Materials Today  Volume 19, Number 4  May 2016
Transition metal based layered double
hydroxides tailored for energy conversion
and storage
Xia Long, Zilong Wang, Shuang Xiao, Yiming An and Shihe Yang*
Department of Chemistry, William Mong Institute of Nano Science and Technology, The Hong Kong University of Science and Technology, Clear Water Bay,
Kowloon, Hong Kong
Layered double hydroxides (LDHs) are a class of clays with brucite like layers and intercalated anions.
The first (3d) series transition metals based LDHs (TM-LDHs) are attracting increasing interest in the field
of energy conversion and storage processes due to their unique physicochemical properties. In this
article, we review recent developments in the synthesis and applications of TM-LDH in these areas
including water splitting, CO2 conversion, metal-air batteries and supercapacitors and the underlying
mechanisms of these processes. In addition, current challenges and possible strategies are discussed from
the viewpoint of material design and performance.
Introduction
Layered double hydroxides (LDHs) are a class of two-dimensional
(2D) anionic clays made up of positively charged brucite-like host
layers and exchangeable charge-balancing interlayer anions
(Fig. 1a) that can be expressed as [M2+1 xM3+x(OH)2]x+(An )x/
2+
n
mH2O [1–4]. A fraction of divalent metal ions (such as Mg ,
2+ 2+ 2+ 2+ 2+
Fe , Co , Cu , Ni , or Zn ) coordinated octahedrally by hy-
droxyl groups in the brucite like layers are uniformly replaced by
trivalent metals (such as Al3+, Cr3+, Ga3+, Mn3+ or Fe3+) with the
molar ratio of M3+/(M3+ + M2+) (the value of x) normally between
0.2 and 0.4 [2]. The interlayer charge compensating anion A is
normally CO32 , which is known to have a very high affinity to the
LDH layers [5] but can nevertheless be decarbonated [6–8] and
exchanged with other inorganic (such as Cl , SO42 , etc.) or
organic anions (such as acetate, lactate, dodecyl sulfate, etc.)
[5]. The layered structure and the flexibility of incorporating
mixed valence transition metal ions into the LDH structure in
different compositions open the enormous potential to design
high-performance catalysts on the molecular and nanometer
scales. Moreover, as another attractive feature, such LDH materials
can be converted into the corresponding mixed metal oxides
(MMOs) with a uniform M2+ and M3+ distribution and a high
surface area after calcination treatment.
*Corresponding author:. Yang, S. (chsyang@ust.hk)
1369-7021/ß 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). http://dx.doi.org/10.1016/
j.mattod.2015.10.006
RESEARCH
RESEARCH: Review
Great efforts have been spent to tailor the physical and chemical
properties of LDHs by changing the nature of metal cations, the
molar ratio of M2+/M3+, the type of interlayer anions and so on to
fulfill specific requirements for practical applications of LDHs in
various areas, such as catalysis [9], fire retardants [10,11], phar-
maceuticals [12], photochemistry/electrochemistry [13–21] and
many others [2,22]. In particular, with the improvement of syn-
thetic methods for transition metals based LDHs (TM-LDHs) [5,23]
that have intrinsic electrochemical activities, there has been re-
cently a rapid growth in publications related to the understanding
and applications of LDH based materials in energy conversion and
storage processes. In this review article, we firstly summarize the
methods for synthesizing LDH nanosheets and then focus on the
latest development of TM-LDHs (the TMs in the TM-LDHs
reviewed in this article are mostly the first series transition metals)
based materials as electrochemical/photochemical catalysts for
water splitting and carbon dioxide reduction, as electrode materi-
als for supercapacitors and metal-air batteries. The recurrent chal-
lenge in this rapidly growing area is to increase the performance
including both activity and stability of LDH materials. Therefore,
the structure-performance and chemical composition-perfor-
mance correlations are addressed, which shed light on ways to
develop promising electrode materials and catalysts based on LDH
complexes in the future. In the final section, current challenges
and possible strategies are discussed from the viewpoint of mate-
rial design and performance. It is hoped that this review will attract
213
 RESEARCH
RESEARCH: Review
FIGURE 1
Schemes illustrating (a) the structure of carbonate-intercalated LDHs with the metal hydroxide octahedral layers stacked along the crystallographic c-axis, (b)
the anion exchange process of LDH, (c) the delamination/exfoliation of LDH into single layer nanosheets, and (d) the bottom-up synthesis of LDH
nanosheets in a reverse micelle.
more attention on LDH based nanomaterials and bring about
further developments in this exciting area.
Synthesis of LDH nanosheets
Generally, LDH materials can be prepared by direct precipitation
of mixed metal hydroxides in a solution. In theory, any divalent
and trivalent metal ions with radii close to that of Mg2+ can
constitute the host slabs of LDHs [24]. However, transition metals,
especially Fe3+, prone to form gel like hydroxides at low pH values
[25,26], making it difficult to synthesize transition metal based
LDHs by homogeneous precipitation. On the other hand, by using
urea or hexamethylenetetramine as hydrolysis agents, highly
crystallized TM-LDH microplates were hydrothermally synthe-
sized in a recent study [23]. The crucial point here is the progressive
hydrolysis of urea or hexamethylenetetramine that makes the
solution alkaline and induces homogenous nucleation and crys-
tallization of LDH materials. In addition to the hydrothermal
method, Ma et al. synthesized a series of TM-LDHs with a highly
crystalline hexagonal microplatelet structure through topo-chem-
ical transformation. The advantage of this method lies in the
rational control of the transition metal oxidation states in the
214
Materials Today  Volume 19, Number 4  May 2016
hydroxide precursors [5,24]. Recently, a facile direct electrochem-
ical deposition method and microwave assisted methods were also
used to synthesize LDH based materials including NiCo [17,27],
CoAl LDH [28,29], ZnCo LDH [30], etc., greatly broadening the
landscape of LDH synthesis. In addition to the nanoparticle or
nanoplate structures, LDH based core–shell [17,27,29], nanocone
[30] and nanoflower [31] structures have also been reported. By
studying the prototypes of ZnAl LDH and CoAl LDH, Forticaux
et al. [31] recently found that the growth of LDH was driven by
screw dislocations. By controlling and maintaining a low precursor
supersaturation, LDH nanoplates with well-defined morphologies
could be synthesized. In contrast, the uncontrolled overgrowth led
to the LDH to develop a nanoflower morphology.
Research on the applications of LDH materials continues to
expand crossing many disciplines, such as catalysts [3,20,32–36],
catalyst precursors [32,37,38], anion exchangers [39], and electro-
active/photoactive materials [2,15,18,35,36,40–56]. However,
many of the applications are limited in scope because of the
inaccessibility to the inner surfaces of the host layer. An effective
solution to this problem would be to synthesize LDHs nanosheets
with only a single highly anisotropic layer, which not only exhibit
Materials Today  Volume 19, Number 4  May 2016
high surface area but also fully expose the electrochemically active
sites [5,57,58]. The fabrication of LDH nanosheets can be generally
classified into bottom-up and top-down methods. The top-down
method relies on the exfoliation/delamination of bulk LDH into
single layer nanosheets, which starts with and enabled by the ion-
exchange intercalation involving an anionic surfactant to enlarge
the brucite interlayer distance and weaken the brucite interlayer
interaction (Fig. 1b) [5,57]. More often than not, the exfoliation/
delamination is carried out in a highly polar solvent, such as
butanol [57,59], acrylates [60], CCl4 and toluene [61–63], form-
amide [25,64–69], water [58,70–74] and other solutions (Fig. 1c)
[75,76], which can solvate the hydrophobic tails of the intercalat-
ed anions [5,57,77]. Therefore, several steps need to be taken to
overcome the high interlayer charge density as mentioned above
to achieve the full exfoliation/delamination of bulk LDH. Besides
the top-down method, LDH nanosheets can also be prepared via
the bottom-up synthesis. Typically, it begins with the introduction
of coprecipitation of an aqueous precursor solution into an oil
phase with a surfactant and a cosurfactant (Fig. 1d). The resulting
reverse micelles act as nanoreactors, in which LDH single layers
can be formed due to limited nutrients available in a confined
space. Through such controlled nucleation, MgAl LDH [78–80],
NiAl LDH [81], and CoAl LDH [82] monolayer species were suc-
cessfully synthesized. Notably, the control over the water and oil
phases as well as the metal salts is stringent in order to realize the
synthesis of LDH nanosheets by this method. Moreover, the
successfully synthesized LDH nanosheets by the bottom-up strat-
egy are still limited in both the production quantity and variety. So
till now, the top-down fabrication is thus far the most widely
developed and applied method for preparing LDH nanosheets.
More recently, a new kind of LDH complexes composed of LDH
nanosheets and 2D carbon materials including GO and rGO as
interlayer anions were reported [83,84]. Besides the high surface
area, the 2D heterostructure LDH complexes also showed extreme-
ly high electrochemical activity due to the direct contact between
catalytic metals and conductive carbons. TM-LDHs with intrinsic
electrochemical activities, when further increased by designing
suitable nanosheets structures, will be critical for the application of
LDHs in energy related processes, which will be discussed at some
length in the following section.
Applications of LDH materials in energy conversion and
storage processes
Because of the growing demand for energy and severe environ-
mental pollution from burning fossil fuels across the globe, energy
has become one of the most important topics nowadays [85–89].
The renewable and clean energy sources as well as advanced energy
storage devices, such as supercapacitors, lithium ion battery, and
metal-air batteries are in great demand and need innovative
developments. In these energy conversion and storage devices,
the electrodes are the most important parts that determine the
performance. In common knowledge, an efficient way to improve
the performance of electrodes is synthesis and design new elec-
trode materials with special structures, such as mesoporous mate-
rials, nanorods, nanowires, and nanosheets. Nanosheets, which
can not only increase the specific surface area of materials but
also decrease the diffusion distance for ions from the electrolyte to
the surface of active material due to the atomic to nanometer
RESEARCH
thickness, are attracting more and more attention. LDH, as men-
tioned above, is a kind of ionic lamellar compounds and can be
exfoliated/delaminated into single brucite layers with atomic
thicknesses, which meet the structural requirements of the elec-
trode materials. Moreover, various metal ions including electro-
chemically active transition metal ions, e.g., Fe, Ni, Co, and Mn,
can be octahedrally coordinated into the brucite layer, making the
LDH an electrochemical active material. In addition, the common
low electron conductivity problem of LDH can be overcome by
replacing the exchangeable charge compensating interlayer
RESEARCH: Review
anions by other functional anions such as graphene oxide (GO)
or oxidized carbon nanotube (CNT) that can be reduced to elec-
trically conductive carbon materials. Therefore, LDH based mate-
rials have a great potential application in energy conversion and
storage processes by adjusting the type of metal ions, the atomic
ratio of metal cations in brucite layer, the selection of suitable
interlayer anions, etc. In what follows, the fabrication of electrode
materials from LDHs nanosheets for the applications in catalysis
for electrochemical/photochemical water splitting, metal-air bat-
teries, and supercapacitors will be summarized.
Application in electrochemical catalysis toward water splitting
As an ideal energy carrier, hydrogen (H2) has been regarded as a
promising alternative to fossil fuels due to its lightweight, environ-
mentally benign oxidation product and high energy density
(143 kJ/g) [90–92]. One of the most efficient and attractive ways
of generating H2 is to split water with electricity or sunlight
[93–95]. The oxygen evolution reaction (OER) is the more critical
half-reaction of water splitting and involves demanding four
proton-coupled electron transfer (PCET) processes and one oxy-
gen–oxygen bond formation step, which are kinetically sluggish
and require speeding up by suitable catalysts [96–98]. Though
iridium dioxide (IrO2) and ruthenium dioxide (RuO2) are the state
of the art OER electrocatalysts [99–102], the elemental scarcity and
high cost greatly limit their utilization in water splitting indus-
tries. Therefore, the design and development of earth abundant
element based catalysts with high catalytic activity and stability
are of paramount importance and have attracted intense interests.
TM-LDH materials, particularly Ni- and Co-containing LDHs, are
the most promising candidates, which show advanced OER elec-
trocatalytic performance outshining other non-precious metal
based OER electrocatalysts.
Although LDHs have been widely used as supports for noble
metal based oxidation catalysts, it was not until 2013 that LDH on
its own was used as an OER electrocatalyst for the first time [103].
In that work, ZnCo LDH was synthesized and showed advanced
OER performance with a very low overpotential and a high turn-
over frequency (TOF), over 10 times higher than that of Co(OH)2
and Co3O4. The high catalytic performance was thought to result
from the relatively open structure of LDH that allows access to
more electrocatalytically active sites, faster diffusion of reactants/
products, and thus more rapid PCET processes. Before long, core–
shell structured CoNi LDH was synthesized from a CoNi hydroxide
precursor by a topotactic process using iodine as the oxidizing
agent [104]. A low overpotential was achieved by using the as
prepared CoNi LDH as a catalyst for OER without any sacrificial
agent. Both the presence of more Co active sites and the rapid
movement of interlayer ions within the layered structure were
215
 RESEARCH
RESEARCH: Review
FIGURE 2
(a) Schematic of exfoliating bulk LDH to form LDH monolayers. (b) XRD pattern of LDH with different anions and after the exfoliation processes. (c) LSV
curves of FeNi, NiCo, and CoCo LDH and the corresponding LDH monolayer nanosheets catalyzed OER in alkaline solution. Reprinted with permission from
Ref. [77]. Copyright 2014 Nature.
believed to be held responsible for the high performance. Recently,
Song et al. [77] prepared exfoliated LDH by an anion exchange
process followed by delamination in a formamide solution
(Fig. 2a). XRD measurements confirmed the successful anion
exchange and exfoliation processes (Fig. 2b). Moreover, all of
the exfoliated LDH nanosheets (NiFe, NiCo, and CoCo LDH)
exhibited a significantly improved OER electrocatalytic activity
than the corresponding bulk LDH with lower onset potentials
(Fig. 2c). Further along the line, Long et al. [36] synthesized
TM-LDH ultrathin nanosheets directly and found that the catalyt-
ic performance of binary LDH (FeNi LDH) could be tailored by
incorporating a third cation (Co2+). Interestingly, with the in-
crease of Co content, the FeNiCo LDH nanosheets showed in-
creased electrocatalytic performance on OER.
As mentioned above, TM-LDH compounds were not used as
OER catalysts until recently despite the early success in their
synthesis with high crystallinity [5,23]. One of the major problems
associated with the LDH materials in energy conversion processes
is their low conductivity. Researchers have attempted to solve the
problem by either hybridizing it with a conductive material or
directly growing LDH on conductive substrates including nickel
foam/Ni foil and carbon materials such as CNT, graphene, etc. or
growing LDH on the electrode substrates such as nickel foam,
carbon fiber cloth, etc. Li et al. [105] reported a binary ZnCo LDH
film grown directly on a conductive Ni foil by electrodeposition.
Due to the open structure and the easily accessible active sites on
the vertically grown LDH nanosheets, the as prepared film showed
a good OER performance in alkali solution with the TOF value of
3.56 s 1 at the overpotential of 0.7 V. Gong et al. [106] found that
FeNi LDH grown on mildly oxidized CNTs had advanced OER
216
Materials Today  Volume 19, Number 4  May 2016
performance that outperformed the commercial precious metal Ir
catalyst. The high performance was attributed to the intrinsic high
catalytic activity of NiFe LDH, the high conductivity of CNT
network, and the strong coupling between these two materials.
To overcome the tendency of aggregation, the insulating nature
and the poor stability of LDH nanosheets, ionic hetero-assembly of
hydroxide nanosheets of LDH and graphene, both being layered
materials, was proposed to realize the full potential of the two
combined. In the heterostructure, graphene, with an extremely
high specific surface area of 2600 m2/g in theory and good
electrical conductivity of 106 S/cm, enhanced charge transfer
and mass transport during the catalytic reaction [107,108]. More-
over, the face-to-face stacking of positively charged LDH
nanosheets and negatively charged graphene (oxide) at the mo-
lecular level enabled direct contact between catalytically active
transition metals and conductive sp [2] carbon atoms, which could
significantly shorten the diffusion distance. Following this line of
thinking, Long et al. [83] successfully designed and synthesized
such a superlattice electrocatalyst for water splitting through the
intercalation of GO nanosheets into the interlayers of FeNi LDH
nanosheets (Fig. 3a), which is essentially a 2D ionic heterostruc-
ture. After the reduction treatment, the FeNi LDH/rGO complex
showed excellent electrochemical catalytic performance on water
oxidation with an overpotential as low as 210 mV (Fig. 3b) and a
Tafel slope of 39 mV/dec (Fig. 3c). More recently, Ma et al. [84]
reported a follow-up work that confirmed the advanced OER
performance of the 2D heterostructure of FeNi LDH and graphene
and further found that the catalytic activity of the catalyst was
enhanced with increasing Fe content in the bimetallic NiFe
system.
Materials Today  Volume 19, Number 4  May 2016
FIGURE 3
(a) Scheme for the synthesis of FeNi LDH/GO hybrid. (b) LSV curves and (c) Tafel slopes of OER catalyzed by the as-prepared catalysts. Reprinted with
permission from Ref. [83]. Copyright 2014 Wiley-VCH.
Compared to the conventional 2D planar architecture, the 3D
porous architecture of electrode offers several advantages, includ-
ing facilitated electron transportation and electrolyte penetration
and increased electrochemically active surface area. Therefore,
synthesizing catalysts on 3D porous substrates and applying them
directly as the electrode, have also attracted much attention. Lu
et al. [18] reported a 3D film of vertically aligned NiFe LDH
nanoplates on nickel foam (Fig. 4) and used it directly as an
electrode for OER to overcome the limitation of low specific
surface area and conductivity of common catalysts. The as pre-
pared NiFe LDH film afforded a low onset potential of 1.46 V and a
fast current increase due to the synergistic effect of the intrinsi-
cally high activity of the catalyst and the unique 3D structure
(Fig. 4d). Soon after, Jiang et al. [55] synthesized NiCo LDH
nanosheet arrays on nickel foam and used as OER electrode as
well, again showing good OER activity and stability in an alkaline
medium. Yu et al. [109] further reported an electrodeposition
process to immobilize NiFe LDH nanoplates on 3D electrochemi-
cally reduced graphene oxide (rGO) for electrocatalyzing water
oxidation. The NiFe LDH was uniformly decorated on graphene
sheets and the electrochemical active surface area was 3.3 times
larger than that of a conventional planar electrode, resulting in a
good OER performance with a small overpotential of 0.259 V and
a low Tafel slope of 39 mV/dec.
RESEARCH
RESEARCH: Review
The specific activity of a catalyst for a target reaction largely
depends on the chemical composition and electronic structure of
the material. For OER, a low-level Fe doping was found to be
effective for enhancing the catalytic activities of Ni based hydro-
xides or oxides, possibly caused by the enhanced structural disor-
der and conductivity. As to ORR, Co and Fe ions are believed to be
the active centers with unique electronic structures in a specific
crystalline environment. Meanwhile, recent studies have recog-
nized Co-based compounds as bifunctional materials for OER/ORR
electrocatalysis. LDHs, for their wide tunability in terms of diverse
metal species, ratios of the intralayer metal ions and large inter-
layer spacing conducive to ion diffusion, should have a great
potential for the bifuncitional electrocatalysis. Ma et al. [84] firstly
found that the hybrid of exfoliated NiFe LDH and rGO not only
show excellent catalytic activity on OER with an overpotential as
low as 0.21 V and a Tafel slope of 40 mV/dec, it is also effective for
catalyzing HER. Later, Qian et al. [33] investigated both the OER
and the ORR performance of a trinary NiCoFe LDH. They found
that the preoxidation treatment of LDH increased the valence state
of cobalt ions from Co2+ to Co3+, leading to an improved conduc-
tivity of the material and the concomitant enhancement of both
the OER and ORR performance. The research on the bifunctional
catalytic properties of LDH is still in its infancy, fundamental
insights on the catalytic mechanisms should be gained by studying
217
 RESEARCH
RESEARCH: Review
FIGURE 4
(a) Scheme and (b) SEM image of the 3D film of vertically aligned NiFe LDH nanoplates grown on nickel foam as the OER working electrode. (c) Schematic
structure of NiFe LDH, which zooms in a small region in (a). (d) LSV curves of catalyzed OER by NiFe LDH, Ni(OH)2, Ni foam and Ir/C. Reprinted with
permission from Ref. [18]. Copyright 2014 The Royal Society of Chemistry.
the relationship among the catalytic performance, chemical com-
position and electronic structure of the LDH materials.
As mentioned above, LDH materials can be converted to mixed
metal oxides (MMO) nanocomposites after the thermal treatment.
Compared to the metal oxides made by traditional chemical and
physical method, the MMO nanocomposites made from LDH
precursors showed a uniform dispersion of metal ions as well as
a high surface area. Wang et al. [110] synthesized a class of Co3O4/
Co2MnO4 nanocomposite by calcination of a single source of
CoMn LDH. Due to the highly OER-active Co3O4 component
and the ORR-active Co2MnO4 component, the resultant nano-
composite showed excellent performance as a bifunctional cata-
lyst for both OER and ORR in alkaline solution, which was
comparable to that of precious metal catalysts. The advanced
catalytic activity was proposed to be attributed to the high surface
area and well-dispersed heterogeneous nanostructure of the nano-
composites. Recently, a Co/CoO/CoFe2O4/graphene composite
was produced by the same method using graphene supported
CoFe LDH as the precursor [111]. The as-prepared Co/CoO/
CoFe2O4/graphene composite exhibited comparable electrocata-
lytic activity and even better durability for ORR when compared
with the Pt/C catalysts, likely resulting from the high dispersion
and the strong coupling of the MMO nanocomposite on the
highly conductive graphene support. However, more in-depth
studies are needed to figure out the distribution of these metal
oxides and how they work as OER/ORR catalysts.
One of the most important applications for OER is water elec-
trolysis, which is a promising way of producing high-purity hy-
drogen gas yet at a low cost for fuel cell powered electric vehicles
with zero emission. By paring up the OER active LDH based
materials as the anode with other low-cost but active HER catalysts
as the cathode, overall water splitting devices were developed.
Gong et al. [112] firstly used a FeNi LDH catalyst and a NiO/Ni-CNT
complex as the anode and cathode of water splitting device
respectively. The as prepared device showed a current density of
20 mA/cm2 at a voltage as low as 1.5 V and a current density of
218
Materials Today  Volume 19, Number 4  May 2016
100 mA/cm2 at a voltage of 1.58 V at room temperature. Another
potential application of OER and ORR electrocatalysts is in re-
chargeable metal-air batteries, which have attracted much interest
as a possible energy storage system. With ample supply of oxygen
from the atmosphere, metal-air batteries have much higher theo-
retical energy density than traditional aqueous batteries and lithi-
um ion batteries. However, it is challenging to find active and
durable electrocatalysts on the cathode side, which are required to
catalyze ORR while discharging and OER while charging for the
rechargeable batteries. As mentioned above, FeNi based materials
are good OER electrocatalysts and thus can be used for recharge-
able Zn-air batteries, which often operate in an alkaline solution
containing dissolved zincate ions. Hence, a tri-electrode configu-
ration was taken, viz., FeNi LDH nanosheets were applied as the
OER catalyst for charging, an ORR catalyst of CoO/CNT served as
the cathode as in a conventional primary Zn-air battery, and Zn
foil was used as the anode, together forming a rechargeable Zn-air
battery (Fig. 5a) [113]. The resultant Zn-air battery showed an
extremely small charge-discharge polarization voltage of 0.7 V at
20 mA/cm2 (Fig. 5b,c), arising from the high performance of the
electrocatalysts used, which are featured by the novel phases of the
inorganic nanoparticles and the intimate bonding and electrical
wiring to the underlying CNT networks. Moreover, by separating
the OER and ORR electrodes for charging and discharging, respec-
tively, the problem of the reduced ORR catalytic activity can be
resolved, leading to an excellent cycling stability of the as prepared
Zn-air battery with a negligible voltage change during the charging
and discharging processes (Fig. 5c,d). This exemplifies the impor-
tance of finding advanced electrocatalysts for OER/ORR on
the electrode and designing suitable battery architectures for
the practical applications of energy conversion devices. Despite
the preliminary success of using LDH materials as OER/ORR elec-
trocatalysts for energy conversion/storage devices, many issues
remain to be addressed, such as the dendritic growth of Zn metal
on charging and CO2 management, before Zn-air batteries can be
deployed for practical applications.
Materials Today  Volume 19, Number 4  May 2016
FIGURE 5
The rechargeable Zn-air battery in a tri-electrode configuration. (a) A scheme of the tri-electrode with CoO/N-CNT ORR catalyst and NiFe LDH OER catalyst
for discharge and charge, respectively. (b) Charge and discharge polarization curves of the batteries. Cycling performance of the battery at 20 mA/cm2 and a
20 h cycle period (c), and at 50 mA/cm2 and a 4 h cycle period (d). Reprinted with permission from Ref. [113]. Copyright 2013 Nature.
Application in photochemical/photoelectrochemical energy
conversion processes
The notion of using sunlight to split water into H2 and O2 is
appealing and has attracted great interest. However, most of the
developed photocatalysts are only effective under UV light be-
cause of their wide bandgap energy and mismatched valence band
(VB) position. An efficient way to change the band structure of the
material is to tune its chemical composition. As mentioned above,
diverse transition metal ions can be stabilized in the octahedral
sites of an LDH lattice, making the chemical composition of LDH
tunable for photocatalytic water splitting. Silva et al. [48] synthe-
sized a series of ZnTi, ZnCe, and ZnCr LDHs at different Zn/Metal
atomic ratios (from 4:2 to 4:0.25) and tested them for the visible
light photocatalytic oxygen generation. The most active material
was found to be ZnCr LDH with an atomic ratio of 4:2, and the
quantum yields for oxygen generation were measured to be as high
as 60.9% and 12.2% at the two maximum absorption bands of
410 nm and 570 nm, respectively. Moreover, the overall efficiency
of ZnCr LDH for visible light induced oxygen generation was 1.6
times higher than that of WO3 under the same conditions, dem-
onstrating the intrinsic high photocatalytic activity of the LDH
materials on visible light induced water splitting, which was
attributed to the structural features that allow water sorption
inside the particles and the light absorption properties of the
LDH in the visible spectral range. Recently, hierarchical nanowire
arrays based on TiO2 core–NiCr LDH shell [114] and ZnO core–
CoNi LDH shell [17] were reported, which showed a largely en-
hanced photoelectrochemical water splitting performance with
high photocurrent density as well as stability. The excellent
RESEARCH
RESEARCH: Review
performance was attributed to the successful integration of photo-
generated electron–hole separation originating from the semicon-
ductor core and the excellent electrocatalytic activity of TM-LDH
shell.
The advent of perovskite solar cells with high power conversion
efficiency and high photovoltage triggered exploration into the
feasibility of using them for designing tandem water splitting
devices. By using two perovskite solar cells in tandem each with
a high open-circuit voltage of 1.06 V, sufficient to drive water
splitting, and a bifunctional electrocatalyst of NiFe LDH, for
greatly decreasing the overpotentials of both OER and HER, Luo
et al. [115] reported a highly efficient and low-cost water splitting
cell (see Fig. 6a). The as assembled cell yielded a water splitting
photocurrent density of 10 mA/cm2, corresponding to a solar-
to-hydrogen efficiency of 12.3% (Fig. 6b). This work provided an
appealing archetype for designing advanced water splitting cells.
In prospect, alternative architectures, such as those obtained by
directly attaching the catalysts onto the back sides of solar cells to
form an integrated system instead of wiring the solar cells with the
Ni foam electrodes as in the aforementioned work, could be
practicable in the future.
Titanium based materials are perhaps the best known photo-
catalysts for water splitting under UV light illumination, however,
they are inefficient under visible light irradiation for their wide
bandgap. Lee et al. [116] combined the advantages of titania and
LDH by synthesizing a new type of titanium-embedded LDH–NiTi
LDH and CuTi LDH. Different from the fact that pure titanium
oxide only absorbs in the UV region, the prepared titanium-
embedded LDH exhibited two absorption bands in the red and
219
 RESEARCH Materials Today  Volume 19, Number 4  May 2016
RESEARCH: Review

FIGURE 6
The combination of a perovskite tandem cell with a NiFe LDH/Ni foam electrode for sunlight-induced water splitting. (a) Schematic of the device and the
relevant energy levels. (b) J–V curves of the perovskite tandem cell under dark and simulated AM 1.5 G 100 mW/cm2 illumination, and of the NiFe/Ni foam
electrode based water-splitting cell in a two-electrode configuration. Reprinted with permission from Ref. [115]. Copyright 2014 AAAS.

blue regions under visible light. Moreover, the NiTi LDH showed a
very high reaction rate due to the high surface area, producing
49 mmol O2 in 5 h, whereas the pure TiO2 only generated a very
small amount of O2 within the measurement error range. Plausi-
bly, the visible absorption band range and the large surface area of
the titanium-embedded LDH could result in the high water oxi-
dation photocatalytic activity under visible light. Subsequently,
Gunjakar et al. [117] reported a mesoporous ordered nanohybrid
fabricated by self-assembly between oppositely charged 2D
nanosheets of ZnCr LDH and layered titanium oxide (Fig. 7).
Besides the intact in-plane atomic arrangement and the electronic
structures of the components, the obtained heterolayered
nanohybrids showed a strong absorption of visible light but a
remarkably quenched photoluminescence signal, signaling an
effective electronic coupling between the two component
nanosheets. Moreover, the porosity of the nanohybrid could be
controlled by changing the ratio of layered titanate/ZnCr LDH,
resulting in a high surface area of the hybrid. Indeed, the nanohy-
brid has proved to be highly active for visible light induced O2
generation with a rate of 1.18 mmol/h/g, demonstrating the effec-
tiveness of improving the photocatalytic activity through the or-
dered self-assembly between the inorganic component nanosheets.
Considering that nanostructured carbon species such as gra-
phene, rGO and CNT can act as good acceptors of photoinduced

FIGURE 7
(a) TEM image of mesoporous ordered nanohybrid of ZnCr LDH and layered titanium oxide. (b) Enlarged TEM image of the area indicated by the white
rectangle in (a) and corresponding scheme to describe the alternatively stacked of LDH and titanate. Reprinted with permission from Ref. [117]. Copyright
2011 American Chemical Society.

220
Materials Today  Volume 19, Number 4  May 2016
FIGURE 8
(a) Schematic of ZnCr LDH grown on graphene. (b) TEM image of the
nanohybrid of ZnCr LDH and graphene oxide. Reprinted with permission
from Ref. [118]. Copyright 2013 The Royal Society of Chemistry.
electrons, the hybridization of LDH with these species provides an
alternative effective way to enhance the photocatalytic efficiency
of catalysts through depression of charge recombination. For
example, the hybrid of ZnCr LDH/rGO showed greatly increased
photocatalytic activity for visible light induced O2 generation with
a rate of 0.5 mmol/h/g [118]. The positively charged ZnCr LDH
nanoplates were immobilized on the surface of negatively charged
rGO nanosheets, forming a highly porous stacked structure
(Fig. 8). The intimate contact of subnanometer-thick ZnCr LDH
nanoplates with rGO resulted in strong electron coupling of these
two materials, leading to the high catalytic performance of the
nanohybrid.
LDH materials have also been used as photocatalysts for con-
version of CO2 into CO and carbon/hydrogen rich molecules such
as HCOOH, HCHO, CH3OH and CH4 [34,35,119,120]. The photo-
catalytic conversion of CO2 is attractive from the viewpoint of
sustainable energy production and greenhouse gas reduction. In
2011, copper modified LDH was found to show activity for the
photocatalytic conversion of CO2 in the presence of H2, in which
LDH was used as a CO2 adsorbent while Cu species acted as
catalytic active sites [119]. Later, the photocatalytic reduction
of CO2 into methanol was reported by using ZnGa or ZnCuGa
LDH in the presence of hydrogen and it was found that the partial
desorption of structural water stuffed between the cationic layers
promoted the photocatalytic performance that was further in-
creased by replacing the interlayer carbonate anions with
[Cu(OH)4]2 [35]. Recently, Teramura et al. [34] investigated
the intrinsic photocatalytic performance of various LDH materi-
als with M2+/M3+ = 3 (M2+ = Mg2+, Zn2+, Ni2+; M3+ = Al3+, Ga3+,
In3+) on conversion of CO2 in water. They found that the surface
base sites of LDH had high water tolerance and showed superior
activity for the photocatalytic conversion of CO2 into CO. More
recently, the photocatalytic reaction mechanism for the conver-
sion of CO2 into methanol and CO using LDH containing Zn, Cu,
and Ga were investigated by extended X-ray absorption fine
structure (EXAFS) [120]. By monitoring the structure of active
sites on LDH and the diffusion of photogenerated electrons, it
was found that the photogenerated e trapping at the Cu sites was
fast enough to achieve the CO2 conversion. Moreover, the elec-
tron diffusion to Cu sites was an order of magnitude faster in
the direction of the cationic layers than in the perpendicular
direction.
RESEARCH
Application in supercapacitors
Supercapacitors (SCs), also called electrochemical capacitors (ECs),
are considered as a promising modality for energy storage because
of high power density, low maintenance cost, and long cycle life
[121–123]. The common drawback of low energy density may be
overcome by the so-called pseudocapacitors (PCs), a type of ECs
that utilize the faradic redox reaction of active materials including
transition metal hydroxides [46,124–126], transition metal oxides
[127–130], and polymers [131–133]. The specific capacitance and
energy density of such PCs have kept increasing [123,134–136].
RESEARCH: Review
The first thin film electrode for SC application fabricated from
delaminated LDH nanosheets was reported by Wang et al. [42] in
2007. The highly oriented and densely packed thin film was
obtained by drying a transparent colloidal suspension of CoAl
LDH nanosheets (delaminated in formamide) on a pretreated ITO-
coated glass plate substrate. Electrochemical investigations
showed that this thin film electrode had a good supercapacitor
behavior with a high specific capacitance up to 2000 F/cm3 (667 F/
g). The good electrochemical behavior was attributed to its special
microstructure, which had an open framework and highly exposed
electrochemically active Co sites, and hence resulted in a massive
utilization of electrochemical active materials and gave a high
specific capacitance. In a similar way, a ZnCo LDH thin film
electrode for supercapacitor application was also fabricated [51].
It is known that building a hierarchical micro-/nanostructure with
high specific surface area could greatly enhance the performance
of SCs. Along this line, NiAl LDH with porous structure were
developed by solvothermal method using ethanol as solvent.
The effective utilization of active Ni ions due to the porous
structure and high surface area for charge transfer reaction greatly
improved the specific capacitance of NiAl LDH [54]. Later, Shao
et al. [53] synthesized NiAl LDH microspheres with tunable interi-
or architectures and found that the microspheres with hollow
interior structure exhibited excellent pseudocapacitance perfor-
mance, including high specific capacitance and rate capability,
good charge/discharge stability and long-term cycling life, owing
to the greatly improved faradic redox reaction and mass transfer.
Besides nickel ion, cobalt ions are also active elements for revers-
ible faradic reactions; therefore, NiCo LDH materials were pre-
pared and investigated as electrodes of supercapacitors. It was
found that the chemical composition of NiCo LDH has significant
effects on the specific capacitances [43,47,137], and the highest
value of 2104 F/g at a current density of 1 A/g was obtained when
the Ni/Co ratio was fixed at 3/7 [43].
Although the transition metal hydroxides have high pseudoca-
pacitance and fast redox kinetics, the low mechanical stability and
cycle life may limit their application. Moreover, compared to
lithium ion batteries, the energy storage capability of SCs is still
low. It is highly desirable to improve the energy density of PCs
toward that of batteries as well as to improve the cycle life. To
tackle these problems, carbon materials have been introduced into
LDH with a view to enhance the power densities and life cycles of
PCs. The carbon materials/LDH composites that have been
explored including multiwall CNT/LDH [45], graphene/LDH
[49,50,138–141], GO/LDH [52,28] carbon nanoparticle/LDH
[41,142], and graphene nanocup/LDH [143]. For example, Xin
et al. [52] fabricated a layered composite by assembling carboxyl-
ated GO and CoAl LDH nanosheets and applied it as an electrode
221
 RESEARCH
RESEARCH: Review
FIGURE 9
(a) Schematic of the formation and structure of the CoAl LDH/GO composite. (b) Cross-sectional SEM image of the CoAl LDH/GO composite. (c) Specific
capacitance of the composite at various discharge current densities. (d) Average capacitance of the composite at various scan rates. Reprinted with
permission from Ref. [52]. Copyright 2011 The Royal Society of Chemistry.
material for a pseudocapacitor (Fig. 9). The LDH/GO composites
showed excellent performance in energy storage, e.g., a high
specific capacitance of 1031 F/g at a current density of 1 A/g
and a high energy density of 7.7 W h/kg at power density of
4.8 kW/kg. The high performance was attributed to the fact that
face-to-face assembly of the CoAl LDH nanosheets and GO maxi-
mized the area of close contact and hence led to an efficient
electron transport during the faradic redox reaction. Recently,
Zhao et al. [14] reported a hierarchical nanostructure composed
of NiMn LDH microcrystals grafted on CNT backbone by an in situ
growth route and studied its supercapacitive performance. The
electrochemical investigation showed that the NiMn LDH/CNT
electrode was rather active, and delivered a maximum specific
capacitance of 1960 F/g at 1.5 A/g, an excellent rate capability of
79.5% retention at 30 A/g, and a good cyclic stability.
As another way to promote performance of the PCs, TM-LDH
materials were also grown directly on 3D substrates and applied as
the electrode of supercapacitors. Through a combined vapor de-
position and electrochemical deposition method, a novel ultra-
thin NiCo LDH nanoflakes on conducting ZTO nanowires were
synthesized [144]. The composite exhibited outstanding electro-
chemical performance with a high specific capacitance of 1805 F/g
at a current density of 0.5 A/g and an excellent rate performance of
1275 F/g at a current density of 100 A/g. Later, a series of flexible
nanocomposite electrodes were fabricated by electrodeposition
of CoNi LDH nanosheets on porous NiCo2O4 nanowires grown
radially on carbon fiber paper for supercapacitors and showed
222
Materials Today  Volume 19, Number 4  May 2016
increased performance [145]. Recently, Chen et al. [13] reported
a facile and novel one step method of growing NiCo LDH hybrid
films with ultrathin nanosheets and porous nanostructure on
nickel foam and applied it as a pseudocapacitor (Fig. 10). The
as-obtained NiCo LDH hybrid film based electrodes displayed a
significantly enhanced specific capacitance (2682 F/g at 3 A/g) and
energy density (77.3 Wh/kg at 623 W kg). Moreover, with the
NiCo LDH film as the positive electrode and porous freeze-dried
rGO as the negative electrode, the as-fabricated asymmetric super-
capacitor showed an ultrahigh energy density of 188 Wh/kg at an
average power density of 1499 W/kg based on the mass of active
materials. Apparently, the high SC performance resulted from the
highly oriented layered single crystal structure and the ultrathin
nature of the hybrid nanosheets as well as the well-defined porous
nanostructure.
Mechanistic studies
A variety of LDH based nanomaterials have been developed with
excellent properties useful for many energy conversion and stor-
age processes. As already presented above, they can work as
catalysts for OER, ORR and HER and as electrode materials for
supercapacitors. The uniformly distributed metal ions at the atom-
ic level and relatively open structure that facilitate the transporta-
tion of charges and electrolytes are proposed to be two advantages
of LDH based materials used in energy conversion and storage
devices. Moreover, hybridizing LDH nanosheets with conductive
carbon materials, the low conductivity of LDH that is a common
Materials Today  Volume 19, Number 4  May 2016
FIGURE 10
(a) The formation of NiCo LDH film on Ni foam and the illustration scheme of the asymmetrical supercapacitor. (b) SEM image of the formed NiCo LDH film.
(c) CV curves of the NiCo LDH hybrid-, nickel hydroxide-, and cobalt hydroxide-based electrodes at a scan rate of 10 mV/s. (d) Cs of NiCo LDH/rGO
asymmetric supercapacitor at different current densities. Reprinted with permission from Ref. [13]. Copyright 2014 Wiley-VCH.
problem for a hydroxide, could be solved and hence increase the
electrochemical performance. However, the detailed mechanisms
for working of the novel LDH materials in these processes still
largely remain to be unraveled. The difficulty comes from the
lacking of advanced techniques to access in operando the infor-
mation about the reaction pathways and the structures of the
active sites. However, great efforts are still being vigorously
made to understand the structural and compositional relevance
to the electronic structures and to the device performance in order
to expedite the development of the LDH based materials.
As OER catalysts, LDH materials showed much better perfor-
mance than the corresponding single metal hydroxides. Corrigan
and Bendert first attributed the improved activity of Ni(OH)2 after
Fe incorporation to the improvement in electrical conductivity
[146]. The enhanced conductivity was later confirmed by steady
state in situ film conductivity measurements, but the huge over-
potential difference at low current densities cannot be explained
by a more conducting Fe-incorporated film [147]. Different types
of in situ spectroscopy have recently attracted increasing atten-
tion as useful tools for probing the catalyst while operating
under catalytic conditions. In situ extended X-ray absorption
fine structure revealed that under OER conditions, the average
coordination number of Fe atoms increases, corroborating the
participation of Fe in enhancing the OER catalytic activity [32].
RESEARCH
RESEARCH: Review
Later, Oliver-Tolentino et al. [148] synthesized LDHs with differ-
ent Ni/Fe ratios and found that the iron content in the structure
played an important role on their magnetic properties and pos-
tulated that superexchange interaction was one of the main
causes that promoted the enhancement of the NiFe LDH catalytic
activity toward OER.
In general, the activity of transition metal based OER catalysts
are thought to relate to the 3d electron number and the electronic
configuration of transition metal ions involved in the catalysis, the
enthalpy for the lower to higher oxide transition, and the surface
oxygen binding energy [149–151]. Early in 1980s, Trasatti et al.
[149,152] reported a series of works on the OER mechanisms on
rutile, spinel, and perovskite oxides. By focusing on oxide proper-
ties that reflect the nature of the metal–oxygen bond strength,
they found a volcano relationship between the enthalpy of transi-
tion from a lower to a higher oxidation state and the OER over-
potential for binary oxides (Fig. 11a) [149,152]. In fact, this finding
is in the spirit of the Sabatier principle, that is, an optimal catalyst
should bind neither too strongly nor weakly to oxygen. This
principle might also be suitable for the rational design of other
transition metals based OER catalysts such as the TM-LDH materi-
als reviewed here. By and large, identifying the relationship be-
tween the OER activity and the catalyst electronic structure
is important for gaining mechanistic insights and finding new
223
 RESEARCH
RESEARCH: Review
FIGURE 11
Volcano trends of OER catalysis. (a) OER overpotential of binary oxides reported by Trasatti as a function of the enthalpy (from Mn+ to M(n+1)+). Reprinted
with permission from Ref. [149] Copyright 1980 Elsevier. (b) OER overpotentials as a function of the eg electron occupancy of various perovskites. Reprinted
with permission from Ref. [150] Copyright 2011 AAAS.
design strategies for the LDH catalysts of OER. Suntivich et al. [150]
examined more than 10 transition metal oxides and found that
the intrinsic OER activity exhibited a volcano-shaped dependence
on the occupancy of the 3d electron orbital of eg symmetry of
transition metal cations on the catalyst surface, peaking at an eg
occupancy close to unity (Fig. 11b). Similar results were found in
transition metal multiple hydroxides based OER catalysts by Long
et al. [36] recently. Specifically, the introduction of a third transi-
tion metal of Co into FeNi LDH resulted in a pronounced increase
in OER performance. From the XPS results, it was found that the
Co 2p feature of FeNiCo LDH was best fitted to Co2+ and Co3+ spin–
orbit doublets with electronic structures of t2g6eg1 and t2g5eg1
respectively. Moreover, the Ni 2p region was positively shifted
and besides Ni2+, Ni3+ with electronic configuration of t2g6eg1
could also be deconvoluted. Therefore, the authors proposed that
in addition to the increased surface area and conductivity of the
catalysts, the modulated electronic structures of the transition
metal centers with eg filling close to unity may also contribute
to the improved OER activity.
For the TM-LDHs to work as electrode materials of supercapa-
citor, the chemical composition, viz., the identity of M, the molar
ratio of M2+/M3+, etc., and the morphology of LDH have large roles
to play. For example, the LDH with bi-active elements (such as
CoNi LDH, FeNi LDH, CoMn LDH, etc.) showed better perfor-
mance than the LDH with single active component (such as AlNi
LDH, CoZn LDH, etc.). Moreover, suitable M2+/M3+ ratio is also
important for the electrode performance. On the other hand, LDH
microspheres with hollow interior structure exhibited higher spe-
cific capacitance and rate capability, better charge/discharge per-
formance and long-term cycling life, owing to the greatly
improved faradic redox reaction and mass transfer kinetics than
other morphologies. However, as far as we know, the detailed
information on LDH active sites in the electrocatalytic processes
that would cast new light on the reaction mechanism has not been
reported and sorely need further investigation.
224
Materials Today  Volume 19, Number 4  May 2016
Conclusion and outlook
Various kinds of LDHs and LDH based composites have been
successfully fabricated and widely applied in the fields of energy
conversion and storage. In this article, we are attempting to sum-
marize the synthesis method of LDH nanosheets and their applica-
tion in energy conversion areas such as electrocatalysis, PEC water
splitting, supercapacitor, metal-air batteries, etc. The good perfor-
mance of the LDH based materials arises from the wide tunability of
metal cations and M2+/M3+ ratio, uniform distribution of electro-
chemical active transition metal ions at the atomic level and
the layered structure. More importantly, the much more exposed
active sites arising from exfoliation/delamination of bulk LDH into
the ultrathin single layer nanosheets, and the design of hybrid LDH/
conductive materials further enhance the electrochemical perfor-
mance of the LDH based materials. In addition, attempts to study
the mechanism of LDH based compounds in energy conversion and
storage processes have also been made. It has been found that the
better electrochemical performance of FeNi LDH than the single
metal hydroxide of Ni(OH)2 results from the improved electron
conductivity by the incorporation of the iron ions and the addition
of the third cation of Co can further tune the electronic structure of
catalytic active sites, leading to further improved performance of
LDH materials. Although much success has been achieved in de-
signing and synthesizing LDH based materials for energy conver-
sion and storage applications, daunting challenges still remain to
achieve a precise control over the structure of LDH based materials
on multiple-length scales and identify the active sites during the
operating processes. Looking ahead, efforts are still needed to design
and synthesize low cost and high quality LDH based materials to
meet the requirements of applications. These include controlling
the chemical composition, size and morphology, preventing aggre-
gation of the delaminated LDH nanosheets in solvents and deposit-
ing/patterning the LDH-based materials on electrode surfaces on
demand with good control. Meanwhile, it is also important to make
the synthesis processes greener and more environmental benign.
Materials Today  Volume 19, Number 4  May 2016 RESEARCH

Furthermore, to facilitate the design of novel high-performance [54] Y. Song, et al. Microporous Mesoporous Mater. 148 (2012) 159–165.
[55] J. Jiang, et al. J. Power Sources 278 (2015) 445–451.
LDH materials for energy conversion and storage, new characteri-
[56] W. He, et al. J. Mater. Chem. A 3 (2015) 17977–17982.
zation techniques need to be developed and deployed to understand [57] M. Adachi-Pagano, et al. Chem. Commun. (2000) 91–92.
the nature of active sites, the synergistic effects among the active [58] T. Hibino, M. Kobayashi, J. Mater. Chem. 15 (2005) 653–656.
sites, especially in systems with a heterogeneous composition, and [59] M. Singh, et al. J. Mater. Chem. 14 (2004) 871–874.
[60] S. O’Leary, et al. Chem. Commun. (2002) 1506–1507.
the underlying catalytic reaction mechanisms. These studies will be [61] M. Jobbágy, A.E. Regazzoni, J. Colloid Interface Sci. 275 (2004) 345–348.
of crucial significance for the LDH-based materials to make a big [62] V.V. Naik, et al. J. Phys. Chem. Lett. 2 (2011) 1193–1198.
impact in energy arenas in the future. [63] V.V. Naik, S. Vasudevan, Langmuir 27 (2011) 13276–13283.
[64] R. Ma, et al. J. Mater. Chem. 16 (2006) 3809–3813.
[65] T. Hibino, W. Jones, J. Mater. Chem. 11 (2001) 1321–1323.
Acknowledgements

RESEARCH: Review
[66] T. Hibino, Chem. Mater. 16 (2004) 5482–5488.
This work was supported by the NSFC/RGC Joint Research Scheme [67] L. Li, et al. Chem. Mater. 17 (2005) 4386–4391.
(N_HKUST610/14) and the HK-RGC General Research Funds [68] Q. Wu, et al. J. Mater. Chem. 15 (2005) 4695–4700.
[69] G. Abellán, et al. J. Mater. Chem. 20 (2010) 7451–7455.
(HKUST 606511).
[70] E. Gardner, et al. Adv. Mater. 13 (2001) 1263.
[71] C. Jaubertie, et al. Chem. Mater. 18 (2006) 3114–3121.
References [72] M. San Román, et al. Solid State Sci. 10 (2008) 1333–1341.
[1] P.J. Sideris, et al. Science 321 (2008) 113–117. [73] W. Hou, et al. Colloids Surf. A 312 (2008) 92–98.
[2] Q. Wang, D. O’Hare, Chem. Rev. 112 (2012) 4124–4155. [74] G. Manohara, et al. Langmuir 26 (2010) 15586–15591.
[3] G. Fan, et al. Chem. Soc. Rev. 43 (2014) 7040–7066. [75] Y. Zhao, et al. J. Mater. Chem. 21 (2011) 4869–4874.
[4] S. He, et al. Chem. Commun. 49 (2013) 5912–5920. [76] C.R. Gordijo, et al. J. Solid State Chem. 180 (2007) 1967–1976.
[5] Z. Liu, et al. J. Am. Chem. Soc. 128 (2006) 4872–4880. [77] F. Song, X. Hu, Nat. Commun. 5 (2014).
[6] N. Iyi, et al. Chem. Lett. 34 (2005) 932–933. [78] G. Hu, et al. Chem. Commun. (2006) 287–289.
[7] N. Iyi, et al. Chem. Lett. 33 (2004) 1122–1123. [79] G. Hu, D. O’Hare, J. Am. Chem. Soc. 127 (2005) 17808–17813.
[8] N. Iyi, et al. Chem. Mater. 16 (2004) 2926–2932. [80] G. Hu, et al. J. Mater. Chem. 17 (2007) 2257–2266.
[9] B. Sels, et al. Nature 400 (1999) 855–857. [81] M.E. Pérez-Bernal, et al. J. Solid State Chem. 182 (2009) 1593–1601.
[10] C. Nyambo, et al. J. Mater. Chem. 18 (2008) 4827–4838. [82] C.J. Wang, et al. Chem. Mater. 23 (2010) 171–180.
[11] C. Manzi-Nshuti, et al. Polym. Degrad. Stab. 94 (2009) 782–788. [83] X. Long, et al. Angew. Chem. 126 (2014) 7714–7718.
[12] A. Alcantara, et al. J. Mater. Chem. 20 (2010) 9495–9504. [84] W. Ma, et al. ACS Nano 9 (2015) 1977–1984.
[13] H. Chen, et al. Adv. Funct. Mater. 24 (2014) 934–942. [85] T.R. Cook, et al. Chem. Rev. 110 (2010) 6474–6502.
[14] J. Zhao, et al. Adv. Funct. Mater. 24 (2014) 2938–2946. [86] A. Kudo, Y. Miseki, Chem. Soc. Rev. 38 (2009) 253–278.
[15] Y. Wang, et al. J. Power Sources 184 (2008) 682–690. [87] N.S. Lewis, D.G. Nocera, Proc. Natl. Acad. Sci. U. S. A. 103 (2006) 15729–15735.
[16] S. Huang, et al. ACS Appl. Mater. Interfaces 4 (2012) 2242–2249. [88] M.G. Walter, et al. Chem. Rev. 110 (2010) 6446–6473.
[17] M. Shao, et al. Adv. Funct. Mater. 24 (2014) 580–586. [89] H. Wang, H. Dai, Chem. Soc. Rev. 42 (2013) 3088–3113.
[18] Z. Lu, et al. Chem. Commun. 50 (2014) 6479–6482. [90] G.W. Crabtree, et al. Phys. Today 57 (2004) 39–44.
[19] F. Song, X. Hu, J. Am. Chem. Soc. 136 (2014) 16481–16484. [91] M. Dresselhaus, I. Thomas, Nature 414 (2001) 332–337.
[20] Y. Zhao, et al. ACS Nano 3 (2009) 4009–4016. [92] A. Pandey, Biofuels: Alternative Feedstocks and Conversion Processes, Academic
[21] X. Xiang, et al. Rev. Adv. Sci. Eng. 3 (2014) 158–171. Press, 2011.
[22] H.B. Yao, et al. Angew. Chem. Int. Ed. 49 (2010) 10127–10131. [93] M. Carmo, et al. Int. J. Hydrogen Energy 38 (2013) 4901–4934.
[23] Y. Han, et al. Chem. Mater. 20 (2007) 360–363. [94] J.D. Holladay, et al. Catal. Today 139 (2009) 244–260.
[24] R. Ma, et al. J. Am. Chem. Soc. 129 (2007) 5257–5263. [95] K. Zeng, D. Zhang, Prog. Energy Combust. Sci. 36 (2010) 307–326.
[25] Z. Liu, et al. Langmuir 23 (2007) 861–867. [96] M.T. Koper, J. Electroanal. Chem. 660 (2011) 254–260.
[26] Y. Xu, et al. Chem. Mater. 14 (2002) 3844–3851. [97] M.W. Kanan, D.G. Nocera, Science 321 (2008) 1072–1075.
[27] Z. Zhao, et al. Adv. Funct. Mater. 24 (2014) 4698–4705. [98] V.I. Birss, et al. J. Electrochem. Soc. 133 (1986) 1621–1625.
[28] J. Fang, et al. Electrochim. Acta 85 (2012) 248–255. [99] D. Galizzioli, et al. J. Appl. Electrochem. 4 (1974) 57–67.
[29] Y. Dou, et al. Adv. Funct. Mater. 25 (2015) 2243–2249. [100] Y. Lee, et al. J. Phys. Chem. Lett. 3 (2012) 399–404.
[30] X. Liu, et al. Adv. Mater. 24 (2012) 2148–2153. [101] C.C. McCrory, et al. J. Am. Chem. Soc. 135 (2013) 16977–16987.
[31] A. Forticaux, et al. Nano Lett. 15 (2015) 3403–3409. [102] H. Over, Chem. Rev. 112 (2012) 3356–3426.
[32] J. Landon, et al. ACS Catal. 2 (2012) 1793–1801. [103] X. Zou, et al. J. Am. Chem. Soc. 135 (2013) 17242–17245.
[33] L. Qian, et al. Adv. Energy Mater. (2015), http://dx.doi.org/10.1002/aenm. [104] Y. Zhang, et al. Phys. Chem. Chem. Phys. 15 (2013) 7363–7369.
201500245. [105] Y. Li, et al. J. Mater. Chem. A 2 (2014) 13250–13258.
[34] K. Teramura, et al. Angew. Chem. 124 (2012) 8132–8135. [106] M. Gong, et al. J. Am. Chem. Soc. 135 (2013) 8452–8455.
[35] N. Ahmed, et al. Catal. Today 185 (2012) 263–269. [107] M.D. Stoller, et al. Nano Lett. 8 (2008) 3498–3502.
[36] X. Long, et al. Chem. Commun. 51 (2015) 1120–1123. [108] G. Hong, et al. Chem. Rev. (2015), http://dx.doi.org/10.1021/acs.chemrev.
[37] Q. Wu, et al. Electrochem. Commun. 5 (2003) 878–882. 5b00008.
[38] Y. Lu, Y. Zhao, Particuology 8 (2010) 202–206. [109] X. Yu, et al. J. Mater. Chem. A 3 (2015) 6921–6928.
[39] F. Millange, et al. Chem. Mater. 12 (2000) 1990–1994. [110] D. Wang, et al. Nanoscale 5 (2013) 5312–5315.
[40] Y. Lu, et al. J. Solid State Chem. 180 (2007) 1775–1782. [111] R. Huo, et al. Nanoscale 6 (2014) 203–206.
[41] L.H. Su, X.G. Zhang, J. Power Sources 172 (2007) 999–1006. [112] M. Gong, et al. Nat. Commun. 5 (2014).
[42] Y. Wang, et al. Electrochem. Solid-State Lett. 10 (2007) A233–A236. [113] Y. Li, et al. Nat. Commun. 4 (2013) 1805.
[43] V. Gupta, et al. J. Power Sources 175 (2008) 680–685. [114] W. He, et al. ChemSusChem 8 (2015) 1568–1576.
[44] J. Liu, et al. Adv. Funct. Mater. 18 (2008) 1448–1458. [115] J. Luo, et al. Science 345 (2014) 1593–1596.
[45] L.H. Su, et al. J. Solid State Electrochem. 12 (2008) 1129–1134. [116] Y. Lee, et al. Energ. Environ. Sci. 4 (2011) 914–920.
[46] G.W. Yang, et al. Chem. Commun. (2008) 6537–6539. [117] J.L. Gunjakar, et al. J. Am. Chem. Soc. 133 (2011) 14998–15007.
[47] Z.A. Hu, et al. Electrochim. Acta 54 (2009) 2737–2741. [118] J.L. Gunjakar, et al. Energ. Environ. Sci. 6 (2013) 1008–1017.
[48] C.G. Silva, et al. J. Am. Chem. Soc. 131 (2009) 13833–13839. [119] N. Ahmed, et al. J. Catal. 279 (2011) 123–135.
[49] X. Dong, et al. Langmuir 28 (2011) 293–298. [120] M. Morikawa, et al. Appl. Catal. B: Environ. 144 (2014) 561–569.
[50] Z. Gao, et al. Chem. Mater. 23 (2011) 3509–3516. [121] M. Winter, R.J. Brodd, Chem. Rev. 104 (2004) 4245–4270.
[51] M.A. Woo, et al. J. Mater. Chem. 21 (2011) 4286–4292. [122] A. Burke, J. Power Sources 91 (2000) 37–50.
[52] Y.D. Xin, et al. Chem. Commun. 47 (2011) 3556–3558. [123] P. Simon, Y. Gogotsi, Nat. Mater. 7 (2008) 845–854.
[53] M. Shao, et al. Chem. Mater. 24 (2012) 1192–1197. [124] L.B. Kong, et al. J. Power Sources 194 (2009) 1194–1201.

225
 RESEARCH Materials Today  Volume 19, Number 4  May 2016

[125] J.W. Lang, et al. J. Solid State Electrochem. 13 (2009) 333–340. [139] Y. Niu, et al. Electrochim. Acta 94 (2013) 360–366.
[126] U. Patil, et al. J. Power Sources 188 (2009) 338–342. [140] W. Zhang, et al. RSC Adv. 3 (2013) 2483–2490.
[127] C. Yuan, et al. J. Mater. Chem. 19 (2009) 5772–5777. [141] L. Zhang, et al. J. Power Sources 199 (2012) 395–401.
[128] K.W. Nam, et al. J. Power Sources 182 (2008) 642–652. [142] X. Liu, et al. J. Mater. Chem. A 2 (2014) 1682–1685.
[129] Y. Wang, I. Zhitomirsky, Langmuir 25 (2009) 9684–9689. [143] Y. Lin, et al. Electrochim. Acta 95 (2013) 146–154.
[130] N. Nagarajan, et al. Electrochim. Acta 51 (2006) 3039–3045. [144] X. Wang, et al. Nanoscale 4 (2012) 7266–7272.
[131] Y. Fang, et al. J. Power Sources 195 (2010) 674–679. [145] L. Huang, et al. Nano Lett. 13 (2013) 3135–3139.
[132] M.E. Roberts, et al. J. Mater. Chem. 19 (2009) 6977–6979. [146] D.A. Corrigan, J. Electrochem. Soc. 134 (1987) 377–384.
[133] K. Zhang, et al. Chem. Mater. 22 (2010) 1392–1401. [147] L. Trotochaud, et al. J. Am. Chem. Soc. 136 (2014) 6744–6753.
[134] H. Li, et al. Nat. Commun. 4 (2013) 1894. [148] M.A. Oliver-Tolentino, et al. J. Phys. Chem. C 118 (2014) 22432–22438.
[135] T. Brezesinski, et al. Nat. Mater. 9 (2010) 146–151. [149] S. Trasatti, J. Electroanal. Chem. 111 (1980) 125–131.
[136] H. Wang, et al. J. Am. Chem. Soc. 132 (2010) 7472–7477. [150] J. Suntivich, et al. Science 334 (2011) 1383–1385.
RESEARCH: Review

[137] X.M. Liu, et al. Electrochim. Acta 49 (2004) 3137–3141. [151] W.T. Hong, et al. Energ. Environ. Sci. 8 (2015) 1404–1427.
[138] Z. Wang, et al. J. Colloid Interface Sci. 396 (2013) 251–257. [152] S. Trasatti, Electrochim. Acta 29 (1984) 1503–1512.

226