Noble Metalfree Hydrogen Evolution Catalysts For Water Splitting2015chemical Society Reviews

Featuring work from the research group of Dr Yu Zhang, As featured in:
School of Chemistry and Environment, BeiHang University,

Beijing, China
Noble metal-free hydrogen evolution catalysts for water

splitting
This review highlights the recent research efforts towards the

synthesis of noble metal-free electrocatalysts, especially at
the nanoscale, and their catalytic properties for the hydrogen
evolution reaction (HER).
See Xiaoxin Zou and Yu Zhang,

Chem. Soc. Rev., 2015, 44, 5148.
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Noble metal-free hydrogen evolution catalysts

for water splitting†
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Cite this: Chem. Soc. Rev., 2015,

44, 5148
Xiaoxin Zouc and Yu Zhang*ab
Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis
driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on
photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen
production. All these techniques require, among many things, highly active noble metal-free hydrogen
evolution catalysts to make the water splitting process more energy-efficient and economical. In this review,
we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at
the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several
important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal
selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the
discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of
Received 2nd December 2014 performance improvement, and the structure/composition-catalytic activity relationship. We also summarize
DOI: 10.1039/c4cs00448e some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for
promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water
www.rsc.org/csr splitting systems, when combined with suitable semiconductor photocatalysts.
1. Introduction hydrogen content.1–23 Very recently, considering the high

hydrogen content and easy recharging as a liquid, hydrous
Strong dependence on fossil fuels has made our economy hydrazine and formic acid have been generally considered as
susceptible to price spikes, and overuse of fossil fuels is also very promising chemical hydrogen storage materials. Develop-
intensifying air pollution and global warming. Thus, development of a highly selective and efficient catalyst to significantly
ing a clean, renewable alternative to fossil fuels is a matter of improve the kinetic properties for the catalytic decomposition
utmost urgency. Among the various alternative energy strategies, of these liquid hydrogen storage materials at room temperature
constructing an energy infrastructure that uses hydrogen as the is urgently important for its practical application. Particularly,
primary carrier connecting a host of energy source to diverse end Zhang et al. firstly found that the Rh–Ni–graphene hybrid
uses may enable a secure and clean energy future. To this end, material exerts 100% selectively and exceedingly high activity
effective storage and production of hydrogen are key elements of to complete the decomposition reaction of hydrous hydrazine
the hydrogen economy. at room temperature owing to the role of graphene as a
Besides the storage of hydrogen as a compressed gas or as a communicating platform in facilitating the electron transfer
cryogenic liquid, many kinds of hydrogen storage materials and mass transport kinetics during the catalytic reaction
including metal hydrides, nanostructured materials, and chemical process.22 For the formic acid system, Yan’s group reported
storage materials have been widely studied due to their high that CoAuPd/C can lead to the efficient decomposition of
formic acid for CO-free hydrogen generation at room tempera-
ture.23 This is the first time that a non-noble metal (i.e., Co) has
a
Key laboratory of Bio-Inspired Smart Interfacial Science and Technology of
been used as the active part of the catalyst in the formic acid
Ministry of Education, Beijing Key Laboratory of Bio-inspired Energy Materials
and Devices, School of Chemistry and Environment, BeiHang University,
system. This improvement would lead to a new approach to
Beijing, 100191, P. R. China. E-mail: jade@buaa.edu.cn further develop cost-effective and highly efficient solid catalysts
b
International Research Institute for Multidisciplinary Science, Beihang University, for generation of hydrogen from formic acid.
Beijing, P. R. China On the other hand, unlike oil and natural gas, hydrogen is
c
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,
not energy, but only an energy carrier for storing and trans-
International Joint Research Laboratory of Nano-Micro Architecture Chemistry,
College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012,
porting energy. Hydrogen does not exist naturally on earth, and
P. R. China thus we have to make it before we can use it. At present, more
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c4cs00448e than 500 billion cubic meters (or 44.5 million tons) are produced
5148 | Chem. Soc. Rev., 2015, 44, 5148--5180 This journal is © The Royal Society of Chemistry 2015
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reaction is driven by solar-, wind- or other renewable resources-

derived electricity. In fact, solar and wind technologies are
booming worldwide, especially in China, Europe, the United
States and Japan.27 This might lay a good foundation for the
water electrolysis technique. On the other side, hydrogen can
also solve other issues along the way, such as making best use
of wind energy. The trouble with wind energy is its intermit-
tency and unpredictability. At times of low demand such as
during the night, excess wind power is wasted. If we can use the
excess power to split water to make hydrogen, we will store
Fig. 1 Three main pathways for industrial hydrogen production. electricity indirectly as the form of hydrogen.
The potential use of hydrogen, instead of petroleum-based
fuels, for transportation applications is attracting more and more
annually worldwide.24,25 Most of this hydrogen is used for attention. Hydrogen-powered vehicles (also known as fuel cell
industrial purposes, such as refining petroleum and producing electric vehicles, FCEVs) might offer performance similar to that
ammonia for fertilizers and other chemicals. There are currently of combustion ones, but better pollution control (zero emissions
three main pathways for hydrogen production industrially of CO2 and pollutants). Many of the world’s major car manu-
(Fig. 1), that is, steam methane reforming, coal gasification and factures, such as Ford, Toyota, BMW and Hyundai, have made
water electrolysis. Steam methane reforming and coal gasifica- their sustained efforts to bring FCEVs into clear and realistic
tion make more than 95% of the whole hydrogen, while only 4% future. If hydrogen-powered vehicles are to enter our lives, our
of the hydrogen is produced by water electrolysis. Obviously, demand for hydrogen will increase sharply. At that time, we
current primary hydrogen production is still strongly dependent would have to produce hydrogen on a larger scale in a more
on the fossil fuels—the finite and nonrenewable resource. environmentally friendly way.
The hydrogen production techniques based on fossil fuels Water electrolysis might be such a technique that can meet
cannot really solve the pollution and CO2 emission problems. our requirements (Fig. 2).26 However, the practical widespread
For example, during steam methane reformation, the high- application of this technique is constrained by its high cost.
temperature reaction between hydrocarbon and water results Although water electrolysis has a long history, continuous
in the simultaneous generation of hydrogen and carbon dioxide. technological improvement and material innovation are still
CO2 as a greenhouse gas is finally released into the atmosphere. highly desirable to drastically reduce the cost of this process. In
This hydrogen production method, apparently, violates our original particular, while Pt-based materials are the hydrogen evolution
intention—reducing air pollution and global warming by the catalysts for electrochemical water splitting, developing efficient
employment of hydrogen power. non-noble metal electrocatalysts, composed of earth-abundant
Among these three main hydrogen production pathways, elements, is quite appealing with the aim of providing cost-
water electrolysis still provides hope that it is possible to competitive hydrogen.28–32 Moreover, direct solar-to-hydrogen
produce hydrogen in a sustainable way, because its feedstock conversion based on photochemical and photoelectrochemical
is water—an abundant and renewable hydrogen source.26 But water splitting is another promising scheme for sustainable
this is still based on a premise that the hydrogen production hydrogen production (Fig. 2). Currently, direct solar-to-hydrogen
Xiaoxin Zou was awarded a PhD in Yu Zhang received his doctoral

Inorganic Chemistry from Jilin degree in Chemistry from Jilin
University (China) in 06/2011; and University in 2007. Then, he
then moved to the University of worked as a new energy and
California, Riverside and Rutgers, industrial technology develop-
The State University of New Jersey, ment organization (NEDO) fellow
as a Postdoctoral Scholar from at Hiroshima University, Japan. In
07/2011 to 10/2013. He is cur- March 2013, he joined Beihang
rently an associate professor at University as a ‘‘Zhuoyue’’
State Key Laboratory of Inorganic program Associate Professor.
Synthesis and Preparative His interests mainly focus on
Chemistry in Jilin University. His advanced materials for hydrogen
Xiaoxin Zou research interests focus on the Yu Zhang storage/production, lithium/sodium
design and synthesis of noble ion battery and fuel cells.
metal-free, nanostructured and/or nanoporous materials for water
splitting and renewable energy applications.
This journal is © The Royal Society of Chemistry 2015 Chem. Soc. Rev., 2015, 44, 5148--5180 | 5149
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Fig. 2 Sustainable pathways for hydrogen production from renewable

energy, such as solar energy.26 Copyright 2014 with permission from The
American Association for the Advancement of Science. Fig. 3 Schematic diagram of an electrolyzer.
conversion is in the conceptualization stage still. But ongoing the water reduction reaction (or hydrogen evolution reaction).
technological progress will ultimately make this approach enter According to different media in which water splitting takes
the stage of actual application in the future. This also requires, place, the water splitting reaction can be expressed chemically
among many things, efficient hydrogen evolution catalysts, in different ways (see below).
preferably based on earth-abundant elements.33–36 Against Total reaction H2O - H2 + 1/2O2
such a backdrop, researchers have been exploring noble
metal-free hydrogen evolution (electro)catalysts with great In acidic solution
enthusiasm in the past few years, and their efforts have
already led to abundant achievements, especially with the Cathode 2H+ + 2e - H2
help of nanoscience and nanotechnology.33–36
In this review, we summarize recent developments in the area Anode H2O - 2H+ + 1/2O2 + 2e
of noble metal-free electrocatalysts for the hydrogen evolution
reaction (HER)—one of the two half reactions of the water In neutral and alkaline solutions
splitting reaction. We specially review several important kinds
Cathode 2H2O + 2e - H2 + 2OH
of heterogeneous non-precious metal electrocatalysts, including
metal sulfides, metal selenides, metal carbides, metal nitrides,
Anode 2OH - H2O + 1/2O2 + 2e
metal phosphides, and heteroatom-doped nanocarbons. In the
discussion, particular attention is paid to the synthetic methods
Regardless of the media in which water splitting takes place,
of these HER electrocatalysts, the strategies of performance
the thermodynamic voltage of water splitting is 1.23 V at 25 1C
improvement, and the structure/composition–catalytic activity
and 1 atm. It is worth noting that the thermodynamic voltage of
relationship. We also highlight the employment of HER electro-
water splitting is temperature-dependent, and it can be reduced
catalysts as non-Pt cocatalysts for promoting solar-to-hydrogen
by increasing the electrolytic temperature. However, in fact, we
conversion in both photochemical and photoelectrochemical
must apply voltages higher than the thermodynamic potential
water splitting systems. Based on the results achieved in this
value (i.e., 1.23 V at 25 1C) to achieve electrochemical water
area, several future directions are proposed and discussed
splitting. The excess potential (also known as overpotential, Z)
finally.
is mainly used to overcome the intrinsic activation barriers
present on both anode (Za) and cathode (Zc), as well as some
other resistances (Zother), such as solution resistance and contact
2. Electrochemistry of the hydrogen resistance. Thus, the practical operational voltage (Eop) for water
evolution reaction splitting can be described as:37
As shown in Fig. 3, an electrolyzer has three component parts: Eop = 1.23 V + Za + Zc + Zother
an electrolyte (i.e., H2O), a cathode and an anode. The hydrogen
evolution catalyst (HEC) and the oxygen evolution catalyst It is clearly seen from this equation that reduction of the
(OEC) are coated on the cathode and anode, respectively, to overpotentials by suitable methods is the central issue in order
speed the water splitting reaction. When driven by an external to make the water splitting reaction energy-efficient. Indeed,
voltage applied to the electrodes, water molecules are decom- Zother can be reduced by optimizing the design of the electrolytic
posed into hydrogen and oxygen. The hydrogen can be stored cell, whereas Za and Zc have to be minimized by highly active
for fuel and the oxygen is released into the atmosphere. Thus, oxygen evolution and hydrogen evolution catalysts, respectively.
the water splitting reaction can be divided into two half-reactions: In this context, the development of efficient water splitting
the water oxidation reaction (or oxygen evolution reaction) and catalysts, preferably based on sustainable and earth-abundant
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elements, is highly desirable in order to make the overall water- superficial geometric electrode area in the literature. In some
splitting more economical. Besides electrode materials, the cases, the currents we measured are also normalized to the
effective active area of electrode is another important factor in sample quality in order to achieve the activity per unit mass.
determining the reaction overpotential. The improvement of the To compare the activities between the samples, two special
effective active area of the electrode can be achieved by the overpotentials in HER are often provided deliberately. One is
optimization of the electrode preparation method (e.g., nano- the so-called ‘‘onset overpotential’’. The onset overpotential is
structuring). In addition, the bubble effect is also an issue that actually a poorly-defined term. If one wants to use this term in
cannot be ignored. During water electrolysis, lots of bubbles are the research paper, a suitable current density value (0.5–2 mA cm 2)
generated on the electrode surface and simultaneously some of should be clearly shown. The other relevant overpotential is that the
them do not get away from the electrode immediately. This electrocatalyst needs to yield a current density of 10 mA cm 2
directly leads to the loss of the effective active area, and thus the (which is the current density expected for a 12.3% efficient solar
increase of the reaction overpotential. water-splitting device).
The HER generally involves three possible reaction steps in
acidic media, while the HER mechanism in alkaline media is (ii) Tafel plot
still ambiguous. The first one in acidic media is the so-called Tafel plot depicts the dependence of steady-state current den-
Volmer step: H+ + e - Hads. The reaction of an electron with a sities on a variety of overpotentials. Generally, the overpotential
proton produces an adsorbed hydrogen atom (Hads) on the (Z) is logarithmically related to the current density ( j) and the
electrode surface. After generation of Hads, the hydrogen evolu- linear portion of the Tafel plot is fit to the Tafel equation:
tion reaction can proceed by the Tafel step (2Hads - H2) or the Z = a + b log j; where b is the Tafel slope. From the Tafel
Heyrovsky step (Hads + H+ + e - H2) or both. Regardless of the equation, we can derive two important parameters, Tafel slop
routes by which the HER occurs, Hads is always involved in (b) and exchange current density ( j0). b is generally related to
the HER. Thus, the free energy of hydrogen adsorption (DGH) is the catalytic mechanism of the electrode reaction, whereas j0,
widely accepted to be a descriptor for a hydrogen-evolving which is obtained when Z is assumed to be zero, describes
material. For example, DGH is approximately zero for Pt, and the intrinsic catalytic activity of the electrode material under
correspondingly Pt is the best solid-state hydrogen evolution equilibrium conditions. A catalytic material having a high j0
catalyst. If DGH is large and positive, the Hads is bound strongly and a small Tafel slop (b) is desirable actually.
with the electrode surface, making the initial Volmer step easy,
but the subsequent Tafel or Heyrovsky steps difficult. If DGH is (iii) Stability
large and negative, Hads has a weak interaction with the
Good structural and catalytic stabilities of a HER catalyst are of
electrode surface, resulting in a slow Volmer step that limits
crucial importance for a material that has some practical
the overall turnover rate. Therefore, an optimal non-Pt HER
applications potentially, especially considering that the HER
catalyst should also provide appropriate surface properties and
catalyst mostly works in a strongly reductive environment at the
have a nearly zero DGH.
pH extremes (pH 0 or 14). There are two methods for charac-
terizing the electrocatalytic stability of a HER catalyst. One
3. Experimental method for method is to measure the current variation with time (i.e., the
I–t curve). For this measurement, it would be better to set a
characterizing the electrochemical current density larger than 10 mA cm 2 for a long period of
activity of HER catalysts time (410 h). The other method is to conduct the recycling
experiment by performing CV or LSV. The number of cycles
To elucidate the catalytic activity of a given HER electrocatalyst,
should be larger than 5000 times to elucidate the stability of a
there are some important parameters that are required to be
material.
measured/calculated carefully. They mainly include total electrode
activity, Tafel plot, stability, Faradic efficiency, as well as turnover
(iv) Faradic efficiency
frequency.
Faradic efficiency describes the efficiency with which electrons
(i) Total electrode activity participate in a desired reaction in an electrochemical system.
The total electrode activity is generally estimated first by For the electrochemical hydrogen evolution reaction, Faradic
performing cyclic voltammetry (CV) or linear sweep voltam- efficiency is defined as the ratio of the experimentally detected
metry (LSV). Because non-Faradaic capacitive current may con- H2 amount to the theoretical H2 amount, which can be calcu-
stitute a certain portion of the total current we observed, lated from the current density based on a 100% Faradaic yield.
especially for those carbon-containing catalysts, we only get a
preliminary assessment of the material’s electrocatalytic activity (v) Turnover frequency
from the CV or LSV results. To more exactly determine the Turnover frequency (TOF) is defined as the number of reactant
catalytic activity of a material, we need to measure its steady- that a catalyst can convert to a desired product per catalytic site
state currents at various applied voltages with a dwell time of at per unit of time, which can exhibit the intrinsic activity of each
least 5 min. The obtained currents are usually normalized to the catalytic site. However, it is very difficult to get a precise TOF
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value for many solid-state (heterogeneous) catalytic materials,

such as HER nanocatalysts, that generally possess easily acces-
sible surface atoms/catalytic groups as well as some inaccessible
internal atoms/catalytic species. In such cases, many researchers
try to calculate and report the TOFs based solely on the surface
atoms or the easily accessible catalytic sites of the materials,
which is of course a reasonable approach. In other cases, the
TOFs are calculated based on the total catalytic species present
in the materials, no matter whether they are all accessible, not
equally accessible, or some even not accessible at all. Although
this clearly does not give the exact value (gives an underesti-
mated value actually), it is sometimes done because of unavail-
Fig. 4 Elements that are used for constructing HER electrocatalysts.
ability of ways to completely determine all the accessible active
sites in the catalytic system. Despite being relatively imprecise
though, the latter may still give insights into the comparative
catalytic activity or efficiency of two or more materials if carefully
executed. For instance, in most cases, one can only get TOFs
calculated per unit mole of atoms present in the HER nano-
catalyst, despite it is very likely that only the surface atoms,
whose number may be hard to figure out precisely, may only be
responsible for the catalysis. This will obviously result in TOFs
that would be grossly underestimated compared with the real
TOF values of the active sites, because it is almost impossible
to have every atom in a material like nanoparticles to be
catalytically active or equally accessible. Nevertheless, when
similar materials are compared, such results could still be
relevant and useful. Fig. 5 Crustal abundance of metals that are used for constructing HER
electrocatalysts.
4. A general view of the elements used

have the two highest abundance and lowest price among them,
for constructing HER electrocatalysts developing efficient iron- or nickel-based HER electrocatalysts
Fig. 4 shows a general view of the elements that are used for should be highly desirable in order to make the hydrogen
constructing HER electrocatalysts. These elements, according production reaction economically viable. This challenging target
to the general physical and chemical properties, roughly fall is also accordant with the ideas of biomimetic chemistry because
into three groups: (i) noble metal platinum (Pt)—the state- hydrogenases, which catalyze the conversion of protons and
of-the-art HER electrocatalysts; (ii) transition metals that are electrons into dihydrogen, are widespread in nature and their
used for constructing noble metal-free HER electrocatalysts, active sites always contain iron and/or nickel ions.
mainly including iron (Fe), cobalt (Co), nickel (Ni), copper (Cu),
molybdenum (Mo), and tungsten (W); (iii) nonmetals that are
used for constructing noble metal-free HER electrocatalysts, 5. Metal sulfides
mainly including boron (B), carbon (C), nitrogen (N), phos-
phorus (P), sulfur (S), and selenium (Se). To date, almost all the Developing functional bio-inspired catalysts is an important
efficient noble metal-free HER electrocatalysts have been advance to bridge the gap towards large-scale sustainable
synthesized based on the above twelve non-precious elements. hydrogen production. Albeit the presence of nitrogenase and
Fig. 5 shows the crustal abundance of the metals constructing hydrogenase in nature that can mediate the HER, it is impos-
HER electrocatalysts in weight percent. The following conclu- sible that enzyme-based devices will make a significant contri-
sions can be made by comparing their abundance in the crust. bution to high-level hydrogen generation.38–43 These elegant
(i) The abundance of Pt is about 3.7 10 6%, which is orders of biocatalysts are capable of functioning in the natural environ-
magnitude smaller than that of other non-precious metals. This ment with superb catalytic selectivity, but under extreme con-
is in agreement with the fact that noble metal Pt has a highest ditions (such as strong acidic and alkaline media) they will lose
cost among them. (ii) The abundance of the six non-noble metals their ability rapidly. Inspired by the structure/composition of
increases in the order of W = Mo o Co o Cu o Ni { Fe. It is nitrogenase and hydrogenase, researchers have exploited a
worthwhile to note that we should keep in mind the difference in series of metal sulphides as efficient HER electrocatalysts (see
their abundance and potential cost when we attempt to design below). This is a profound achievement in the field of noble
such non-noble metal HER catalysts. Because iron and nickel metal-free HER electrocatalysts.
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5.1 Crystalline MoS2 conductibility engineering’’. The active site engineering mainly
5.1.1 Active sites of MoS2. The study of MoS2 on electro- includes three aspects: (i) increasing the number of exposed active
chemical HER can be traced to the 1970s,44 which showed that sites, (ii) enhancing the reactivity of active sites, and (iii) improving
bulk MoS2 crystals were non-reactive toward HER. As a result, the electrical contact to active sites. The electronic conductibility
MoS2 has not been considered as a promising hydrogen evolution engineering can be achieved by two ways: (i) doping suitable
electrocatalyst for a long time. This tide was totally reversed by heteroatoms into the lattice of MoS2 and (ii) coupling MoS2 with
Hinnemann et al. in 2005. They found that the (1010) Mo-edge conductive species, such as carbon nanotubes and graphene. In
structure in MoS2 had a close resemblance to the active site of some cases, the two aforesaid strategies have been integrated in a
nitrogenase.45 Furthermore, they showed that the computational single material system, either intentionally or unintentionally. In
free energy of atomic hydrogen bonding to the MoS2 edge was this section, we will summarize these achievements classified by
close to that of Pt (Fig. 6), raising the possibility of MoS2 as a different yet specific tactics.
promising HER electrocatalyst in theory. In their study, they
also prepared MoS2 nanoparticles supported on graphite, and
experimentally verified the catalytic activity of nanoscale MoS2 (i) Constructing active site-rich nanosheets. Compared with
for HER. This is the first time that the MoS2 edge structure is bulk materials, nanostructured materials usually have larger
considered to be the actual active site. To further identify the specific surface areas and higher density of surface reactive sites.
active sites of MoS2, Jaramillo et al. prepared different sizes of Thus, a convenient method to enhance the catalytic activity of
MoS2 nanoparticles with the predominance of the sulfide MoS2 towards HER is preparing them in a nanostructured form.
Mo-edges.46 Electrocatalytic activity measurements showed that With the aim of increasing the active sites of MoS2, some
the catalytic performance of MoS2 nanoparticles is related to methods have been developed by different groups to prepare
the edge state length, rather than the area coverage, directly its nanostructured counterpart.50–60 Because MoS2 possesses a
establishing the relationship between MoS2’s edges and the unique layered crystal structure, it shows a quite strong tendency
catalytic active sites. to form sheet-like nanocrystals. This is also why nanosheet
Homogeneous catalysts with precise molecular structures morphology dominates the whole MoS2 nanostructures.
usually have explicit definition and quantitation of the active Chemical exfoliation of bulk MoS2 by the lithium intercala-
sites relative to heterogeneous catalysts. Thus, it is a smart way tion method is widely used to obtain single- or few-layered
to employ appropriate molecular catalysts to imitate the possible MoS2 nanomaterials. This method typically includes an inter-
active sites of heterogeneous catalysts. Keep this in mind, three calation process of lithium compounds (e.g., n-butyllithium)
molecular catalysts, including [Mo3S4]4+, [(PY5Me2)MoS2]2+ and between MoS2 layers followed by a furious exfoliation of Li-
[Mo3S13]2 , which mimic the structure of triangular active edge intercalated compounds via reacting with water. Interestingly,
sites in MoS2, have been prepared by different groups (PY5Me2 = chemically-exfoliated MoS2 nanosheets exhibit an unexpected
2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine).47–49 The expected electro- phase transformation from the thermodynamically favored 2H
catalytic activities of these discrete molecular units verified again phase to the metastable 1T polymorph partially (Fig. 7).55 The
the active site of nanoscale MoS2 from a different perspective. structure of the 2H phase can be described by two S–Mo–S
5.1.2 Strategies for improving the catalytic activity of MoS2. layers composed of edge-shared MoS6 trigonal prisms, whereas
Based on the instructional studies on active sites, as stated the structure of the 1T phase is described by a single S–Mo–S
above, and the semiconductive nature of MoS2, researchers have layer built from edge-sharing MoS6 octahedra. In 2013, Jin’s
conducted some rational designs on nanoscale MoS2 catalysts for group first demonstrated that the 1T polymorph of MoS2 had
improving their catalytic activity. The strategies can be roughly higher metallic character and more competitive HER activities
divided into the categories ‘‘active site engineering’’ and ‘‘electronic than the 2H phase because of the better electrical conductivity
of the former.56 Chhowalla’s group further found that the active
sites of 1T MoS2, different from the ones limited by the edges
of the 2H phase, mainly located in the basal plane.57 Thus,
the authors proposed that the enhanced catalytic activity of 1T
MoS2 was attributed to both the increase of active sites and the
improvement of conductivity. Furthermore, Pumera’s group
investigated the effects of lithium intercalation compounds
on the degrees of exfoliation and the catalytic activity of exfoliated
MoS2 nanomaterials.58 Their results showed that the MoS2
nanosheets, which were produced using n-butyllithium and
tert-butyllithium as the intercalator, exhibited higher degrees
of exfoliation and better catalytic properties than that obtained
with methyllithium. The catalytic activities of the exfoliated
Fig. 6 Calculated free energy diagram for hydrogen evolution relative to
MoS2 can be further enhanced by a simple electrochemical
the standard hydrogen electrode at pH 0.45 Reprinted with permission pretreatment.59 The electrochemical activation process might
from ref. 45. Copyright 2014 American Chemical Society. lead to the 2H–1T transition, as confirmed by DFT calculations.
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Fig. 8 Schematic representation of the synthesis procedure to obtain

MoS2 quantum dots interspersed in MoS2 nanosheets using a liquid
exfoliation approach in a 1-methyl-2-pyrrolidone solution.62 Reprinted
with permission from ref. 62. Copyright 2014 American Chemical Society.
Fig. 7 Structures of 2H and 1T MoS2.55 Reprinted with permission from

ref. 55. Copyright 2014 American Chemical Society.
Besides lithium intercalation, ball-milling and sonication

techniques can also be used to acquire highly active MoS2
nanosheets. Wu et al. synthesized MoS2 nanosheets with high
active site density via a ball-milling-assisted microdomain
reaction method by using MoO3 and S microparticles as the
starting materials.60 In addition, Wang et al. successfully con-
verted commercial bulk MoS2 into distorted nanosheets by
using the high-energy ball milling technique.61 The resulting
MoS2 nanomaterial showed significantly enhanced catalytic Fig. 9 (a) Structural models of defect-free and defect-rich structures.
activity compared to its commercial counterpart because of (b) As-designed synthetic pathways to obtain the above two structures.63
Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA Weinheim.
the lattice defects and dislocations generated by mechanical
milling. Furthermore, Shaijumon’s group reported a sonication-
assisted synthetic method to make a hybrid nanostructure of and H2O.64 They confirmed the presence of bridging S22 or
1 nm-sized quantum dots interspersed in few-layered MoS2 apical S2 in the nanosheet structure by XPS analyses, and the
nanosheets (Fig. 8).62 The resulting hybrid nanomaterial showed positive role of these unsaturated sulfur sites on HER perfor-
excellent HER activity with a large exchange current density of mance of MoS2 nanosheets. In another study, Chung et al.
3.2 10 2 mA cm 2, probably due to the enhanced edge to prepared edge-exposed MoS2 nanosheet-assembled structures
basal plane ratio resulting from the unique morphology of the using L-cysteine as the sulfur source and Na2MoO4 as the Mo
material. source in a hydrothermal reaction.65 However, the driving force
Hydro(solvo)thermal synthesis, one of the bottom-up syn- for the self-assembly of MoS2 nanosheets is still unclear. More-
thetic methods, has also been proven to be an effective way to over, the authors revealed the linear relationship between
prepare MoS2 nanosheets. Xie et al. reported the large scale exchange current density and the number of sulfur edges,
synthesis of the defect-rich MoS2 nanosheets with a thickness demonstrating that the active site for HER was the sulfur edge
of B5.9 nm in a solvothermal system (Fig. 9).63 The authors of MoS2 nanosheets. Very recently, Lu et al. hydrothermally
found that excess thiourea in the reaction system played a prepared a MoS2 nanostructured film, which was composed of
crucial role in the formation of defect-rich nanosheet morpho- vertically aligned nanoplates.66 More importantly, the authors
logy, and thiourea functioned as a reductant to reduce Mo(VI) to revealed that the resulting nanostructured film had a ‘‘super-
Mo(IV) and as an additive to stabilize the sheet-like morphology. aerophobic’’ surface, which significantly improved the removal
Due to the introduction of defects as additional active sites in speed of small gas bubbles during HER.
the nanosheets, this material displayed an obvious enhance- Compared to the above-mentioned methods, the chemical
ment of catalytic activity compared to defect-free MoS2 sheets. vapor deposition (CVD) technique has shown some unique
In addition, Yan et al. synthesized MoS2 nanosheets with a advantages, especially in terms of creating high-quality uniform
thickness of 4–6 nm via simple solvothermal treatment of MoS2 nanosheets and controlling the thickness of nanosheets.
(NH4)2MoS4 in the mixture solvent of N,N-dimethylformamide In this regard, Cao’s group successfully grew MoS2 thin films
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a high-quality dendritic monolayer MoS2 material with abundant

edges was synthesized on a large scale.69 Furthermore, a
centimeter-scale, nearly complete, monolayer MoS2 film was
prepared on STO by controlling the growth parameters (such
as time and temperature).
(ii) Creating porous structure. A traditional, yet effective way

to enhance the performance of heterogeneous catalysts is
increasing their specific surface areas by creating a porous
structure in them. For the sake of maximizing the number of
highly energetic exposed active sites, MoS2 with a nanoporous

Fig. 10 Hopping of electrons in the vertical direction of MoS2 layers. The
right side illustrates the potential distribution in the multilayer film and the
structure is actively pursued.70–74 Apart from a larger surface
hopping of electrons through the potential barrier in the interlayer gap.67 area, the porous structure might provide the catalysts with
Reprinted with permission from ref. 67. Copyright 2014 American other advantages, such as a greater contact area with reactants
Chemical Society. and sufficient transport of reactants and products.
Jaramillo’s group successfully synthesized a highly ordered
double-gyroid MoS2 bicontinuous network with nanopores
with the precise control of layer number on glassy carbon
(B3 nm) via electrodepositing Mo onto a silica template,
substrates by a CVD method.67 Their electrocatalytic results
followed by sulphidization with H2S.70 After etching the silica
showed that the exchange current densities decreased by a
template, they obtained a mesoporous MoS2 thin film with a
factor of B4.47 for the addition of every one more layer. The
negative morphology of silica (Fig. 12). The layer-to-layer spacing
authors believed that the electrochemical HER only occurred at
(6.6 Å) of the mesoporous MoS2 material was found to be slightly
the outmost layer of the MoS2 film, and electrons had to
larger than that (6.15 Å) of bulk MoS2, which was attributed to
overcome the interlayer potential barrier to reach the surface
the curvature of the MoS2 structure resulting from the constraint
of the catalyst to drive the HER. Hence, this layer-dependent
of the double-gyroid morphology. For a similar reason, this
catalytic property of MoS2 was related to the layer-dependent
mesoporous MoS2 thin film engendered more exposed edge
efficiency of electron’s interlayered hopping (Fig. 10). The
sites than core–shell MoO3–MoS2 nanowires (which were also
greatest contribution of this work lies in first pointing out that
synthesized by the same group), while nanowires preferentially
the hopping efficiency of electrons in the vertical is an impor-
grew inactive basal planes of MoS2 parallel to the nanowire
tant parameter to determine the electrocatalytic performance of
axis.71 Moreover, Tan et al. produced a monolayer MoS2 film
MoS2. In another study, Liu’s group reported the scalable
using a curved internal surface of 3D nanoporous gold (NPG) as
synthesis of monolayer MoS2 on Au foils via the low-pressure
the substrate (Fig. 13).72 The MoS2 film completely inherited the
CVD (Fig. 11).68 These mono-layered MoS2 with a uniform
3D curvature of NPG substrates, which bent MoS2 lattices with
morphology can be transformed easily onto other substrates
large out-of-plane strains. Further DFT calculations demon-
by a chemical wet etching method, and the coverage of MoS2 on
strated that this out-of-plane lattice bending directly resulted
the substrate can be well controlled by simply tuning the distance
in the continuous changes of S–Mo–S bonding angles, and
between the MoO3 precursor and the Au substrate. In addition,
thereby a local semiconductor-to-metal transition. They also
when the Au substrate was replaced by a SrTiO3(STO) substrate,
confirmed the similarity between the charge density of S atoms
at the bent regions and that of edge S atoms with dangling
bonds, indicating that the structural curvature could generate
catalytically active sites analogous to edge sites of MoS2.
Fig. 11 SEM images of monolayer MoS2 grown on Au foils with different

precursor substrate distance (Dss) and different temperature. (a) A sche-
matic illustration of the coverage or flake size dependence on Dss. (b–d)
SEM images of monolayer MoS2 samples with coverage of B70%, 50%,
and 10% synthesized under the same conditions (grown at 530 1C) but with
different Dss of B10.0, 11.0, and 12.0 cm, respectively. (e) Raman spectra of Fig. 12 Synthesis procedure and structural model for mesoporous MoS2
the monolayer MoS2 flakes shown in (b–d).68 Reprinted with permission with a double-gyroid morphology.70 Copyright 2014 with permission from
from ref. 68. Copyright 2014 American Chemical Society. Nature Publishing Group.
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The deliberate introduction of a foreign metal or nonmetal

element in the MoS2 lattice affords the opportunity to engineer
the electronic and/or surface structures of the host material for
improving the HER performances. To date, metal elements
including Co, Ni, V and Li have been successfully doped into
the MoS2 crystal structure.75–79 And importantly, these dopants
provide some favorable effects on the properties of MoS2. For
example, Co-doped MoS2 nanomaterials have been studied by
different groups.75,76 The cobalt dopants were found to prefer
to locate at the S-edge of MoS2, leading to the reduction of the
Fig. 13 Monolayer MoS2@NPG towards catalytic HER. (a) Schematic diagram
free energy of hydrogen adsorption at the Co-promoted S-edge.

of the fabrication process of monolayer MoS2@NPG hybrid materials by a
nanoporous metal-based CVD approach. (b) Schematic HER catalyzed by the Thus, the promotion effect of Co for MoS2 was the increase in
monolayer MoS2@NPG hybrid material.72 Copyright 2014 WILEY-VCH Verlag the number of active sites.75,76 A similar promotion effect was
GmbH & Co. KGaA Weinheim. also observed for Ni-doped MoS2.77 Different with Co and Ni
dopants, V dopants in MoS2 did not increase the active site, but
obviously improved the conductivity of MoS2.78 In particular,
Besides leveraging various templates to confine the porous Xie’s group successfully prepared ultrathin V-doped MoS2
morphologies, Lu et al. reported a simple hydrothermal reaction nanosheets, which were proven to be superior hydrogen evolution
to prepare MoS2 porous thin films.73 In their synthetic system, catalysts relative to pristine MoS2.
thiourea was used as the sulfur source and the Mo substrate In contrast to Co, Ni and V dopants that were introduced
functioned as both the Mo source and the substrate/current into the intralayer of MoS2, Li ions were intercalated electro-
collector. The thickness of the films could be adjusted from chemically into the interlayer of MoS2 (Fig. 15).79 Cui’s group
400 nm to 1.3 mm by controlling the reaction time. The Tafel slopes systematically studied the structure and catalytic properties
of all the samples were found to be in the range of 41–45 mV dec 1 towards HER of Li-intercalated MoS2. They found that Li-doping
with an exchange current density of 2.5 10 7 mA cm 2, revealing created multiple effects on the structure and properties of MoS2,
the excellent performance of the resulting porous materials. In including the variation of the oxidation state of Mo, the transition
addition, Tour’s group successfully prepared edge-oriented MoS2 of the 2H to 1T phase and the expansion of the van der Waals gap.
nanoporous films with a thickness of B1 mm and a pore size Because of these positive variations, the Li-intercalated MoS2
ranging from 5 to 10 nm.74 The synthetic procedure mainly exhibited an obvious enhancement in HER activity compared to
consisted of two steps: (i) the electrochemical anodization of Mo the pristine MoS2.
metal; and (ii) gas-solid reaction with sulfur vapor. The obtained Besides metal-doping, nonmetal-doping was also used to
sponge-like film also showed a larger layer-to-layer spacing (6.5 Å) enhance the catalytic activity of MoS2.80,81 Xie’s group reported
with regard to bulk MoS2 due to the curvature of the surface the synthesis of oxygen-doped MoS2 ultrathin nanosheets in a
structure. More importantly, this scalable synthetic method could hydrothermal system at a temperature range from 140 to
easily make nanoporous, flexible and conformal electrodes for 200 1C.80 Because of the relatively low synthesis temperature,
HER (Fig. 14). the final MoS2 nanosheets inherited a small amount of Mo–O
(iii) Doping heteroatoms. Doping is one of the effective bonds in the molybdate precursor. First-principle calculations
methods used to tune the structure and HER activity of MoS2. demonstrated that the oxygen-doped MoS2 had a narrower
bandgap (1.30 eV) than that of the pristine MoS2 (1.75 eV).
This indicated that oxygen-doping could result in a higher
intrinsic conductivity for MoS2 (Fig. 16). The reason behind
the reduced bandgap is the oxygen dopants-induced enhanced
hybridization between the Mo d-orbital and the S p-orbital. In
another study, Zhou et al. prepared nitrogen-doped MoS2
nanosheets, which gave an enhanced and stable electrocatalytic
activity towards HER.81 N-doping was proposed to have a
similar role to oxygen-doping in enhancing the electronic
conductivity of MoS2.
(iv) Coupling conductive substrates. Coupling MoS2 with

conductive species is a direct and viable method to improve
Fig. 14 Schematic of the fabrication process and photographs of the its electronic conductibility, and thereby enhance the HER
flexible electrodes. (a) Schematic of the fabrication process and (b)
activity. In this context, a pioneering work was conducted by
photographs of the flexible electrodes. The left photograph shows the
visible difference between the Mo oxide (dark color) and MoS2 (gray color).
Dai’s group.82 In 2011, Dai et al. presented a solvothermal
The right photograph shows the flexibility of the edge-oriented MoS2 synthesis of MoS2 nanosheets on graphene (also known as
film.74 Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA Weinheim. reduced graphene oxide) for the first time (Fig. 17). The resulting
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Fig. 17 Solvothermal synthesis of a MoS2–graphene nanocomposite.

Reprinted with permission from ref. 82. Copyright 2014 American Chemical
Society.
and graphene afforded the site-confined growth of MoS2 nano-

particles free of aggregation. In addition, Zheng et al. leveraged
the confinement effect within the graphene layers to solvo-
thermally fabricate MoS2 nanosheets/graphene composite HER
catalysts in a controllable manner.83 And Firmiano et al. devel-
oped a microwave-assisted synthetic approach to rapidly make
MoS2/graphene HER catalysts.84 Nanosized tungsten carbide
was further discovered to be an effective cocatalyst for further
Fig. 15 Schematics and galvanostatic discharge curve of Li electro-
chemical intercalation into MoS2 nanofilms. (A) Crystal structure of 2H
improving the catalytic activity og MoS2/graphene due to the
MoS2. (B) Schematic of the battery testing system. The cathode is a MoS2 promoted electron transfer rate.85 Besides two-dimensional
nanofilm with molecular layers perpendicular to the substrate, where the graphene, one-dimensional nanocarbons (e.g., carbon nano-
green and yellow colors represent the edge sites and the terrace sites, tube and carbon nanofiber) were also employed to synthesize
respectively. The anode is the Li foil. (C) Galvanostatic discharge curve MoS2-based hybrid materials with enhanced catalytic activity.86–89
representing the lithiation process. Li intercalates into the van der Waals
gaps of MoS2 to donate electrons to the slabs and expand the layer
Generally, one-dimensional nanocarbons had similar functions to
spacing. The voltage monotonically drops to 1.2 V vs. Li+/Li to reach a Li graphene in promoting the electroactivity of MoS2.
content of 0.28, after which the system undergoes a 2H to 1T MoS2 first- Compared to other carbon materials as mentioned above,
order phase transition. The atomic structure is changed from trigonal porous carbons can not only provide a conductive framework,
prismatic to octahedral, along with the electronic semiconducting to but also a high specific surface area as well as an abundant mass
metallic transition.79 Copyright 2014 with permission from PNAS.
transfer channel of the reductant and product. Liu’s group
successfully grew highly dispersed and ultrafine MoS2 nano-
particles onto a mesoporous graphene foam (MGF).90 This
MGF, the 3D structure of which prevented graphene sheets
from restacking, had a high surface area of 819 m2 g 1 and a
pore size of 25 nm. Because of the excellent properties of MGF,
the MoS2–MGF nanocomposite served as an efficient hydrogen
evolution catalyst having low overpotential and high stability.
The same group also used mesoporous carbon spheres as the
support material for preparing MoS2/porous carbon composite
catalysts.91 In another study, graphene-based aerogels, which
have a highly porous carbon framework, large open pores, and
good electrical conductivity, have been proven to be another
Fig. 16 (A) Calculated density of states (DOS) of the oxygen-incorporated
MoS2 slab (top) and the pristine 2H–MoS2 slab (bottom). The orange outstanding carbon support for MoS2 by Hou et al.92 They
shading clearly indicates the decrease of bandgap after oxygen incorporation. prepared hydrothermally a 3D hybrid of MoS2 nanosheets/
(B) The charge density distributions of valence band (left) and conduction nitrogen-doped graphene aerogels, which was used for hydrogen
band (right) near the oxygen atom in the oxygen-incorporated MoS2 ultrathin evolution in microbial electrolysis cells. The catalytic perfor-
nanosheets, respectively. Black lines represent the contour lines of the charge
mance of this composite material was higher than those of
density.80 Reprinted with permission from ref. 80. Copyright 2014 American
Chemical Society. MoS2 nanosheets and nitrogen-doped graphene, and was com-
parable to that of the Pt/C catalyst.
For powdered HER catalysts, their usage must be fixed first
MoS2/graphene nanocomposite exhibited extremely high catalytic on a conductive support electrode (e.g., glassy carbon electrode
activity (Tafel slope, 41 mV decade 1) and durability toward HER. or ITO glass) using Nafion as the binder. To avoid the use of
There were two proposed roles of graphene, electrical coupling expensive Nafion and to ensure the electronic contact between
and chemical coupling. On one hand, the conducting graphene HER catalysts with the support electrode, carbon-based self-
network provided the internal electron transport channels supported MoS2 electrodes were developed recently.93–95 Ma et al.
from the less-conducting MoS2 nanosheets to the electrodes. developed a solvothermal method to grow MoS2 nanoflowers on
On the other hand, strong chemical interactions between MoS2 graphene paper (Fig. 18).93 The resulting MoS2–graphene paper
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Fig. 19 Hydrogen evolution on amorphous MoSx.96b Reprinted with

permission from ref. 96b. Copyright 2014 American Chemical Society.
Fig. 18 SEM images of a MoS2–graphene paper composite.93 Repro-

duced by permission of The Royal Society of Chemistry.
the edge sites of crystalline MoS2 in terms of the catalytic
function. Different from MoS2 nanocrystals, amorphous MoSx
directly served as a free-standing and flexible working electrode has short-range ordered atomic arrangements and significant
for HER. Apart from graphene paper, two commercialized carbon structural disorder, which probably can also offer some catalytic
supports, carbon cloth and carbon fiber paper, were also used active ‘‘defect sites’’.
to form self-supported MoS2 electrodes.94,95 Carbon cloth and While MoS2 nanocrystals are always prepared at elevated
carbon fiber paper are composed of carbon fibers and is highly temperatures, amorphous MoSx can form at a relatively low
conductive and flexible. Note that carbon cloth is much cheaper temperature, and even at room temperature. Electrodeposition
than carbon fiber paper. Very recently, Wang’s group developed a is a simple and effective method to prepare MoSx. It can be
simple solvothermal method to fabricate MoS2/carbon cloth simply achieved by consecutive cyclic voltammetry measure-
electrodes with vertically oriented MoS2 nanosheet layers.94 The ments in an aqueous solution of (NH4)2[MoS4] at room tem-
nanostructured MoS2/carbon cloth electrode exhibited excellent perature. Hu’s group found that by tuning the deposition
HER activity and electrocatalytic stability. The authors proposed parameters, the composition (MoSx, x = 2–3) and thickness
some possible reasons for explaining the high performance of the (40–150 nm) of MoSx can be controlled.96 However, all the films
MoS2/carbon cloth electrode. They mainly included (i) the inti- exhibited similar catalytic activities regardless of the deposition
mate contact of MoS2 nanosheets with carbon cloth; (ii) the rapid methods. To understand the formation mechanism of the MoSx
release of H2 bubbles from the nanostructured electrode surfaces; film, the same group investigated the growth and activation of
(iii) the easy diffusion of the electrolyte into the active sites due to these films using a electrochemical quartz crystal microbalance
the 3D nanostructure; and (iv) the abundant exposed active sites and by XPS analysis.97 The results showed that the formation of
in the vertically oriented S-rich MoS2 nanosheet arrays. the films mainly included three processes: oxidative deposition,
reductive corrosion and reductive deposition. Moreover, the
5.2 Amorphous MoSx catalytically active phases in all films were the MoS2+x species.
Owing to the structural indeterminacy, amorphous materials In another study, Murugesan et al. reported a nonaqueous-
are often ignored unconsciously by the researchers in the field based electrodeposition method for the preparation of a MoSx
of heterogeneous catalysis. The same situation occurs in the film, which exhibited a nanoflower morphology, indicating the
study of amorphous molybdenum sulfide. The discovery of this importance of the electrolyte.98 Apart from electrodeposition,
type of materials can be traced back to 1980, while their wet chemical synthesis is another easy way to prepare an
excellent catalytic activities towards HER were confirmed in amorphous MoSx material. Hu’s group reported that amorphous
2011.96 Hu’s group reported that electrochemically-deposited MoS3 could be obtained upon acidification of an aqueous
amorphous molybdenum sulfide films were efficient HER mixture of MoO3 and Na2S.99 In addition, Benck et al. successfully
catalysts for the first time (Fig. 19).96 Their significant geo- prepared an amorphous molybdenum sulfide material through
metric current densities (15 mA cm 2 at Z = 200 mV), together addition of ammonium heptamolybdate to sulfuric acid, followed
with the fast, mild and scalable synthetic methods, opened up a by mixing with a sodium sulfide solution.100 Moreover, the
new way to achieve economical hydrogen production. authors observed a composition variation from MoS3 to defective
Due to the uncertain structure and atomic-scale hetero- MoS2 during HER and a proportional relevance between the
geneity, it is difficult to identify the catalytic active sites on current densities and the transformation.101
amorphous molybdenum sulfide surfaces, and thereby to reveal Like crystalline MoS2, amorphous MoSx could also afford a
the precise catalytic mechanism. The unsaturated S atoms were higher catalytic activity when suitably doped with heteroatoms.
widely accepted to be catalytically active sites, and they were Hu’s group investigated the promotion effect of first-row tran-
often identified as terminal S22 and S2 via XPS analysis. In sition metal ions (Mn, Fe, Ni, Co, Cu and Zn) on the HER
fact, the unsaturated S atoms in amorphous MoSx are similar to activity of MoSx.102 The results showed that Fe, Co, and Ni ions
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were effective promoters. At pH 7, Co2+ as the best promoter exhibited a small Tafel slope of 29 mV dec 1, and comparable
gave MoSx a 5-fold increase in the current density at Z = 200 mV. activity to that of the commercial Pt/C catalyst (Fig. 20).
At pH 0, the best promoter was Fe2+, which gave a 2-fold
increase in the current density at the same overpotential. This
5.3 Tungsten disulfide
group also found that Fe, Co, and Ni ions promoted the growth
of the MoSx films, resulting in larger surface area, higher Owing to its structural and electronic similarities to MoS2, WS2
catalyst loading and thus better catalytic activity. has also drawn substantial interest in recent years. To realize its
To further enhance the performance of MoSx, coupling it potential application in HER, nanostructured WS2 with well-
with conductive substrates is a viable method.103–108 To date, controlled structures and tunable properties are required.
conducting nanocarbons, nanoporous gold and Ni foam were Recent research studies in this area have already led to some
successful examples of such WS2 nanomaterials.114–119 One of
reported as effective supports to improve the activity of amor-

phous molybdenum sulfide. For example, Li’s group success- the most notable examples is the strained chemically exfoliated
fully grew MoSx (x Z 2) materials on highly conductive 3D WS2 nanosheets (Fig. 21).114 Chhowalla’s group reported the
graphene/Ni foam by thermolysis of ammonium thiomolyb- synthesis of mono-layered nanosheets of chemically exfoliated
dates at elevated temperatures (100–300 1C).109 The resulting WS2 by the lithium intercalation method in 2013. The as-exfoliated
film gave a hydrogen evolution rate of 302 mL g 1 cm 2 h 1 at nanosheets had a high concentration of the strained metallic 1T
an overpotential of 0.2 V. Using a similar method, this group phase, which was proven to be an important factor in enhancing
also used porous 3D sponges or carbon cloth to support MoSx the catalytic activity of WS2 nanosheets. In addition, the strain-
materials.110,111 In the case of carbon cloth-supported MoSx, induced local lattice distortion was also believed to facilitate HER.
the authors found that the nitrogen dopants in carbon cloth In another study, Chhowalla’s group synthesized WS2 nano-
could enhance the amount of Mo5+ and S22 in the MoSx, and sheets in a simple hydrothermal reaction system for the first
reduce the size of the MoSx particles. Correspondingly, the time.115 The selection of the starting materials (tungsten chloride
materials exhibited a very high hydrogen evolution rate up to and thioacetamide) was crucial for the formation of sheet-like
6408 mL g 1 cm 2 h 1 at an overpotential of 0.2 V. Distinct WS2. When graphene oxide was added in the reaction system,
from the synthetic methods stated above, Wang et al. fabricated WS2–graphene composite nanosheets with enhanced HER
untra-small amorphous molybdenum sulfide nanoparticles activity were synthesized. Similarly, Cheng et al. prepared WS2
with a diameter of B1.47 nm from bulk MoS2 by the high- nanosheets with monolayer thickness using WCl6 and S as the
energy ultrasonication method.112 Moreover, the nanoparticles precursors by a high-temperature solution-phase method.116
self-assembled on a Au surface to form a highly active film The resulting nanomaterial had efficient and durable activity
towards HER. The authors believed that the Au film preferably for HER. The authors also claimed that the catalytic activity of
adsorbed those nanoparticles containing high exposed surface nanosized WS2 matched that of widely-studied MoS2 materials.
S sites during the assembling process, as confirmed by the fact Moreover, the sonochemical exfoliation method was used to
that the final film had a Mo to S ratio of 1 : 5. This selective convert WS2 nanotubes into WS2 nanoflakes,117 which possessed
enrichment of S edge-rich molybdenum sulfide might be the higher edge sites and catalytic activity than the mother material.
fundamental cause of the great enhancement of the HER Ball-milling and electrochemical techniques were also effective in
catalytic activity (0.92 mA cm 2 at Z = 0.15 V with an ultra-low assisting the formation of WS2 nanostructured catalysts.118
loading of 1.03 mg cm 2). In another notable example, Wang Recently, cobalt- or nickel-containing WSx films were prepared by
et al. fabricated an extremely active polypyrrole–MoSx hybrid an electrodeposition process using [M(WS4)2]2 (M = Co or Ni) as the
structure via the electrochemical copolymerization method precursor.119 The obtained cobalt–tungsten–sulfide (CoWSx) and
(polypyrrole (PPY) is a conductive polymer).113 This hybrid film nickel–tungsten–sulfide (NiWSx) had WS2-like layered structures
Fig. 21 (a) Typical AFM image of exfoliated nanosheets of WS2. Scale bar,
500 nm. (b) High-resolution STEM images of an as-exfoliated WS2 mono-
layer showing regions exhibiting the 1T superlattice. The inset in b shows
the strain tensor map generated from the STEM-HAADF image using peak
Fig. 20 Polarization curves of electrodes modified with: (a) PPy, (b) MoSx, pair analysis. Light (yellow) and dark (black) colours correspond to regions
(c) (NH4)2MoS4, (d) PPy/MoSx, and (e) Pt/C.113 Copyright 2014 WILEY-VCH where the strain is in tension and compression, respectively. Scale bars,
Verlag GmbH & Co. KGaA Weinheim. 1 nm.114 Copyright 2014 with permission from Nature Publishing Group.
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with MII–S–WIV (M = Co or Ni) bimetallic sulfide centers. A further

electrocatalysis study gave two important conclusions: (i) CoWSx
had a higher catalytic activity than NiWSx. However, the reason
behind this phenomenon is still unclear. (ii) The primary catalytic
activity of these M–S–W clusters was believed to locate within the
MS centers. This work might provide some new insights into the
mechanism of heteroatom-doped metal sulfide catalysts.
5.4 Fe, Co, Ni sulfides

Hydrogenases are a class of bio-enzymes that can catalyze
protons and electrons into molecular hydrogen at a low over-

potential that is close to the thermodynamic potential.38–40 In
fact, their catalytic activity is more effective than that of
platinum, which is the best known catalyst for HER. Regardless
of the type of hydrogenase, metal atoms comprising its active
site are only Fe and/or Ni. Specially speaking, the active sites of
[NiFe] and [FeFe] hydrogenases—two widely studied bioenzymes—
Fig. 22 Crystal structure of FeS2 in (a) pyrite or (b) macarsite phase. Fe and
are made of metal-sulfur clusters that are buried in proteins. S are displayed in orange and yellow respectively. (c) Side-view of the
Inspired by the composition and structure of hydrogenases, stable, nonpolar pyrite (100) surface as an example of the low-index
researchers have been exploring synthetic hydrogen-evolving cata- surface with under-coordinated metal cations. The (100) surface is termi-
lysts based on iron or nickel for energy conversion processes.120–122 nated in the sequence [S–Fe–S].121 Reproduced by permission of The
Royal Society of Chemistry.
In this context, Giovanni et al. studied FeS (pyrrhotite) nano-
particles as a bioinspired catalyst for electrochemical hydrogen
evolution in neutral water.120 Although this material had a surface area, and improved the HER catalytic activity. In other
relatively low catalytic activity, it exhibited attractive stability words, the morphology played a crucial role in determining the
without structural decomposition or activity decrease for at least overall catalytic efficacy of CoS2. (ii) CoS2 micro- and nano-
6 days. Kong et al. found that both FeS2 and NiS2 (pyrite, Fig. 22) structuring could promote the release of evolved gas bubbles
were active non-precious HER catalysts in an acidic electrolyte.121 from the electrode surface, and thereby the increase of its
In their study, FeS2 and NiS2 had a comparable catalytic activity operational stability. In another study, Peng et al. synthesized
towards HER, and FeS2 had a higher stability than NiS2 in acidic a CoS2 nanosheet–graphene–carbon nanotube ternary compo-
solution. Moreover, FeS2 exhibited a higher catalytic activity than site material as a freestanding electrode for efficient HER.125
FeS that was reported by Giovanni et al.120 In another study, the The synthesis of this material was based on a two-step process:
NiS2 nanosheet array was grown on carbon cloth to serve as a the growth of CoS2 nanosheets on graphene, and then the
binder-free cathode for efficient HER in a neutral solution.122a combination with carbon nanotubes by vacuum filtration (Fig. 24).
Owing to the unique nanostructure, this electrode could achieve a This nanohybrid film was one of the most active non-precious
current density at a low overpotential of 243 mV. To sum up, metal hydrogen evolution catalysts, owing to the integration of
despite some progress, as outlined above, Fe-/Ni-based sulfide large specific surface area, high electrical conductivity and nano-
catalysts still have a markedly lower catalytic activity than that of porous structure in one material system.
other nonprecious HER catalysts, such as MoS2. In view of their
natural abundance, it should be of significance to search for high-
performance Fe-/Ni-based sulfides for HER in the future. If so, this
might, in turn, help us to develop insights into hydrogenases.
Cobalt sulfides are now emerging as an attractive HER
catalysts, although cobalt has less abundance than Fe or Ni
and no biological relevance to HER. Recent studies demon-
strated that CoS2 was superior to FeS2 and NiS2 for HER in both
acidic and neutral media.121,123 Moreover, CoS2 materials,
especially those with fine nanostructures, have become very
strong competitors among noble metal-free HER catalysts.
There are two important examples in this regard. Jin’s group
synthesized metallic CoS2 materials with three different mor-
phologies—film, microwire and nanowire.124 The authors sys-
Fig. 23 Electrochemical characterization of CoS2 film, microwire array,
tematically studied their structures, activities and stabilities,
and nanowire array electrodes for HER; and scheme illustrating enhanced
and further established the structure–performance relationship hydrogen gas bubble release from CoS2 nano- and microstructures.124
(Fig. 23). They came to two important conclusions: (i) CoS2 Reprinted with permission from ref. 124. Copyright 2014 American
micro- and nanostructuring could increase the effective electrode Chemical Society.
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with only 2–5 Se–Mo–Se atomic layers via the reaction of

MoO2(acac)2 with dibenzyl diselenide under mild conditions
(Fig. 25).127 The resulting material was found to be rich in Mo
in the composition, and thus lack Se, which might produce
more active sites and increase the conductivity for HER. Their
method had the potential to serve as a general pathway for
making various metal selenides, such as WSe2, SnSe, and PbSe.
In addition, Lewis’ group developed a two-step strategy to make
catalytically active MoSe2 films by first synthesizing a mixture
of molybdenum triselenide (MoSe3), molybdenum trioxide
(MoO3) with small amounts of Se, followed with drop-casting

Fig. 24 Fabrication procedure and hydrogen evolution process of
the mixture on glassy carbon for HER.128 They found that the
the freestanding CoS2/graphene/carbon nanotube hybrid electrode.125
Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA Weinheim.
catalyst was not good for HER at the beginning, however, the
activity increased a lot during the subsequent voltammetric
cycles, as observed by the overpotential shift from 400 mV to
Besides crystalline cobalt sulfides, amorphous cobalt sulfide 250 mV for 10 mA cm 2. During the electrocatalysis, the initial
was also discovered recently to be highly active for HER. This mixture was reduced into a porous MoSe2 film, attributed to
amorphous cobalt sulfide material was simply synthesized on the significant enhanced activity. This kind of synthesis was
conductive substrates via an electrochemical deposition method described as operand since the MoSe2 was formed under the
at room temperature.126 The most important features of this conditions of the reaction that it accelerated.
amorphous material are high activity and stability in neutral Aside from the unsupported Mo selenides, some researchers
media. It was among the most active HER catalysts at pH 7, and it are making hybrid composites to place metal selenides onto
was shown to behave as a durable catalyst for electrochemical for various supports (carbon fiber paper, graphene or tungsten foil)
HER at pH 7 with an operating stability of 440 h. It is worth and take the advantages of the support material to increase the
noting that this amorphous material was unstable in acidic HER activity. MoSe2 and WSe2 share similar crystal structures
media and relatively inactive in alkaline media. with MoS2 (Fig. 26), the single layers stack one by one via the
van der Waals force and expose mostly the basal plane with a
small portion of edge sites, which is not favorable for electro-
6. Metal selenides chemical HER. In order to obtain a material with maximum
amount of edge sites for catalytic application, Cui’s group
Both selenium (Se) and sulfur (S) are nearby group VIA in the prepared a vertically arranged MoSe2 film on a flat oxidized
periodic table, in which Se and S can be found in the fourth silicon substrate to obtain the final material with the whole
period and third period, respectively. Thus these two elements surface covered with edge sites of MoSe2.129 This reaction was
not only share some similarities but also differences. For done by the selenization of a Mo film covered oxidized silicon
similar properties, they all have 6 electrons in the outermost and the vertical growth of MoSe2 was proposed as the relatively
shells, and similar oxidation numbers. The outermost electron
configuration of the elements often determines the chemical
properties of the compound formed by these elements, implying
that metal selenides may also show similar activities for HER
compared with metal sulfides. Followed by the intensive research
of metal sulfide materials for HER as discussed above, the
investigation of various metal selenide materials for HER has
received a lot of attention as well. On the other hand, being
located at different periods in the periodic table for Se and S gives
them several distinct characters: (i) the metallic property of Se is
more obvious than S, suggesting the better conductivity; (ii) the
radius of Se is larger than that of S; (iii) the ionization energy for
Se is smaller than that of S. For these reasons, the metal selenides
might possess some unique activities for HER as compared with
metal sulfides.
6.1 Mo and W selenides Fig. 25 (a) Crystal structure of the layered hexagonal MoSe2 phase. The
Mo atom and Se atom are displayed in grey and yellow, respectively. (b)
Lately, research on Mo or W selenides has attracted consider-
Reaction equation for hierarchical ultrathin MoSe2 x nanosheets. (c) Sche-
able attention and there are some interesting results in this matic illustration of the formation process of hierarltrahin MoSe2 x
area.127–134 Yang’s group reported a simple and fast bottom-up nanosheets by a bottom-up colloidal synthetic route.127 Reproduced by
route to make hierarchical MoSe2 x (x E 0.47) nanosheets permission of The Royal Society of Chemistry.
View Article Online
MoSe2 and the Se-edge on MoSe2 and WSe2 played an impor-

tant role in the HER. Moreover, the (0001) basal planes were not
active for the HER, the activity was mainly from the exposed
edge sites. Their results confirmed the significance of edge
sites for HER.
6.2 Fe, Co, Ni selenides

In 2012, the first row transition metal selenide based HER
catalyst (NiSe) was prepared by Yu’s group.135 The reaction was
performed in a ternary solvent with various ratios of diethylene-

triamine, hydrazine hydrate and deionized water, and the
ratios played an important role in controlling the phase and
morphology of the final material with the best activity obtained
for sea urchin-like NiSe. Recently, Cui’s group prepared a series
of first-row transition metal dichalcogenide films (FeSe2, CoSe2,
NiSe2) on a mirror-polished glassy carbon substrate to investi-
Fig. 26 Nanostructures of layered MoS2 and MoSe2. (a) Layered crystal gate the HER activities and CoSe2 was found to be the best
structure of molybdenum chalcogenide with individual S–Mo–S (or among them.121 These metal dichalcogenides are with cubic
Se–Mo–Se) layers stacked along the c-axis by weak van der Waals pyrite-type or orthorhombic macarsite-type structures, in which
interaction. The highly anisotropic crystal structure is the origin of aniso-
metal atoms are octahedrally connected with the Se atom. They
tropic electrical and chemical properties. (b) Schematics of MoS2 nano-
particles with platelet-like morphology distributed on a substrate (left), and believe that the partially filled eg band of CoSe2 might be linked
nanotubes and fullerene-like nanotubes of MoS2 and MoSe2 (right). to its excellent activity. A CoSe2 nanoparticle was also prepared
(c) Idealized structure of edge-terminated molybdenum chalcogenide using a commercial carbon black nanoparticle as the template
films with the layers aligned perpendicular to the substrate, maximally to compare the HER activity of the CoSe2 films. It is not
exposing the edges of the layers.129 Reprinted with permission from
ref. 129. Copyright 2014 American Chemical Society.
surprising that the nanoparticle catalyst outperforms the film
one due to the exposed catalytic sites. After that, Cui’s group
reported another facile preparation method to synthesize CoSe2
easy diffusion of selenium through the van der Waals gaps. nanoparticles on high surface area carbon fiber paper by the
Subsequently, Cui’s group reported another supported material selenization of cobalt oxide modified carbon microfiber paper
by vertically growing MoSe2 and WSe2 on carbon fiber paper.130 under Se vapor conditions (Fig. 27).136 Such an approach can be
This kind of design could expose the maximum amount of edge easily extended to make other metal chalcogenides, such as
sites, namely the HER active locations, for a dramatic increase NiSe2. And the resulting 3D electrode functionalized with CoSe2
in the activity. The carbon fiber paper was chosen in their generated a high cathodic current (100 mA cm 2) at a low
experiment because it has a curved and rough surface, which overpotential (180 mV) in acidic medium for HER.
could increase the surface area of the final material and help to Besides these, Lewis’s group reported an amorphous film
display more edge sites. The high stability of this hybrid composed of CoSe in a polymeric Se matrix via electrodeposi-
material for HER was ascribed to the strong binding affinity tion from an aqueous solution of Co(C2H3O2)2 and SeO2 onto a
between the metal selenide layers and the carbon fiber paper titanium foil under ambient conditions.137 The prepared cobalt
substrate. Similarly, Chen’s group designed and prepared amorphous films only needed ca. 135 mV overpotential to
perpendicularly oriented MoSe2–graphene nanosheets, which reach a current density of 10 mA cm 2 for HER in 0.5 M
could also expose a lot of active sites for HER.131 Moreover, H2SO4. Sun’s group reported the synthesis of a CoSe2 nanowire
Lewis’ group reported the deposition of WSe2 thin films on array on carbon cloth (CC) through hydrothermal selenization
a conductive tungsten foil via a chemical-vapor-transport of a Co(OH)F nanowire array. This CoSe2/CC electrode exhib-
method.132 The resulting WSe2 platelets were also arranged ited excellent catalytic activity (overpotential of 130 mV to get
perpendicularly to the substrate. Furthermore, Wang’s group 10 mA cm 2) and durability (448 h) in acidic media.138 In
demonstrated a simple electrochemical method to make the addition, another hybrid material Ni/NiO/CoSe2 with Ni/NiO
composite of MoSe2–reduced graphene oxide/polyimide.133 The core–shell nanoparticles decorated on CoSe2 nanobelts was
resulting composite film showed good photoelectrocatalytic made by Yu’s group.139 The presence of CoSe2 was crucial for
activities for HER, demonstrating a large cathode current. the nucleation and growth of Ni because bigger Ni/NiO parti-
The advantage of such photoelectric active materials is the cles were obtained without the CoSe2. The activity of Ni/NiO/
application in solar-driven HER, which also utilizes the energy CoSe2 turned out to be better than either Ni/NiO or CoSe2 due
from the sun and realizes a clean energy conversion technique. to some reasons: (i) more active sites for HER was provided in
Except the above experimental results, the DFT calculation the modified CoSe2, (ii) the Ni core was conductive and thus
method was also employed to explore the origin of HER activity decreases the resistance, (iii) the thin NiO which served as
of MoSe2 and WSe2.134 It has been found that Mo-edge on Lewis acid can help to dissociate the water molecule and this
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materials could have the potential to control the activity and

thus provide better catalysts for HER.
7. Metal carbides
In 1973, R. B. Levy and M. Boudart discovered that tungsten
carbide possessed some platinum-like catalytic behaviors because
of its similar d-band electronic density states to platinum.143,144
This pioneering work immediately evoked great interest among
chemical researchers, and simultaneously great enthusiasm was
devoted to the research of metal carbides with the aim of

replacing expensive noble metal catalysts. This has led to many
promising carbide-based applications, ranging from hetero-
geneous catalysis (e.g., decomposition of alcohols and activation
of oxygen) to electrolysis in fuel cells and electrolyzers.32,34,36 In
this section, we specially highlight the recent research efforts
Fig. 27 (a) Crystal structure of CoSe2 in the cubic pyrite-type phase (left) toward developing nanosized carbide materials as the noble
and the orthorhombic macarsite-type phase (right), in which Co and Se are metal-free hydrogen evolution electrocatalysts. In the discussion,
displayed in orange and yellow, respectively. (b) Photograph of the as-
particular attention is paid to the synthesis of metal carbide
prepared CoSe2 catalyst on a piece of 1.5 cm 10 cm carbon fiber paper.
(c) SEM image of a layer of CoSe2 catalyst grown on carbon fiber paper. nanomaterials with an emphasis on molybdenum and tungsten
(d) High-resolution SEM image revealing the structure of CoSe2 coating, carbides, and the structural effects on the properties of the
consisting of nanoparticles in dimension of tens of nanometers.136 materials.145–167 It is worth noting that some carbide-supported
Reprinted with permission from ref. 136. Copyright 2014 American Pt catalysts are beyond the scope of this review.168–182
Chemical Society.
7.1 Molybdenum carbide

was further enhanced by the chemical synergistic effect of NiO In 2012, Hu’s group made the first observation of molybdenum
and CoSe2. carbide, actually b-Mo2C, showing high activity for HER.145 In
this study, Hu et al. studied the electrocatalytic performance of
6.3 Sulfur doped metal selenides commercial b-Mo2C microparticles, which exhibited unexpect-
Due to the similarities of S and Se, one of them could be doped edly high activity and durability toward HER in both acidic and
into the compound formed by the other one with metal, as a basic media. In addition, Leonard’s group synthesized four
result, the hybrid materials may show different properties phases of Mo–C (Fig. 28), including a-MoC1 x, Z-MoC, g-MoC
because of the differences between S and Se. Sampath’s group and b-Mo2C, and compared their catalytic activity in acidic
reported the few-layered alloy material of MoS2(1 x)Se2x with solution.146 The results revealed that the catalytic activities
various compositions and the highest HER activity was found of the four phases towards HER increased in the order of
when the molar ratio of S and Se was 1 : 1 in the resulting a-MoC1 x o Z-MoC o g-MoC o b-Mo2C. Inspired by these
material, which was even better than the pristine few-layered pioneering studies, fine structural optimization of molybde-
MoS2 and MoSe2.140 Their results indicated that the electro- num carbide catalysts, especially at the nanoscale, has actively
catalytic activity could be easily tuned by changing the compo- been pursued. Liao et al. synthesized nanoparticle-assembled
sition of the target materials, that is, incorporation of Se into Mo2C nanowires by simple thermal treatment of a MoOx–amine
the MoS2 lattice structure or vice versa. He’s group prepared the hybrid precursor under an inert atmosphere.147 The Mo2C
WS2(1 x)Se2x nanotubes with controllable S and Se amounts on nanowires were composed of nanocrystallites of about 10–15 nm
carbon fiber via the chemical vapor deposition method.141 The in size, and had a large surface area of 63.9 m2 g 1. The excellent
as-grown material can serve as an electrocatalyst for HER with catalytic activity of this nanowire material was attributed to its large
small overpotential, high exchange current density and con- surface areas, nanosized crystallites and porous structure. A similar
ductivity. Recently, Yan’s group reported the preparation of synthetic strategy was adopted by Wang’s group to prepare porous
S-doped MoSe2 nanosheets by reacting Mo-oleylamine and Mo2C nanorods using anilinium molybdate as the precursor.148
Se-oleylamine-dodecanethiol mixtures, in which the surfactant This resulting material possessed high electrical conductivity and
was used to reduce the surface energy of edge sites and the catalytic activity in an acid solution, and its catalytic activity could
incorporation of S can create some defects on the basal be further improved by loading Ni nanoparticles.
plane.142 Therefore, more active edge sites were yielded in the Recently some studies demonstrated that carbon nanotube
final ultrathin nanosheet material. Based on these results, and graphene could function as both a carbon source for the
research on other S and Se co-exited metal dichalcogenide formation of Mo2C, and an effective support material to anchor
may still continue in the future and more appealing outcomes as-formed MoC2 nanoclusters. This finally led to high-performance
would show up since the tunable ratio of S and Se in the MoC2–nanocarbon composites for HER. Sasaki’s group prepared a
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Fig. 29 The synthesis from soybeans and ammonium molybdate of a

Fig. 28 X-ray diffraction (XRD) patterns of (a) a-MoC1 x, (b) Z-MoC, solid catalyst suitable for electrochemical hydrogen production. A solid-
(c) g-MoC, and (d) b-Mo2C. The insets show the corresponding crystal state reaction between soybeans and the molybdate leads to their reduc-
structures.146 Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA tive carbonization and nitridation, so as to form b-Mo2C and g-Mo2N
Weinheim. crystals.153 Reproduced by permission of The Royal Society of Chemistry.
MoC2–carbon nanotube composite by in situ carburization of carbide was demonstrated to be an excellent substrate to support
ammonium molybdate on carbon nanotubes without using noble metal catalysts (e.g., Pt), the development of pristine
other carbon sources.149 The as-prepared composite catalyst tungsten carbide as a high-performance catalyst is more
showed superior electrocatalytic activity and stability toward appealing due to the avoidance of noble metals. Wirth et al.
HER compared to the bulk Mo2C. In addition, MoC2–graphene systematically investigated a series of commercial IVB–VIB
and MoC2–nanocarbon–nanotubes were also prepared by two transition metal carbides for HER in an acid solution, and
different groups.150,151 It is worth noting that in the MoC2– among them, tungsten carbide exhibited the best catalytic
nanocarbon–nanotubes ternary composite material, the carbon activity, even better than molybdenum carbide (Fig. 30).155 This
nanotube–graphene hybrid support was believed to play multi- is really a good news for tungsten carbide. However, the
ple roles in avoiding aggregation of nanocrystals, providing a performance of tungsten carbide still needs to be further
large contact area with the electrolyte, facilitating the electron optimized in terms of both activity and stability.
transfer, and thus enhancing the catalytic activity of Mo2C. Tungsten carbide is typically synthesized in a carbon-rich
Furthermore, graphitic carbon nitride was used as a highly reaction system. This often leads to the as-obtained tungsten
active carbon source for the synthesis of the Mo2C/carbon HER carbide material having some additional surface carbons. These
catalyst.152 In particular, Alhajri et al. prepared this material via surface carbons usually have adverse effects on the catalytic
a thermally-driven reaction of a molybdenum precursor with properties of materials because they can block the direct inter-
mesoporous C3N4 under an inert atmosphere. The confinement action between the reactants and the WC surface. Chen’s group
effect of mesopores gave rise to the final material with a small recently reported an atomic oxygen pretreatment method to
particle size (8 nm) and a large surface area (308 m2 g 1). remove the carbon on the surface of WC to a certain extent.156
Biomass, such as soybean and sodium alginate, was recently The atomic oxygens were generated in an oxygen plasma source.
considered as ‘‘green’’ chemical agents for the preparation of This pretreatment was proven to improve the catalytic activity for
Mo2C-based nanocatalysts. Chen et al. reported the synthesis of HER. In another study, Hunt et al. presented a very smart
b-Mo2C and g-Mo2N nanocomposite catalysts via the solid-state method for the preparation of surface-exposed tungsten carbide
reaction between soybeans and ammonium molybdate (Fig. 29).153 nanocatalysts 1–4 nm in size (Fig. 31).157 The key steps for
Their experimental results demonstrated that b-Mo2C was the the synthesis to be successful are: (i) the synthesis of WOx
catalytically active phase and g-Mo2N was the acid-proof phase. nanoparticles encapsulated within the SiO2 matrix; (ii) high-
The hybridization of b-Mo2C and g-Mo2N resulted in the high temperature carburization treatment; (iii) removal of the SiO2
catalytic activity and durability of the material. The activity of shell and anchoring tungsten carbide nanoparticles on a high-
the composite catalyst could be further enhanced by coupling surface-area carbon support.
graphene. In the other study, Cui et al. presented the synthesis Very recently, Garcia-Esparza et al. reported the synthesis of
of Mo2C nanoparticles on graphitic carbon sheets using a carbon-coated tungsten carbide nanocrystals (B5 nm) through
biopolymer, sodium alginate, as the carbon source.154 The the reaction of tungsten precursors with mesoporous graphitic
biomass-assisted synthesis provides us a novel methodology C3N4 as the reactive template.158 Unexpectedly, this material
for low-cost, scaled-up synthesis of noble metal-free water exhibited very high catalytic activity and stability for HER over a
splitting catalysts. wide pH range. It is worth noting that tungsten carbide,
generally, has a poor stability in neutral and basic media.159–162
7.2 Tungsten carbide Thus, this result might indicate the importance of additional
Tungsten carbide, one of the most important metal carbides, carbon on the surface of tungsten carbide. In addition, the most
was first found to have Pt-like catalytic properties. While tungsten incomprehensible thing is how a carbon-coated material could
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Fig. 32 The synthesis of graphene nanoplatelet-supported W2C and WN

nanoparticles from ammonium paratungstate, aniline, and graphene
nanoplatelets.164 Reproduced by permission of The Royal Society of

Chemistry.
amount of iron in the material is very low. In another study,

Fig. 30 Comparison of the electrocatalytic HER of selected electrocata- Chen et al. reported graphene nanoplatelet-supported W2C–WN
lysts by cyclic voltammetry. The catalyst samples were mechanically
nanocomposites via an in situ solid-state reaction between
immobilized on a graphite electrode and immersed in 0.1 M H2SO4.155
Copyright 2014 with permission from Elsevier. aniline and tungstate (Fig. 32).164 This nanocomposite catalyzed
the HER with very low overpotential and was stable for at least
300 h under harsh acidic conditions. The authors proposed that
show good, even excellent catalytic activity. This somewhat vio- the presence of WN moderated the M–H binding strength on the
lates the original concept (see above), that is, achievement of high material surface, inhibited the formation of tungsten oxide, and
catalytic activity over carbon-free tungsten carbide. Thus, this calls thus enhanced the HER activity.
for further mechanistic studies on pristine tungsten carbide and
tungsten carbide–carbon composite materials.
A nitrogen-doping strategy was proposed by Zhao et al. to
8. Metal nitrides
enhance the catalytic activity of tungsten carbide.163 They Transition metal nitrides (TMNs) prossess unique physical and
prepared tungsten carbonitride nanoparticles with polydiamino- chemical properties.183,184 On the one hand, the inclusion of
pyridine as both carbon and nitrogen sources as well as Na2WO4 nitrogen atoms modifies the nature of the d-band of the parent
as the tungsten source. A small amount of iron as a graphitiza- metal, resulting in a contraction of the metal d-band. This
tion catalyst was necessary to realize the synthesis of a N-rich makes the electronic structure of TMNs more similar to noble
tungsten carbonitride material. The authors believed that the N metals (e.g., Pd and Pt).185 On the other hand, nitrogen can
species in the material substantially decreased the electron nest in the interstices of the lattices due to the small atomic
density of the W atoms, and N-bound W species were related radius, so that the arrangement of metal atoms always main-
to the HER activity of Fe-WCN materials. However, the possible tains close-packed or near close-packed. This endows TMNs
role of iron in the material was not discussed, although the with an attractive electronic conductivity.186 These promising
features, coupled with their high resistance against corrosion,
make this kind of materials more reliable relative to metal or
metal alloys.
Chen et al. demonstrated the catalytic activity of molybde-
num nitride (MoN) towards HER in 2012.187 To improve the
catalytic activity, the authors introduced Ni into MoN to form
Ni–Mo bimetallic nitrides for the purpose of moderating Mo–H
binding strength. The as-obtained Ni–Mo nitride with a
nanosheet morphology contained a majority of g-Mo2N and
Ni2Mo3N phases. The thickness of the sheets ranged from 4 to
15 nm, and the gap between two single sheets was found to be
about 2 nm. According to EXAFS studies, the authors found
that Ni species segregated to the surface of NiMoNx, forming a
Ni-rich domain. This segregation of the Ni phase during the
nitridation process was proposed to be the reason behind the
formation of nanosheets. It is self-evident that this sheet
Fig. 31 Synthesis of ultrasmall tungsten carbide material. (a) STEM image
nanostructure can afford plenty of highly accessible reactive
of silica-encapsulated tungsten oxide nanoparticles. (b) STEM image of
silica-encapsulated WC nanoparticles. (c) STEM image of WC nano-
sites to enhance the HER activity. In addition, the EXAFS results
particles supported on carbon black.157 Copyright 2014 WILEY-VCH Verlag also revealed an increase of Ni–Ni distance and a decrease of
GmbH & Co. KGaA Weinheim. Ni–Mo distance during nitride formation, further indicating
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the strong interaction between Ni and Mo in the bimetallic observed that the surfaces of the atomically-thin MoN nanosheets
nitride structure. Accordingly, this NiMoNx catalyst exhibited were wholly comprised of apical Mo atoms, and the surface Mo
an excellent activity for the HER with a small overpotential of atoms could act as the active sites for catalyzing protons into
78 mV and a Tafel slope as small as 35 mV dec 1. And the hydrogen. Therefore, the rich active surface sites, together with the
material could maintain the structure and catalytic activity in better conductivity, made the MoN nanosheets achieve a high
acidic media, affording strong evidence for the stabilizing current density of 38.5 mA cm 2 at Z = 300 mV. In another study, a
effect of nitridation. tungsten nitride nanorod array was first synthesized by Sun et al.,
In another significant work, Cao et al. successfully prepared and it could serve as an all-pH efficient and durable HER catalyst
a cobalt molybdenum nitride (Co0.6Mo1.4N2) via annealing a with an overpotential of 198 mV to achieve a current density of
Co3Mo3N precursor under flowing NH3 at 400 1C for 1 h.188 This 10 mA cm 2.190
bimetallic nitride possessed a four-layered mixed closed packed

structure with alternating layers of octahedral sites and trigonal
prismatic sites (Fig. 33). In this structure, Mo ions preferred the 9. Metal phosphides
trigonal prismatic sites, while a Co–Mo mixture occupies the
ochtahedral site. N ions were found in close packed layers with Metal phosphide is another kind of promising non-Pt HER
a repeating AABB staking sequence. The authors proposed that catalysts. Like metal sulfides, the conjecture about their possi-
this alternative substitution on octahedral sites allowed Co to ble application in this field also originates from the imitation of
tune the electronic states of Mo, and potentially enhance the hydrogenase. In 2005, Rodriguez’s group first brought forward
HER activity of MoN. The HER measurement verified this a standpoint that Ni2P might be the best practical catalyst for
hypothesis. A current density of 10 mA cm 2 at Z = 0.20 V could the HER according to their DFT calculation, which indicated
be achieved by this catalyst, and the activity of ternary the excellent catalytic behavior of Ni2P(001) toward the HER.191
Co0.6Mo1.4N2 was much higher than that of binary d-MoN in In their study, they found that in Ni2P the Ni concentration was
both acidic and alkaline media. diluted by the introduction of P elements, which made
Besides these, Xie et al. recently reported the fabrication of Ni2P(001) behave somewhat like the hydrogenase rather than
metallic MoN nanosheets with atomic thickness (B1.3 nm) by the pure metal surface. The negatively charged nonmetal atoms
liquid exfoliation of MoN bulk materials.189 DFT calculations and isolated metal atoms functioned as proton-acceptor sites
on the density of states (DOS) and the charge density distri- and hydride-acceptor sites, respectively. In other words, the
bution showed that MoN nanosheets had higher electric con- proton-acceptor sites and hydride-acceptor sites co-exist on
ductivity and charge density than its bulk counterpart. This the surface of Ni2P(001), and this so-called ‘‘ensemble effect’’
means that MoN nanosheets can effectively facilitate electron would facilitate the HER. This bore a resemblance to the
transport during the catalytic process. Moreover, the authors catalytic mechanism of [NiFe] hydrogenase and its analogues.
Furthermore, they found that during the HER progress hydrogen
strongly bound with the Ni hollow sites, but with the assistance
of P, the bonded hydrogen could be easily removed from the
Ni2P(001) surface. This important theoretical prediction stimu-
lates enormously the investigation on metal phosphides as
HER catalysts.
Basically, metal phosphides have similar physical properties
to ordinary metallic compounds such as carbides, nitrides,
borides and silicides. They have relatively high mechanical
strength, electrical conductivity and chemical stability. Different
from carbides and nitrides with relatively simple crystal struc-
tures (e.g., face-centered cubic, hexagonal close-packed or simple
hexagonal), the crystal structure of phosphides is based on
trigonal prisms due to the large radius of phosphorus atoms
(0.109 nm). These prismatic building blocks in phosphides are
similar to those in sulfides. But metal phosphides tend to form a
more isotropic crystal structure (Fig. 34), rather than a layered
Fig. 33 (a) Lab X-ray powder diffraction patterns of Co3Mo3N, CoMoN2,
structure that is observed in metal sulfides.192 This structural
and d-MoN. Asterisk marks the impurity peak of cobalt metal. (b) Four- difference possibly results in metal phosphides having a greater
layered crystal structure of CoMoN2. (c) Rietveld refinements of neutron number of coordinatively unsaturated surface atoms than
diffraction for CoMoN2 showing observed data (black line), calculated metal sulfides. Thus, metal phosphides might have an intrin-
pattern (red line) and difference curve (bottom line). Lab X-ray diffraction
sically higher catalytic activity than metal sulfides. To sum up,
data (blue line) in the same Q (=2p/d) range between 2 and 7 Å 1 do not
clearly show superstructure peaks such as the 013 and 015 reflections
since the past two years metal phosphides have attracted
which are intense in neutron diffraction data.188 Reprinted with permission particular attention in the field of HER, and numerous research
from ref. 188. Copyright 2014 American Chemical Society. studies are ongoing.
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nanoparticles showed a enhanced stability without activity loss

at Z = 170 mV in 1 M H2SO4 for 48 hours. In addition, Pu et al.
successfully prepared Ni2P nanoparticle films supported on a Ti
plate via electro-deposition of nickel hydroxide nanoparticle
films on a Ti plate followed by phosphidation using NaH2PO2.195
The as-obtained binder-free electrode afforded current densities
of 20 and 100 mA cm 2 at small overpotentials of 138 and
188 mV, respectively. Kucernak et al. subsequently investigated
the effect of phosphorus content on hydrogen evolution activity
and corrosion resistance in acidic medium.196 In their study,
the three samples with different phosphorous content, nickel–

phosphorus alloy (8 at% P), Ni12P5 (29 at% P) and Ni2P (33 at% P).
The results showed that the materials with higher phosphorus
content were more corrosion-resistant and more HER-active.
Besides Fe2P-type Ni2P, other phases of nickel phosphide
with different stoichiometry and crystal structure (e.g., NiP2 and
amorphous nickel phosphide) are also investigated for HER
Fig. 34 Crystal structures of some transition metal phosphides.192 Copyright recently.197–199 For example, Jin et al. reported a grain-mediated
2014 with permission from Elsevier. electroless method to prepare amorphous undoped, tungsten-
doped nickel phosphide microspheres supported on Ni foam.199
This is the first time that the HER performance of amorphous
9.1 Nickel phosphide
nickel phosphide was investigated. In addition, tungsten-doped
Popczun et al. first confirmed experimentally the HER effi- nickel phosphide exhibited enhanced activity than undoped nickel
ciency of Ni2P nanoparticles (Fig. 35).193 In their study, they phosphide, and the former could achieve a high current density
synthesized Ni2P nanoparticles (21 nm) through themolysis of of 20 mA cm 2 at Z = 110 mV. However, the role of W-doping is
nickel(II) acetylacetonate in 1-octadecene, oleylamine and tri-n- still unclear.
octylphosphine (TOP). It is worth noting that this reaction is
highly corrosive and flammable, and thus must be carried out 9.2 Cobalt phosphide
under rigorously air-free conditions. The resulting Ni2P nano- Cobalt phosphide is another metal phosphide which has
particles were hollow and faceted to expose the (001) planes of recently been confirmed to show great catalytic activities
Ni2P. As for HER measurement, Ni2P nanoparticles were depos- towards HER. Different from Ni2P with a Fe2P-type structure,
ited onto a Ti foil substrate followed by annealing treatment. CoP has a B31 MnP-type structure type. In the CoP structure,
The as-prepared Ni2P/Ti electrode exhibited excellent HER phosphorus atoms are surrounded by six metal atoms at the
activity with an exchange current density of 3.3 10 5 mA cm 2 corners of a highly distorted triangular prism, further forming a
and a Tafel slope of B46 mV decade 1. However, the stability of zig-zag chain extending in the b direction with a P–P distance of
the Ni2P/Ti electrode was not satisfactory. 2.70 Å. Popczun et al. first reported in 2014 that CoP is a highly
To optimize the synthesis conditions and to improve the active and acid-stable HER catalyst (Fig. 36).200 They synthe-
stability of Ni2P, Hu’s group developed a simple and scalable sized multi-faceted, hollow CoP nanoparticles via reaction of
solid-state reaction route to prepare Ni2P nanoparticles with a Co nanoparticles with thioctylphosphine (TOP). Then these
diameter of 10–50 nm via a thermal-driven reaction between nanoparticles were deposited on a Titanium (Ti) support,
NaH2PO2 and NiCl26H2O at 250 1C.194 The resulting Ni2P followed by annealing treatment, to construct CoP/Ti working
electrodes. The as-prepared electrodes produced a cathodic
current density of 20 mA cm 2 at an overpotential of 85 mV,
and showed great stability in 0.5 M H2SO4 for 24 h.
In addition, Sun’s group has made the greatest contribution
to this area, especially pioneering the low-temperature toptactic
transformation preparation of metal phosphide nanostructures
and their arrays. This group reported the synthesis of CoP
nanocrystals decorated on carbon nanotubes (CoP/CNT), which
showed a notable HER catalytic activity with a current density
of 10 mA cm 2 at an overpotential of 122 mV.201 The CoP/CNT
was prepared by a low-temperature phosphidation of a Co3O4/
CNT precursor with NaH2PO2. Using a similar method, this
Fig. 35 Crystal structures of some transition metal phosphides.193
group successfully grew nanoporous cobalt phosphide nano-
Reprinted with permission from ref. 193. Copyright 2014 American wire arrays on carbon cloth (CC) (Fig. 37).202 The authors also
Chemical Society. found that the obtained CoP/CC was quite stable to sustain
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Fig. 37 (a) XRD patterns of the Co(OH)2 precursor and CoP. (b) Low- and
(inset) high-magnification SEM images of Co(OH)2/CC. (c) Low- and (inset)
high-magnification SEM images of CoP/CC. TEM images of (d) Co(OH)2
and (e) CoP nanowire. (f) HRTEM image of the CoP nanowire. (g) STEM
image and EDX elemental mapping of P and Co for the CoP nanowire.202
Reprinted with permission from ref. 202. Copyright 2014 American
Chemical Society.
In another important study, Saadi et al. prepared an amor-

phous cobalt phosphide film on a copper substrate by cathodic
Fig. 36 (a, b) TEM images, (c) SAED pattern, and (d) HRTEM image of CoP
depositon from a boric acid solution of Co2+ and H2PO2 .210
nanoparticles. (e) Two views of the MnP-type crystal structure of CoP.200
Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA Weinheim. The as-deposited thin film with a Co : P ratio of 20 : 1 included
multiple constituents, such as metallic cobalt, phosphide, and
amorphous-oxide forms. After the HER measurement, the Co : P
hydrogen production over 80 000 s at all-pH values. The most ratio in the film decreased to 1 : 1, indicating that high-valent
contribution of this work to the related community is that the Co and P species were removed under HER conditions. This
authors proposed a novel concept for constructing binder-free in situ film purification yielded a highly active electrocatalyst
3D metal phosphide arrays as efficient hydrogen evolution actually, which showed a current density of 10 mA cm 2 at an
cathodes. Besides these two efforts stated above, this group overvoltage of 85 mV.
further grew CoP nanoparticles, nanosheet arrays and nano-
wires on carbon cloth or Ti plate, and all these binder-free
electrodes showed high catalytic performances.203–205 9.3 Iron and copper phosphides
Sun’s group also investigated the effects of morphology on Compared with Co and Ni, more abundant metal elements
the hydrogen evolution activity of CoP.206,207 The authors (Fe and Cu) have been introduced into the growing family
reported a template-assisting synthesis to make CoP nano- of metal phosphide catalysts. Zhang et al. first reported the
tubes through low-temperature phosphidation of Co salt electrocatalytic hydrogen evolution activity of nanoporous FeP
inside a porous anodic aluminium oxide template followed nanosheets in acidic medium.211 This material was prepared
by dilute HF etching. The catalytic activity and durability by an anion exchange reaction of Fe18S25–TETAH (TETAH =
of CoP nanotubes were superior to nanoparticle counter- protonated triethylenetetramine) nanosheets with phosphorous
parts.206 This group further compared the electrocatalytic ions. In addition, other approaches were also exploited to prepare
performance of CoP nanowires, nanosheets and nanoparticles.207 FeP nanomaterials. Callejas et al. synthesized MnP-type FeP
They found that CoP nanowires exhibited the highest catalytic nanoparticles (B11 nm) via decomposing Fe(CO)5 in a mixture
activity and stability compared to CoP materials with other of oleylamine and 1-octadecene at 190 1C, followed by reaction
morphologies. with TOP at 340 1C for 1 h (Fig. 38).212 Moreover, a low-temperature
Besides CoP, the catalytic activity of Co2P was also explored phosphidation reaction was carried out with NaH2PO2 as the
by different groups. Huang et al. successfully synthesized Co2P phosphorous source to grow FeP nanowire arrays on both Ti
nanomateials using cobalt acetate and thiphenylphosphine plate and carbon cloth, FeP–graphene hybrid nanosheets and
as the starting materials in oleylamine.208 The product has a FeP–carbon nanotube materials.213–216 Specially, the FeP
rod-like morphology with 9.8 1.3 nm diameter and 110.0 nanoparticles-modified carbon cloth exhibits ultrahigh catalytic
11.8 nm length. In addition, the Co2P exhibited a comparable activity comparable to that of commercial Pt/C and good stability
catalytic activity to CoP. Lu et al. further compared the HER in acidic media.216
activities and stabilities of Co2P, Co1.33Ni0.67P and Ni2P nano- Copper phosphide was demonstrated to be HER-active by
rods, and their results showed that the Co2P nanorods showed Sun’s group.217 They prepared self-supported Cu3P nanowire
the highest activity and durability among them.209 arrays on commercial porous copper foam. This material
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Fig. 39 Schematic graph to show the structural evolution upon phos-

phorization.218 Reproduced by permission of The Royal Society of
Chemistry.
Fig. 38 TEM image of FeP nanoparticles.212 Reprinted with permission

from ref. 212. Copyright 2014 American Chemical Society. showed that the material was active in both acid and neutral
electrolytes, and the carbon flake enhanced the HER activity of
MoP effectively. Kibsgaard et al. introduced sulfur (S) into the
showed a high catalytic performance in acidic solution, and it surface of MoP, producing a molybdenum phosphosulfide
could achieve a current density of 10 mA cm 2 at a low over- (MoP/S) catalyst with superb activity and stability for the HER
potential of 143 mV. in an acidic environment.221 Sulfur-doping was achieved by a
post-sulfidation treatment of MoP in an H2S atmosphere.
9.4 Molybdenum and tungsten phosphides According to the XRD measurement, the short sulfidation
Molybdenum phosphide (MoP) as a well-known hydrodesulfur- treatment did not alter the bulk crystal of MoP. The obtained
ization (HDS) catalyst. Although HDS and HER are different MoP/S only required an overpotential of 86 mV to reach
catalytic processes, there are still some similarities in both 10 mA cm 2, whilst MoP with the same morphology reached
reactions, such as the reversible binding and dissociation 10 mA cm 2 at an overpotential of 117 mV. The incorporation
of H2. In addition, its rhodium- and palladium-like properties of sulfur into the surface apparently was believed to mitigate
were also revealed by DFT calculation. These positive results surface oxidation of the phosphide.
prompted some researchers to explore the HER activity of MoP. Apart from crystalline MoP, Schaak’s group successfully
Wang’s group first confirmed the efficient HER catalytic activity prepared discrete, uniform, and amorphous MoP nanoparticles
of MoP in 2014.218 In their study, they prepared bulk MoP and with diameters of approximately 4 nm through heating Mo(CO)6
Mo3P by tuning the reaction parameters such as reaction and trioctylphosphine in squalane at 320 1C, followed by thermal
temperature (Fig. 39). Comparison of the HER performances treatment at 450 1C in H2(5%)/Ar(95%).222 The group further
of Mo, Mo3P and MoP revealed that phosphorization could synthesized amorphous tungsten phosphide (WP) nanoparticles
modify the properties of the metal, and degrees of phosphor- with an average diameter of 3 nm through the same method
ization also had an important effect on the HER activities and (Fig. 40).223a This material exhibited a very high catalytic perfor-
stabilities. Different from Mo and Mo3P suffering from severe mance with a current density of 10 mA cm 2 at an overpotential
performance degradation in both acidic and alkaline media, of 120 mV in acidic solution. Recently, crystalline tungsten
bulk MoP exhibited high activity and stability under both phosphide micro–nano structures were successfully prepared
conditions.
Sun’s group prepared a closely interconnected network of
MoP nanoparticles with a high specific surface area of 143.3 m2 g 1
through a temperature-programmed reduction method.219
The network-like MoP nanomaterial gave a high catalytic
activity with an onset overpotential of 40 mV and a Tafel slope
of 54 mV dec 1 in acidic solution, and maintained its catalytic
activity for 24 h. The authors believed that the closely inter-
connected network of MoP nanoparticles was the key to realize
the high HER activity. This group also prepared MoP nano-
sheets supported on biomass-derived carbon flake via a solid-
state reaction, in which (NH4)6Mo7O244H2O, NaH2PO42H2O
and sodium alginate were the source of Mo, P and C.220 The
thickness of one MoP nanosheet was measured to be around Fig. 40 (a) TEM image and (b) SAED pattern of as-synthesized, amorphous WP
1.6 nm, and only bulk MoP could be obtained without the nanoparticles. (c) HRTEM image of a single amorphous WP nanoparticle.223a
addition of sodium alginate. The electrochemical measurements Reproduced by permission of The Royal Society of Chemistry.
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by Sun’s group, and they exhibited similar catalytic activity with

the amorphous counterpart.223b,c
10. Heteroatom-doped nanocarbons

As seen from the above sections, nanocarbons (e.g., graphene
and carbon nanotube) are often selected to support HER
nanocatalysts for promoting the catalytic performances (activity
and stability) of the latter. Generally, nanocarbons could provide
either favorable structural supports (e.g., large surface area) or

cooperative electrical effects (e.g., enhanced electron transfer
and transport) or both in those cases. However, these nano-
carbon materials are HER-inert intrinsically. In this section, we
will introduce a new class of HER catalysts, that is, heteroatom-
doped nanocarbons.224–229 The fundamental difference between
nanocarbon catalysts and conventional metal-based catalysts
Fig. 41 (a) NBO population analysis of six different nonmetallic hetero-
(e.g., MoS2) is that the catalytically active sites of nanocarbon
atoms in a graphene matrix. pN and gN represent pyridinic and graphitic
catalysts do not involve metal ions. Even if some nanocarbon type of N, respectively. Inset shows the proposed doping sites for different
catalysts contain a small amount of metals in them, these metals elements, sites 1 and 2 are the edge and center in-plane sites, respectively,
are well encapsulated inside the carbon shells, and they are and site 3 is an out-of-plane center site in graphene. (b) The calculated
not accessible to reactants.227–229 The charms of nanocarbons as free energy (DGH*) diagram for HER at the equilibrium potential (URHE =
0 V) for N- and/or P-doped graphene models. (c) Relationship between
‘‘non-conventional’’ HER catalysts might mainly originate from
DGH* and Ediff for various models.225 Reprinted with permission from
the cheapness and excellent physicochemical properties (e.g., ref. 225. Copyright 2014 American Chemical Society.
high chemical stability) of carbon materials.
Intentional introduction of some heteroatoms is necessary
to make the catalytically inactive pristine nanocarbon materials The excellent catalytic performance of the resulting hybrid mate-
highly active. This might lead to the creation of defect sites that rial originated from the synergistic effect of g-C3N4 and N-doped
can modulate the physical and chemical properties of nano- graphene. g-C3N4 provided highly active hydrogen adsorption
carbon, and more importantly, the addition of reactive sites sites, and N-doped graphene facilitated the electron-transfer
that mediate the conversion of atomic/molecular species to process for proton reduction.
the desired products. This is particularly well-demonstrated by Besides graphene-based catalysts, heteroatom-doped carbon
heteroatom-doped graphene-based HER catalysts. Sathe et al. nanotubes have also been discovered to be efficient HER
reported a B-substituted graphene with an enhanced activity catalysts. Zou et al. prepared cobalt-embedded, nitrogen-rich
for HER. This material was synthesized by doping defective carbon nanotubes by a simple, easily scalable route that involved
graphene with B atoms using borane tetrahydrofuran (BH3-THF) thermal treatment of the Co2+-embedded graphitic carbon nitride
as the borylating agent.224 In electrochemical water reduction, precursor.227a The resulting heteroatom-doped carbon nanotubes
the material exhibited a lower overpotential, by B100 mV, than have been proven to be highly efficient, non-noble metal electro-
its undoped counterpart. To explore the effects of various catalysts, which can catalyze the HER with activities close to that
dopants (N, B, O, S, P, F) in graphene toward HER activity, of 1 wt% Pt. Because cobalt nanoparticles were well encapsulated
Qiao’s group conducted DFT calculations to study the electronic by carbon nanotubes with high chemical stability, this carbon
properties of differently doped graphene models (Fig. 41).225 The nanotube material was demonstrated to be catalytically stable
DFT calculation provided us some important information: enough at all pH values (pH 0–14). This characteristic of carbon
(i) N and O acted as electron acceptors for the adjacent C, while nanotube HER catalysts is, usually, not observed in metallic
F, S, B, and P served as electron donors. (ii) N and P codoped catalysts. In addition, the same author synthesized another
graphene had the most favorable H* adsorption–desorption Co,N-codoped carbon nanotube material (Fig. 42) using cheaper
property among several doped graphene models, indicating the urea as the starting material instead of carbon nitride.227b This
best HER catalytic activity. (iii) The different H* adsorption material had the ability to operate stably at not only all pH
behavior on graphene correlated with graphene’s valence orbital values (pH 0–14), but also in unpurified seawater (pH 7). The
energy. Based on theoretical predictions, the authors prepared excellent durability was attributed to the tolerance of nano-
N,P-coped graphene that showed a much lower HER overpoten- carbon materials toward the impurities in seawater. This work
tial than those of other pure and single-doped graphene samples, also provided an attractive possibility of direct usage of sea-
and comparable performance to some of the traditional metal- water for generating H2 to avoid the cost of seawater desalina-
containing catalysts. In another study, Qiao’s group found that tion and purification. In order to reveal the origin of high
coupling graphitic carbon nitride (g-C3N4) with nitrogen-doped catalytic activity, Deng et al. conducted density functional
graphene could lead to a highly active composite HER catalyst.226 theory (DFT) calculations on heteroatom-doped carbon
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claimed that the HER activity of carbon nanotubes was corre-

lated with the amount of surface acidic groups (–COOH),
which could act as proton relays. The nanocarbon catalyst
reported here provides an illuminating example for creating
low-cost, metal-free HER catalysts.
11. Photochemical water splitting with

HER electrocatalysts as cocatalysts
In 1972, Fujishima and Honda discovered the photo-induced

water splitting phenomenon on TiO2 electrodes. Since then,
photocatalysis over semiconductor materials has long been
deemed as a promising approach for direct solar-to-hydrogen
conversion.230,231 The photocatalytic hydrogen evolution reac-
tion generally takes place on the surface of semiconductor
materials. When an incident light possessing energy greater
Fig. 42 (A) SEM, (B) TEM and (C) HRTEM images of Co,N-codoped
carbon nanotubes. Reproduced by permission of The Royal Society of
than the band gap hits the material, electrons in the valence
Chemistry.227b band are excited to the conduction band, concomitantly leaving
holes in the valence band. The photo-generated electrons could
reduce the protons or water molecules on the material’s surface
nanotubes (Fig. 43).228 Their results showed that the introduc- into molecular hydrogen. Typically, a hydrogen-evolution semi-
tion of metal and nitrogen dopants synergistically optimized conductor photocatalyst must have two basic qualities (i.e.,
the electronic structure of carbon nanotubes, and the adsorp- thermodynamic factors): a suitable bandgap to harvest photons,
tion free energy of H atoms on carbon nanotubes. Furthermore, and a more negative bottom level of the conduction band than
they suggested that the predominant route of HER in this the redox potential of H+/H2. These thermodynamic factors are
catalytic system was based on the Volmer–Heyrovsky mecha- strongly dependent on the structural and electronic properties of
nism. In another important work,229 Cui et al. found that HER- the semiconductor photocatalyst. Besides the thermodynamic
inert pristine carbon nanotubes could be activated by acidic factors, some kinetic processes related to photogenerated charge
oxidation to become an active HER electrocatalyst, and the separation and the surface hydrogen evolution reaction also play
catalytic performance of this catalyst could be further enhanced important roles in determining the efficiency of photocatalytic
significantly by cathodic pretreatment. The authors also water splitting. Based on the kinetic considerations, cocatalysts
are often loaded on the surface of semiconductor photocatalysts
to promote the charge separation, reduce the activation energy
barrier, and thereby improve the catalytic activity of photo-
catalysts.230a In the photochemical hydrogen production system,
the most frequently used cocatalyst is Pt nanoparticles, which
are also the best HER catalyst in the electrochemical hydrogen
production system. Recent studies demonstrated that non-Pt
HER electrocatalysts could also deliver their catalytic abilities to
the photocatalytic system as non-Pt cocatalysts, when combined
with suitable semiconductor photocatalysts. The methods for
characterizing the catalytic activities of the HER photocatalysts
have been summarized by Kudo et al. in a recent review paper.231
The pioneering work in this context was conducted by Li’s
group.232–234 The authors reported that MoS2 nanoclusters
served as an excellent cocatalyst for the CdS photocatalyst in
2008.232 After loading by MoS2, the photocatalytic activity of
Fig. 43 (a) Comparison of projected density of states (DOS) of H(1s) and
CdS increased substantially with an optimal MoS2 loading
its bonded C(2p) when H is adsorbed on the surface of pristine CNTs, amount of 0.2 wt%. The activity was increased 36 times after
Fe@CNTs, and Fe@NCNTs. The dashed lines present the center of the loading 0.2 wt% MoS2 on CdS. More importantly, the photo-
occupied band. (b) The free energy profiles of Tafel and Heyrovsky routes catalytic activity of MoS2/CdS was even higher than that of
for Fe@CNTs. (c) The free energy profiles of the Heyrovsky route for
Pt/CdS under the same reaction conditions (Fig. 44). This
pristine CNTs, Fe@CNTs and Fe@NCNTs. (d) A schematic representation of
the HER process on the surface of Fe@NCNTs. The gray balls represent C
unexpectedly high activity of MoS2/CdS was attributed to the
atoms, yellow for Fe, blue for N, red for O and white for H.228 Reproduced formation of a nanojunction between CdS and MoS2. Upon
by permission of The Royal Society of Chemistry. light irradiation, the electron–hole pairs were photogenerated
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Fig. 44 (a) The rate of H2 evolution on CdS loaded with 0.2 wt% of different
cocatalysts. (b) The HRTEM image of the MoS2/CdS catalyst.230 Reprinted with Fig. 45 Activity comparison of different photocatalysts. NiS/CdS**: reac-
permission from ref. 232. Copyright 2014 American Chemical Society. tion was conducted in Na2S (0.25 M) and Na2SO3 (0.35 M) solution, and
NiS + CdS*: physical mixture of CdS and NiS.254 Reproduced by permission
of The Royal Society of Chemistry.
in CdS under visible light irradiation. The photogenerated
electrons would transfer from CdS to MoS2 at their interface,
while the photogenerated holes remained in CdS. As a result, production systems.254–263 For example, Xu’s group demon-
the lifetime of photogenerated charges in the MoS2/CdS photo- strated the positive effect of the NiS cocatalyst on the CdS
catalyst increased significantly, finally leading to the enhance- photocatalyst for the first time.254 They prepared NiS/CdS
ment of photocatalytic hydrogen evolution on CdS. In addition, photocatalysts via a hydrothermal loading method by precipi-
MoS2 was considered by the authors to be the reactive sites tating nickel acetate in the presence of thiourea, and then
in the composite catalyst. The same group further verified that studied their photocatalytic activities using lactic acid as the
WS2 had a similar function to MoS2 for enhancing the photo- sacrificial reagent under visible light. The NiS/CdS photocatalyst with
catalytic activity of CdS.234 After Li’s work, there were several the optimized NiS amount of 1.2 mol% gave a hydrogen production
reports on new methods to synthesize MoS2/CdS nanostruc- rate of 2.18 mmol h 1, which was about 35 times as high as that
tures with different morphologies,235–240 as well as extension obtained on pristine CdS (see Fig. 45). The quantum efficiency was
of MoS2 cocatalysts to other semiconductor photocatalysis as high as 51.3% at 420 nm. Subsequently, the authors extended the
systems, ZnS,241 ZnxCd1 xS,242,243 CdSe,244 ZnIn2S4,245–247 NiS cocatalyst into the g-C3N4 system.255 g-C3N4 is an organic metal-
TiO2,248 Cu2O,249 niobate250 and g-C3N4.251,252 free semiconductor material, and Pt as the cocatalyst was previously
In another important work,253 amorphous MoS3 clusters used to enhance its catalytic activity. Xu et al. found that the optimal
were explored for enhancing the photocatalytic activity of semi- loading amount of NiS on g-C3N4 is about 1.1 wt%,
conductor materials. Tang et al. grew amorphous MoS3 clusters and this NiS/g-C3N4 material gave a hydrogen evolution rate
on a CdSe-seeded CdS (CdSe/CdS) nanorod material via a of 48.2 mmol h 1 under visible irradiation in aqueous triethanol-
microwave heating reaction. The CdSe/CdS heterostructure amine solution. The optimal catalytic activity was about 250 times
was prepared for the purpose of controlling the separation higher than that of native g-C3N4.
of photogenerated holes and electrons. This unique nano- Apart from metal sulfides, metal carbide and phosphide
structure could ensure that the hole preferred to localize in electrocatalysts have been proven to be effective cocatalysts for
the CdSe seed, whilst the electron was largely delocalized. photocatalytic hydrogen evolution.158,212 For example, tungsten
These CdSe/CdS nanorods showed negligible rates of photo- carbide (WC) nanoparticles were demonstrated by Garcia-Esparza
catalytic H2 production, whereas deposition of amorphous et al. to function a cocatalyst for Na-doped SrTiO3 photocatalyst
MoS3 resulted in a photochemically active system for hydrogen (STO:Na).158 WC-loaded STO:Na gave H2 and O2 in a stoichiometric
generation. In the MoS3-containing photocatalytic system, a ratio from water splitting (i.e., overall water splitting), whereas
hydrogen production rate of 100 mmol h 1 g 1 of was obtained, STO:Na only afforded a low hydrogen evolution rate without the
with an apparent quantum efficiency of 10% at l = 450 nm. O2 product. Based on the authors’ studies, the roles of the WC
Interestingly, the author found that all the samples underwent cocatalyst can be summarized as follow: (i) improving charge
a 30–50 min induction period before hydrogen generation separation, (ii) serving as the hydrogen-evolution active site,
started, indicating that activation of amorphous MoS3 species (iii) preventing the back reaction, H2 + O2 - H2O. In addition,
occurred during the photocatalytic progress. Based on XPS, Ni2P and FeP nanoparticles have been used for enhancing the
XANES, and EXAFS results, the authors claimed that the initial photocatalytic activities of CdS and TiO2, respectively.212,262
MoS3 precatalyst was photoreduced to form an under-coordinated
species structurally similar to MoS3 during the induction period,
and this reduced form of MoS3 was an active phase for hydrogen 12. Photoelectrochemical water
generation. This transformation was similar to the eletrocatalytic splitting with HER electrocatalysts
reduction of amorphous MoS3, which also in situ transformed as cocatalysts
MoS2+x species as the real active catalyst.
Ni, Co sulfides, which are good electrocatalysts for HER, Photoelectrochemical water splitting is a main research area in
have also been used to establish Pt-free photocatalytic hydrogen so-called artificial photosynthesis, and has been suggested as a
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promising way to store solar energy as hydrogen fuel.24,33,264–274

The photoelectrochemical water splitting system can be con-
sidered to be an integration of a light harvesting system and a
water splitting system into a single monolithic device. Corre-
spondingly, the most key component in this system is the
photoelectrode (i.e., photocathode or photoanode). In parti-
cular, a photocathode, where the HER occurs, is generally
composed of a light absorber (a semiconductor material) and
a HER electrocatalyst.
Silicon is a widely-studied light-harvesting material because
of its high abundance, strong visible-light absorption, and

well-established semiconductor in photovoltaic devices. And
Pt is the best HER electrocatalyst. With the aim of replacing Fig. 46 LSV scans (dark and white light) for p-Si and p-Si/W2C photo-
noble metal Pt, MoS2 or MoSx has been investigated to be cathodes with and without Pt nanoparticles deposited on the surface.
Current controlled pulsed deposition was used to deposit the Pt nano-
combined with a silicon electrode for the HER.33,266–270 Tran particles (total deposition times shown in parentheses). Before PEC mea-
et al. deposited a MoS2 cocatalyst on a Si nanowire electrode by surements and Pt nanoparticle deposition, the p-Si/W2C photocathode
a photo-assisted method.266 When the Si nanowire electrode was annealed in Ar at 450 1C. The LSV scan for a dense Pt film on FTO was
was interfaced with an aqueous solution containing [MoS4]2 , included. Measurements were conducted in N2 purged 1 M H2SO4 using a
upon visible light irradiation, [MoS4]2 would be reduced by scan rate of 25 mV s 1 and a white light intensity of 100 mW cm 2.274
Reprinted with permission from ref. 274. Copyright 2014 American
the photoexcited electrons in Si. This made as-formed MoS2 Chemical Society.
directly load on the surface of Si nanowires. The authors next
employed the MoS2/Si nanowire electrode for hydrogen evolu-
tion. They found that MoS2 acted as an efficient cocatalyst that environments, whereas the photocathode with Pt nanoparticles
led to a decrease of the overpotential for HER by 200 mV. To as cocatalysts deactivated rapidly under identical conditions.
load a MoS2 or MoSx cocatalyst on a Si electrode, other groups Very recently, Berglund et al. reported the synthesis of
also explored some methods.33,267–269 For example, an electro- W2C/p-Si photocathodes with W2C as the cocatalyst for
chemical deposition method was used by Chorkendorff’s p-Si.274 They fabricated this electrode by evaporating tungsten
group to load MoSx on the TiOx-protected n+p-silicon photo- metal in an atmosphere of ethylene gas to form a W2C thin film
cathode.267 TiOx protection was demonstrated to be necessary on top of a p-Si substrate. The p-Si/W2C photocathode gave a
because the Si electrode was susceptible to oxidation. In addi- cathodic photocurrent at potentials more positive than 0.0 V vs.
tion, Jin’s group directly dropcasted 1T–MoS2 nanosheets on a RHE, while bare p-Si photocathodes did not (see Fig. 46).
Si photoelectrode, resulting in an improved catalytic activity.269 Furthermore, the authors demonstrated that the W2C film
Furthermore, Huang et al. fabricated a MoS3/silicon nanowire could function as a support for Pt nanoparticles, leading to a
photocathode by the spin-coating of (NH4)2MoS4–methanol p-Si/W2C/Pt photocathode. This p-Si/W2C/Pt photocathode
onto Si nanowires, followed by calcination at 260 1C.33 This afforded comparable photocurrent onset potentials and limiting
electrode exhibited excellent catalytic activity, which was com- photocurrent densities to p-Si/Pt photocathodes, but the former
parable to that of the Pt-modified Si electrode. The authors also had a much lower Pt loading than the latter. This work provides
used the same method to prepare a WS3 modified Si nanowire an important example for creating low-cost photocathodes with
electrode.270 high efficiency.
Besides Si, InP and Cu2O are attractive photocathodes
for hydrogen evolution,271–273 and their activities can also be
increased by modifying MoSx cocatalysts. Gao et al. coated 13. Conclusions and further outlook
vertically aligned p-type InP nanowire arrays with MoS3 nano-
particles.271 The resulting MoS3/InP material served as a cathode The future hydrogen economy is a proposed system of storing
for photoelectrochemical hydrogen production from water. and transporting energy using hydrogen. As shown in Fig. 47,
A high photocathode efficiency of 6.4% under Air Mass 1.5G there are three main processes during the hydrogen energy
illumination was obtained. In contrast, in the literature the cycle: harvesting renewable energy (e.g., solar and wind), split-
solar conversion efficiencies for hydrogen evolution are normally ting water into hydrogen and oxygen using renewable energy,
limited to 2.5% even upon using noble metals as cocatalysts. and re-releasing usable energy by reacting H2 with O2. In this
In addition, Morales-Guio et al. electrochemically deposited review, we specially highlight the advances on hydrogen-
MoS2+x films as cocatalysts on TiO2-protected copper(I) oxide evolving electrocatalysts for efficient water splitting (i.e., pro-
photocathodes,272 which are the state-of-the-art p-type oxide for cess II). Particular attention is paid to one of the major goals in
photoelectrochemical hydrogen evolution. The composite photo- this field—replacing expensive and rare noble metal electro-
cathode produced a photocurrent as high as 5.7 mA cm 2 at 0 V catalysts with inexpensive and earth-abundant ones. Despite
versus RHE under simulated AM 1.5 solar illumination. This the enormous strides and many achievements we have made,
photocathode also exhibited excellent stability (410 h) in acidic as outlined in this review, there is still a long way ahead before
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a benchmarking study of the existing catalysts by an impartial

third party should be strongly encouraged. Objective compar-
isons of electrocatalyst performance using standard methods
under identical conditions are helpful to evaluate the viability
of existing electrocatalysts as well as to inform the develop-
ment of new catalytic systems. In this regard, McCrory et al.
at California Institute of Technology have done some very
meaningful studies.275
(iii) Exploration of new materials

Exploring new HER electrocatalysts will be one of our core

Fig. 47 The future hydrogen energy cycle.
research goals in the next few years. An ideal non-Pt HER
electrocatalyst should meet several standards: (1) high effi-
ciency similar to that of Pt; (2) good durability over a period
water splitting can find a wide range of commercial uses for of at least several years; (3) high chemical/catalytic stability over
sustainable hydrogen production with both economic and a wide pH range, even at all pH values; (4) low cost to ensure
environmental benefit. In order to realize such an ambition, inexpensive hydrogen production; and (5) scalability to ensure
or even come close, we will have a lot of things to do in the a wide range of commercial uses. However, to date, none of
future, with regard to the hydrogen-evolving electrocatalysts. the known HER electrocatalysts possess all the above merits.
Therefore, a viable method is to choose the right HER catalyst
(i) Mechanism investigation for the particular application. As for chemical composition,
Investigation on the mechanism of the known HER electro- transition metal Fe and Ni compounds (e.g., FeP) would be the
catalysts is not only of scientific importance, but can also offer first choice for future HER electrocatalysts due to their natural
rational guidance to optimization of materials’ performances. abundance and potential catalytic activity. In addition, the
This has been confirmed by the fact that the relatively clear HER catalysts with high tolerance against seawater should
catalytic mechanism of MoS2 in acidic media has significantly be actively pursued because they might make the direct use of
boosted the rapid development of MoS2-related materials. seawater possible.
Nevertheless, for most of the known HER electrocatalysts,
especially these composite catalysts, there is still lack of in-depth (iv) Integration of HER electrocatalysts with oxygen evolution
mechanistic investigation on an atomic level. Moreover, the electrocatalysts and/or semiconductor photocatalysts
HER mechanism in alkaline media for all the materials is very On one hand, the efficiency of electrochemical water splitting is
ambiguous at present. This, therefore, might call for an determined by not only the HER electrocatalyst and oxygen
integration of theoretical simulation and in situ characteriza- evolution electrocatalyst themselves,276 but also their compat-
tion techniques to clarify the catalytic mechanism. ibility. On the other hand, the efficiency of photocatalytic or
photoelectrochemical water splitting is also strongly influenced
(ii) Standardized testing by the suitable combination of HER electrocatalysts and semi-
Establishing standardized testing will be useful to compare conductor materials. Thus, a final evaluation for a HER electro-
different materials obtained by different researchers, and to catalyst is necessary to put it in a real electrochemical, or
screen the optimal HER electrocatalysts. It is difficult to directly photo(electro)chemical water splitting system.
compare various materials due to different mass loadings of
catalysts on the electrode, different preparation methods of the
electrode, and different reaction solutions (i.e., the electrolytes) Acknowledgements
that are used finally. For example, in most of the studies the
measured currents are only normalized to the superficial geo- This work was financially supported by the fundamental
metric electrode area, but the loading amount of the catalyst is research funds for the central universities, startup funds from
often ignored. Because the overall currents we measured are Jilin University, the National Natural Science Foundation of
also related to the amount of the catalyst, the normalization China (Grant no. 51372007, 21301014 and 21401066), Jilin
only by the electrode area might lead to an unfair performance province science and technology development projects
evaluation among different materials. Thus, the researchers (20150520003JH). X. Zou and Y. Zhang deeply appreciates
should provide as much information about electrode activity as the assistances of Prof. Guo-Dong Li and his group members
possible so that the researchers can easily compare the results (Jilin University), Prof. Xin-Bo Zhang (Changchun Institute
with each other. The important performance parameters of Applied Chemistry), Xiaoxi Huang (Rutgers University),
mainly include Tafel slop, exchange current density, loading Prof. Guang-Sheng Wang (BeiHang University), Prof. Huan
amount of catalyst, catalytic activities normalized by both mass Liu (BeiHang University), Yang Li (BeiHang University) and
and electrode area, Faradic efficiency and stability. In addition, Wang Li (BeiHang University).
View Article Online
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Noble Metalfree Hydrogen Evolution Catalysts For Water Splitting2015chemical Society Reviews

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Featuring work from the research group of Dr Yu Zhang, As featured in:

School of Chemistry and Environment, BeiHang University,

Noble metal-free hydrogen evolution catalysts for water

This review highlights the recent research efforts towards the

See Xiaoxin Zou and Yu Zhang,

Noble metal-free hydrogen evolution catalysts

Cite this: Chem. Soc. Rev., 2015,

1. Introduction hydrogen content.1–23 Very recently, considering the high

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reaction is driven by solar-, wind- or other renewable resources-

Xiaoxin Zou was awarded a PhD in Yu Zhang received his doctoral

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Fig. 2 Sustainable pathways for hydrogen production from renewable

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Chem Soc Rev Review Article

value for many solid-state (heterogeneous) catalytic materials,

4. A general view of the elements used

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Chem Soc Rev Review Article

Fig. 8 Schematic representation of the synthesis procedure to obtain

Fig. 7 Structures of 2H and 1T MoS2.55 Reprinted with permission from

Besides lithium intercalation, ball-milling and sonication

Review Article Chem Soc Rev

a high-quality dendritic monolayer MoS2 material with abundant

(ii) Creating porous structure. A traditional, yet eﬀective way

highly energetic exposed active sites, MoS2 with a nanoporous

Fig. 11 SEM images of monolayer MoS2 grown on Au foils with diﬀerent

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The deliberate introduction of a foreign metal or nonmetal

free energy of hydrogen adsorption at the Co-promoted S-edge.

(iv) Coupling conductive substrates. Coupling MoS2 with

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Fig. 17 Solvothermal synthesis of a MoS2–graphene nanocomposite.

and graphene aﬀorded the site-confined growth of MoS2 nano-

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Fig. 19 Hydrogen evolution on amorphous MoSx.96b Reprinted with

Fig. 18 SEM images of a MoS2–graphene paper composite.93 Repro-

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reported as effective supports to improve the activity of amor-

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with MII–S–WIV (M = Co or Ni) bimetallic sulfide centers. A further

5.4 Fe, Co, Ni sulfides

protons and electrons into molecular hydrogen at a low over-

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with only 2–5 Se–Mo–Se atomic layers via the reaction of

(MoO3) with small amounts of Se, followed with drop-casting

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MoSe2 and the Se-edge on MoSe2 and WSe2 played an impor-

6.2 Fe, Co, Ni selenides

performed in a ternary solvent with various ratios of diethylene-

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materials could have the potential to control the activity and

devoted to the research of metal carbides with the aim of

7.1 Molybdenum carbide

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Fig. 29 The synthesis from soybeans and ammonium molybdate of a

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Fig. 32 The synthesis of graphene nanoplatelet-supported W2C and WN

nanoplatelets.164 Reproduced by permission of The Royal Society of

amount of iron in the material is very low. In another study,

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bimetallic nitride possessed a four-layered mixed closed packed

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