface of
RGO. UV/Vis absorption spectroscopy has shown that the
introduction of RGO enhances the visible-light absorption
range of the photocatalysts, and this has been further verified
by the large decrease in the band gap ( … 1.78 eV), as studied
by cyclic voltammetry measurements. The authors have also
performed further work on the tuning of type/morphology of Figure 9. a) The fabrication of NiTi LDHs/RGO composite materials by an
both LDHs, and graphene gives rise to improved photocata- in situ growth method as the visible-light-responsive photocatalysts toward
lytic performance of these nanocomposites (e.g., ZnCr LDH/ water oxidation. b) Comparison study on the photocatalytic O2 production ac-
tivity under visible-light irradiation over NiTi LDHs/xRGO composites denot-
RGO).
ed as NT-xG (x = 0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 %), with pristine RGO and ZnCr
In addition, Kim et al.[101] have demonstrated that Co¢O¢ LDHs material as reference samples. Reproduced with permission from
Fe oxo bridges connecting different metal ions in CoFe Ref. [100].

Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 364
anion exchange. However, one of the major issues associated
with LDHs is their low conductivity.[102, 103] Gong et al.[102]
report the synthesis of NiFe LDH nanoplates on mildly oxi-
dized multiwalled carbon nanotubes (CNTs) for electrocata-
lytic O2 generation, as shown in Figure 10. The ultrathin
Figure 10. a) Schematic view of the hybrid architecture and NiFe LDH struc-
ture. b) TEM image of the NiFe LDH/CNT hybrid. Arrows point to NiFe LDH
plates and iron oxide (FeOx) particles. c) IR-compensated polarization curves
of the NiFe LDHs/CNT hybrid and commercial Ir/C catalyst on carbon fiber
paper (CFP) loaded at 0.25 mg cm¢2 for both catalysts electrode in 0.1 and
1 m KOH. RHE = reversible hydrogen electrode. Reprinted with permission
from Ref. [102].
NiFe LDH nanoplates ( … 5 nm) are covalently attached to
the CNTs (Figure 10 a, b). The crystalline NiFe LDH phase
in the nanoplate form is highly active for O2 generation in
1 m KOH solution. The hybrid material delivers a current
density of 5 mA cm¢2 at an overpotential of 250 mV with
a Tafel slope of 31 mV decade¢1 (Figure 10 c). For NiFe
LDHs grown on a network of CNTs, the resulting NiFe
Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
LDH/CNT complex exhibits higher electrocatalytic activity
and stability for oxygen evolution than commercial precious
metal Ir catalysts. The high performance of the material can
be mainly attributed to the LDH phase and is further facili-
tated by the ultrathin nature of the nanoplates and the
strong coupling to the carbon nanotubes.
Trotochaud et al.[106] have investigated the catalytic per-
formance of Ni1¢xFex(OH)2/Ni1¢xFexOOH thin-film catalysts
in the oxygen evolution reaction (OER) in 1 m KOH electro-
lyte. From the reported cyclic voltammetry on the Ni(OH)2/
NiOOH catalyst, Ni redox features are observed and no sig-
nificant OER current is visible until the overpotential is
> 400 mV. Besides, they have found that disordered g-
NiOOH displays much better activity than the b-NiOOH
catalyst and the addition of Fe results in a > 30-fold increase
in the conductivity of the fabricated film. The high intrinsic
OER electrocatalytic activity of the NiFe LDHs has been
further confirmed by later studies of NiFe LDHs grown on
graphene,[109] carbon quantum dots,[110] and Ni foam sub-
strates.[111] Tang et al.[110] report the formation of hybrids be-
tween carbon quantum dots (CQDs, … 5 nm) and ultrathin
NiFe LDHs nanoplates, in which the CQDs have a tiny size
and high conductivity.[89, 112, 113] The structure, size, and mor-
phology of the fabricated hybrid have been determined by
SEM and transmission electron microscopy (TEM). Fig-
ure 11 a shows the SEM images of the CQD/NiFe LDH com-
posite and confirms that the nanoplates are ultrathin and
have a variable size of approximately 50–200 nm. The TEM
image (Figure 11 b) shows that the NiFe LDHs nanoplates
and CQDs (size … 5 nm) successfully form a composite. The
high-resolution (HR)-TEM (Figure 11 c) image of the CQD/
NiFe LDHs composite further reveals that the fringe spacing
of 0.25 nm fits well with the spacing of the (0 1 2) lattice
plane of the NiFe LDHs, whereas the interplanar spacing of
approximately 0.321 nm corresponds to the (0 0 2) crystallo-
graphic planes of graphitic carbon, which is strong evidence
for the formation of the CQD/NiFe LDH composite struc-
ture. Figure 11 d shows the XRD patterns of the as-prepared
CQD/NiFe LDH electrocatalyst. No extra characteristic
peaks are detected from the patterns, which indicates that
there are no impurities in the products. The resulting CQD/
NiFe LDH composite exhibits high electrocatalytic activity
(with an overpotential of … 235 mV in 1 m KOH at a current
density of 10 mA cm¢2) and high stability for oxygen evolu-
tion; these values almost exceed those of all previously re-
ported Ni–Fe compounds and are comparable to those of the
most active perovskite-based catalyst.
4. Summary and Outlook
Layered double hydroxide (LDH)-based materials possess
many beneficial properties, including high tunability of the
types of metal cations, the M2 + /M3 + molar ratios, exchangea-
ble inorganic and organic charge-compensating anions, small
size, and high interfacial area. With these properties, en-
hanced photocatalytic and electrocatalytic activities for H2
and O2 production on LDH-based materials have been ach-
365

Figure 11. a) SEM image of the CQD/NiFe LDHs nanoplate catalyst; b) TEM
image, c) HR-TEM images, and d) XRD pattern of the CQD/NiFe LDHs
hybrid; e) diagram of oxygen evolution; f) the catalytic activity of oxygen evo-
lution. Arrows point to individual NiFe LDHs plates. Reprinted with permis-
sion from Ref. [110].
ieved. With the increasing need for sustainable energy sour-
ces, LDH-based materials may play a crucial role in develop-
ing solutions to many of these problems.
LDH-based materials can be efficiently produced from
urea hydrolysis, sol–gel, coprecipitation, and anion-exchange
methods, the choice of which depends on the application.
Furthermore, they can be stored for a period of time without
any significant change in their properties. These well-estab-
lished synthetic protocols have been proven to be effective
strategies for the scale-up synthesis of LDHs. Through care-
Energy Technol. 2016, 4, 354 – 368 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ful control of the synthesis parameters, it is possible to
change the dimensions, crystallinity, crystal size, and mor-
phologies of the LDHs. Owing to their natural drawbacks
(e.g., poor stability in acidic and neutral electrolytes, low
conductivity), future research should pay special attention
to:
1) Modification of the classic synthesis methods to produce
LDHs with an optimum surface area, anion-exchange ca-
pacity, and thermal stability. An increased number of
active sites, high surface area, and narrow pore-size distri-
bution are requisites for a good catalyst for H2 and O2
generation, because these factors can affect high catalytic
activity and adsorption capacity. The desired properties
of LDHs can be achieved by using a single method or
a combination of approaches for the synthesis of the
LDHs, as discussed in this review. The design and synthe-
sis of low-costing and high-quality LDH-based catalysts
with careful compositional, structural, and morphological
control is desired; important targets are improving cost
efficiency by replacing rare and noble metals with cheap-
er and more abundant ones, as this would make the pro-
cesses greener and more environmentally benign.
2) There are a lot of examples of an active catalyst resulting
from intercalation of specific anionic species in the inter-
layer space of the LDHs, which acts as the host structure.
Shape-selective chemical catalysts, electrochemical cata-
lysts, and photocatalysts have been successfully fabricat-
ed. Their service life and recycling still have much room
for improvement. Understanding the mechanism of im-
proved activity with LDH-based materials by in situ spec-
troscopic studies and joint theoretical–experimental stud-
ies would be more convincing.
3. Presently, the photocatalytic H2 and O2 production rates
obtained are low as a result of quick charge recombina-
tion and the inability to utilize visible light efficiently. To
achieve sustainable hydrogen or oxygen production, sev-
eral strategies can be considered: one, loading of cheap
non-noble metal particles or metal-oxide nanoparticles on
the surface of LDHs can inhibit charge recombination;
two, to develop more efficient visible-light adsorption, it
is necessary to narrow the band gaps to harvest visible
light in the long-wavelength region and to enhance the
photogenerated charge separation in photocatalysis.
Keywords: clays · electrocatalysis · hydrogen evolution ·
layered compounds · oxygen generation
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Received: September 10, 2015
Published online on February 10, 2016
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