Review

pubs.acs.org/acscatalysis

Recent Trends and Perspectives in Electrochemical Water Splitting

with an Emphasis on Sulfide, Selenide, and Phosphide Catalysts of
Fe, Co, and Ni: A Review
Sengeni Anantharaj,† Sivasankara Rao Ede,† Kuppan Sakthikumar,† Kannimuthu Karthick,†
Soumyaranjan Mishra,†,‡ and Subrata Kundu*,†,§
†
Electrochemical Materials Science (ECMS) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi-630006,
Tamil Nadu, India
‡
Centre for Education (CFE), CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi-630006, Tamil Nadu, India
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§
Department of Materials Science and Mechanical Engineering, Texas A&M University, College Station, Texas 77843, United States

ABSTRACT: Increasing demand for finding eco-friendly and

everlasting energy sources is now totally depending on fuel cell
technology. Though it is an eco-friendly way of producing
energy for the urgent requirements, it needs to be improved to
make it cheaper and more eco-friendly. Although there are
several types of fuel cells, the hydrogen (H2) and oxygen (O2)
fuel cell is the one with zero carbon emission and water as the
only byproduct. However, supplying fuels in the purest form
(at least the H2) is essential to ensure higher life cycles and less
decay in cell efficiency. The current large-scale H2 production
is largely dependent on steam reforming of fossil fuels, which
generates CO2 along with H2 and the source of which is going
to be depleted. As an alternate, electrolysis of water has been
given greater attention than the steam reforming. The reasons are as follows: the very high purity of the H2 produced, the
abundant source, no need for high-temperature, high-pressure reactors, and so on. In earlier days, noble metals such as Pt
(cathode) and Ir and Ru (anode) were used for this purpose. However, there are problems in employing these metals, as they are
noble and expensive. In this review, we elaborate how the group VIII 3d metal sulfide, selenide, and phosphide nanomaterials
have arisen as abundant and cheaper electrode materials (catalysts) beyond the oxides and hydroxides of the same. We also
highlight the evaluation perspective of such electrocatalysts toward water electrolysis in detail.
KEYWORDS: water splitting, hydrogen evolution, oxygen evolution, overpotential, Tafel analysis, metal chalcogenides,
metal phosphides, electrolysis

1. INTRODUCTION electrolysis proceeds via the following two half-cell reactions:

An unusually increased rate of depletion of conventional fossil
fuels and the environmental hazards associated with the use of
these carbon-emitting fuels have triggered the research
community to find an abundant, everlasting, zero-emitting,
and eco-friendly combined fuel-combustion technology as an
alternate energy server very urgently.1 Fuel cell technology is
among the ways of producing energy in a more eco-friendly
manner than the other existing ones. The fuel cell operating
with H2 and O2 will be the choice among the available fuel cells
as it emits water as the combustion product.2−7 Currently,
steam reforming of fossil fuels and water electrolysis (H2O(l)
→ H2(g) + 1/2O2(g): ΔG° = +237 200 J/mol, ΔE° = 1.23 V vs
reversible hydrogen electrode (RHE)) are the ways of
producing H2 to afford fuel for these fuel cells. Between
steam reforming and water electrolysis, the first one is not
environmentally friendly because it produces CO2 along with
H2, thereby reducing the purity of H2, which in turn affects the
life cycle and the cell efficiency of fuel cells.2−7 Water
reduction of H+ ions at the cathode (2H+(aq) + 2e− → H2(g)),
i.e., the hydrogen evolution reaction (HER),8−10 and oxidation
of water (2H2O(l) → O2(g) + 4H+(aq) + 4e−), i.e., the oxygen
evolution reaction (OER).11−16 At first look, water electrolysis
may pretend to be an easy and problemless way to produce H2,
but it is not. Electrolysis of water is an area where the science
and technology need to be improved to overcome the issues
associated with it. One such issue is that the noble metals and
their compounds catalyzing the HER (Pt)17−25 and OER (Ir,
Ru)26−43 need to be replaced by the available non-noble metals
and their compounds. To do so, recently attention has been
diverted toward OER catalysts based on non-noble metals such
as Mn,44−47 Fe,48−53 Co,44,49,54−76 and Ni16,47,53,76−101 and
HER catalysts based on Mo58,83,102−110 and W.111,112 Though
Received: August 29, 2016
Revised: October 14, 2016
Published: October 19, 2016

© 2016 American Chemical Society 8069 DOI: 10.1021/acscatal.6b02479

ACS Catal. 2016, 6, 8069−8097
ACS Catalysis
the production of purest H2 is the main objective of water
electrolysis, we cannot neglect the counter-reaction (the OER),
as it is the sluggish one between them and affects the Faradaic
efficiency of the electrolytic cell to a greater extent.
The HER under acidic conditions is facile, as plenty of
protons are available, and it proceeds by a multistep reaction
with two possible mechanisms.113,114 The mechanism by which
the HER proceeds is usually revealed by the experimentally
obtained Tafel slope value.8−10,115 The first step in the
multistep HER is discharging protons on the electrode surface
to form adsorbed hydrogen (Hads), which is called as the
Volmer reaction (H+(aq) + e− → Hads). The Tafel slope for the
Volmer reaction, b1,V, can be expressed as
b1,V = 2.303RT /βF (1)
where R is the ideal gas constant, T is the absolute temperature,
F is the Faraday constant, and β is the symmetry factor (equal
to 0.5). Depending on the coverage of Hads, the second step is
either electrochemical desorption of H2, known as the
Heyrovsky reaction, or chemical H2 desorption, known as the
Tafel reaction. If the coverage of Hads is low and the electrode
surface has sufficient active sites near the Hads sites, the
adsorbed H atoms will preferably join with a proton and an
electron simultaneously to evolve a molecule of H2 (Hads +
H+(aq) + e− → H2(g)). This is called the Heyrovsky reaction,
and its Tafel slope can be expressed as
b2,H = 2.303RT /(1 + β)F (2)
In the case of high Hads coverage, two adjacent Hads will join
together chemically and evolve a molecule of H2. This the Tafel
reaction, and its Tafel slope can be expressed as
b2 ′ ,T = 2.303RT /2F (3)
The calculated Tafel slopes of the above reactions under
standard conditions are 0.118 V/dec, 0.039 V/dec, and 0.029
V/dec for the Volmer, Heyrovsky, and Tafel reactions,
respectively. An electrocatalytic HER with a Tafel slope of
0.029 V/dec is termed to follow the Tafel−Heyrovsky
mechanism, and the rate-limiting step would be the electro-
chemical desorption step. Under alkaline conditions, the HER
is comparatively more sluggish because it directly depends on
the anodic OER, which supplies the protons to the cathode by
the deprotonation of hydroxide ions and affects the HER
kinetics. Under such conditions, the following reaction takes
place at the cathode:
4e− + 4H 2O(l) → 4OH−(aq) + 2H 2(g) (4)
The protons formed by the deprotonation of hydroxides at
anode get combined with the abundant OH− ions in alkaline
solutions, making the HER struggle more to move forward
further.
The OER on the other hand has a different story. The
kinetics of the OER in acidic and alkaline media vary depending
on the material by which it is being catalyzed. Noble metal
catalysts such as Ir and Ru and their compounds catalyze the
OER more easily in acidic media than under alkaline
conditions. On the other hand, the catalysts derived from
VIII group 3d metals (Fe, Co, and Ni) catalyze the OER more
favorably in alkaline media than in acidic media. This is mainly
correlated to the mechanism by which they catalyze it. In 1986,
Matsumoto and Sato13 published a detailed review on various
reported OER mechanisms in acidic and alkaline media,
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including the Krasil’shchkov, Bockris,46,116 Yeager, and Wade
and Hackerman52 pathways in addition to the most recognized
electrochemical oxide pathway and the oxide pathway. Under
alkaline conditions, all of the proposed mechanisms begin with
an essential elementary step of hydroxide coordination to the
active site and proceed via different proposed other elementary
steps.46,116 The kinetic barriers associated with each elementary
step raise the overall overpotential required. An elementary step
with the most sluggish kinetics is the rate-determining step
(RDS).11,14
In general, the electrochemical reactions that occur at the
anode (OER domain) and at the cathode (HER domain) in
acidic and alkaline media are given as follows:
in acid:
4e− + 4H+(aq) → 2H 2(g) (5)
2H 2O(l) → 4H+(aq) + 4e− + O2 (g) (6)
in alkali:
4e− + 4H 2O(l) → 4OH−(aq) + 2H 2(g) (4)
4OH−(aq) → 2H 2O(l) + 4e− + O2 (g) (7)
In practice, there is no electrolytic cell that performs with
100% Faradaic efficiency because of various thermodynamic
and kinetic hindrances. As stated above, the best catalyst that
catalyzes the HER is Pt, and the catalysts that catalyze the OER
are Ir and Ru and their compounds. However, use of such
relatively less abundant precious metals for a corrosive and
destructive water electrolysis is not advisible as it increases the
cost of H2 production, hinders the magnification of productivity
on a large scale, and more. Later, people have found that the
oxides and hydroxides of group VIII 3d metals, viz., Fe, Co, and
Ni alone and with a combination of other metals in the row,
can catalyze the OER as efficiently as Ir and Ru under alkaline
conditions. Nevertheless, the discovery is not fruitful as they did
not consider the kinetics of the counter-reaction (the HER) in
alkali. Moreover, the HER is sluggish even with Pt because of
the reasons stated above.
To overcome this issue, there are two possibilities. The first
one is to find efficient, durable, non-noble OER catalysts in
acidic media as alternates to Ir- and Ru-based catalysts.
However, this could not even eliminate the expensive Pt
from the job of the HER. One way to get rid of the Pt would be
to replace it with other non-noble metal-based catalysts such as
sulfides, selenides, and phosphides, but the resulting electrolytic
cell will be the kind of asymmetric one, leading to other
technical problems. The second way to overcome this pitfall is
to design a bifunctional catalyst out of non-noble metals that
can catalyze both the OER and HER at the same time without
the need for any separator. Such bifunctional catalysts made
from Fe, Co, and Ni are being reported, frequently with parallel
or in some cases better activities for both the HER and OER
compared with Pt, Ir, and Ru. Such reported bifunctional
catalysts are almost always phosphides, sulfides, and selenides
of Fe, Co, and Ni as nanostructures in various forms.
As an emerging field in the energy sector, there are few
reviews of many of these materials and their subsequent
applications to water splitting. However, all of the available
reviews to date have either been focused on one type of catalyst
formed out of these three metals (viz., Fe, Co, and Ni) or all
three types of catalysts formed out of a single metal. Examples
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for the first kind are the reviews of transition metal phosphides
and chalcogenides. Meanwhile, examples of the second kind are
the reviews available on heterogeneous electrocatalysis by
catalysts derived out of Co, Ni, and Fe, in which for a single
metal the catalytic activity trend of its oxides, sulfides, selenides,
phosphides, and borides would have coherently been
summarized. Hence, to have a better experience in under-
standing the basics to frontiers of electrochemical water
splitting, a complete review on sulfide, selenide, and phosphide
catalysts formulated out of Fe, Co, and Ni would highly be
desired. In this review, we present a detailed survey of the
following topics: the parameters involved in the evaluation of
catalysts for both the HER and OER, the effects of the
heteroatoms (S, Se, and P) on the material properties of the
metal and the subsequent catalytic activities, the basic
requirements for an efficient bifunctional water electrolytic
catalyst, a detailed overview of the synthetic methodologies of
metal (Fe, Co, Ni, and their mixed versions) phosphides,
sulfides, and selenides, and the applications of these materials in
the electrochemical HER and OER. Finally, the challenges
ahead in developing new, efficient bifunctional catalysts and
opportunities are stressed.
2. PARAMETERS USED TO EVALUATE THE
CATALYTIC ACTIVITY
The following parameters are the widely recognized ones fpr
evaluating and comparing the catalytic activities of catalysts. In
this part of the review, the merits and demerits associated with
each of these parameters are discussed and justified.
2.1. Overpotential (η). There is no electrochemical
reaction that occurs at the potential predicted only by
thermodynamic considerations excluding the kinetic hindrances
experienced in a real system.11,14,113,114 As a consequence of
these hindrances, an additional driving force in terms of an
extra potential is needed to effect such electrochemical
reactions, which is called the overpotential (denoted by the
symbol η). For both the OER and HER, there are three sources
of overpotential, viz., the activation overpotential, the
concentration overpotential, and the overpotential due to the
uncompensated resistance (Ru), which is the resistance exerted
by the electrochemical interfaces. The activation overpotential
is an intrinsic property of the material that catalyzes the
electrode reaction and varies from one material to another.
Hence, it can be minimized by choosing an efficient catalyst.
The concentration overpotential occurs as soon as the
electrode reaction begins as a result of the sudden drop in
concentration near the interfaces. This can be minimized by
stirring the solution. The resistance overpotential can be
removed by carrying out Ohmic drop compensation, which is
now available in many electrochemical workstations.8 Other-
wise, it can also be done manually just by multiplying the
resultant current density by Ru, the result of which is a potential
(E). This drop in potential, known as the iR drop, needs to be
subtracted from the experimental potential. In case of the HER,
the activation overpotential, which can be termed as the onset
overpotential, is more important than the others, as the kinetics
of the HER is faster than that of the OER.8,9,115,117 This can be
calculated from the polarization curve obtained by plotting the
overpotential versus the current density.
In contrast, the OER case differs and needs more attention
on other parameters too in order to calculate the overpotential.
As we said above, all of the proposed mechanisms of the OER
proceed through the first elementary step of water coordination
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in acidic solution or hydroxide ion coordination in alkaline
solution, which is then followed by a series of other elementary
steps. The kinetic barriers associated with each of these steps
will contribute to the overall activation overpotential of an OER
catalyst. Man et al.14 and others13,116 have studied the
thermodynamics of the OER mechanism and proposed the
following expression for calculating the theoretical OER
overpotential (ηOER) under ideal conditions with U = 0 vs
standard hydrogen electrode (SHE):
ηOER = (ΔGmax /e) − 1.23 V (8)
However, the theoretical and experimental values had very large
difference in the standard free energy change associated with
the elementary step involving the conversion of oxide to
peroxide. This clearly says that the kinetic hindrances are not
considered in the thermodynamic prediction of the over-
potential. Because of the varying kinetics of these elementary
steps from material to material, instead of the onset
overpotential, the overpotential at a fixed current density (j)
such as 10 mA/cm2 (η10) has now widely been accepted as an
essential quantitative activity parameter to evaluate an electro-
catalyst.118−120 The same is also used for the HER. For
materials with a strong redox peak (giving a current density
greater than 10 mA/cm2) within the potential window of gas
evolution and for high-performance catalysts (giving current
densities greater than 500 mA/cm2) such as layered double
hydroxides,100,121−124 the overpotentials at higher current
densities such as 50 and 100 mA/cm2 are also used as alternate
activity parameters.
2.2. Tafel Slope and Exchange Current Density (j0).
The Tafel plot of an electrocatalytic process is generally
obtained by replotting the polarization curve (e.g., linear sweep
voltammogram (LSV)) as a plot of log(j) versus η. The slope of
the linear portion of the Tafel plot is defined11 as the
dependence between the iR-compensated overpotential and the
current density, which is expressed as follows:
d log(j)
= 2.303RT /αnF
dη (9)
The Tafel slope is inversely proportional to the charge transfer
coefficient (α), as the remaining other parameters are constants
(viz., the ideal gas constant (R), temperature (T), Faraday
constant (F), and the number of electrons transferred (n),
which is equal to 4 for the OER and 2 for the HER). This
indicates that a catalyst with a high charge transfer ability
should possess a small Tafel slope. This is the reason why it is
often used as a primary activity parameter in determining the
catalytic activity.
However, with the above-mentioned path (i.e., converting
the LSV into the Tafel plot), there are several issues that can
lead to a misinterpretation of the catalytic activity. In general,
the LSV obtained with lowest possible scan rate gives the Tafel
slope with the least experimental inaccuracy. The scan rate at
which the polarization curve used for Tafel plot was determined
becomes a serious problem when the catalyst is highly
capacitive. This leads to large error while determining the
exchange current density because the exchange current density
is usually obtained by extrapolating the linear fit toward the
corresponding current density on the logarithmic scale at the
equilibrium potential (i.e., at zero overpotential). In such a case
the catalyst with a high overpotential will have a large exchange
current density value, which is not possible because a high
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exchange current density means that transferring electrons
across the catalytic interface will be facile and require a very low
activation energy. Hence, the result would be a low
overpotential.
Besides the problem with capacitive currents, the current
observed in the Faradaic region is also not the true one, as it is
not the steady-state current, and this leads to a considerable
experimental inaccuracy in the determined Tafel slope value.
This can be explained as follows. In a chronoamperometric
analysis (at constant potential), it is common to observe the
steady-state current only after few seconds. In the case of linear
sweep voltammetry, even at a scan rate of 1 mV/s the current
obtained cannot be the real steady-state current. To overcome
this issue, a traditional practice can be employed in which the
steady-state current of the catalyst is obtained from the
chronoamperometric i−t curves obtained at various over-
potentials with regular small intervals (say 5 mV). A similar
experimental comparison of Tafel slopes obtained from cyclic
voltammetry (CV) (run at 5 mV/s) and from the steady-state
currents obtained by chronoamperometric curves for a
commercial IrTiO2 electrode is given in Figure 1.11 The linear
Figure 1. Tafel curves of a commercial IrTiO2 electrode (Umicore AG
& Co.) obtained by a cyclic voltammetry measurement at 5 mV/s and
by a chronoamperometry experiment by holding each potential for 30
s in 20% O2-saturated 0.1 M HClO4 at room temperature and a
rotation speed of 900 rpm. Reproduced with permission from ref 11.
Copyright 2014 Royal Society of Chemistry.
portions of the Tafel plots obtained by the two methods are in
close agreement with one another. However, in the lower-
overpotential region the story is different. It can be seen from
Figure 1 that the Tafel plot obtained from CV shows a larger
exchange current density than the one obtained from the
steady-state current, and the exchange current density from
chronoamperometry will be more precise as it eliminates the
capacitive current. Though the latter method seems to be better
than the method of replotting the polarization curves, it also
does not reflect the intrinsic and exact catalytic activity of a
catalyst because the potential drop due to the uncompensated
resistance cannot be easily excluded in this method as it is
usually done in the former method of replotting polarization
curves by iR compensation.
To avoid this issue, Hu and co-workers very recently
proposed a new method for obtaining a more accurate Tafel
slope for a catalyst from electrochemical impedance spectros-
copy (EIS).125 In this method, the Nyquist plots of the catalyst
at various overpotentials at regular intervals are acquired, and
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the slope of the plot of log(Rct) vs η (where Rct is the charge
transfer resistance) is obtained. This is the exact Tafel slope of
the catalyst and depends only on the charge transfer ability of
the catalyst as Ru is excluded from the calculation. Depending
on the requirements and conditions, any one of these methods
can be chosen for finding the Tafel slope of an electrocatalyst.
Apart from the methods of obtaining Tafel slope, there has
been a serious discussion of considering the exchange current
density (j0) as an activity parameter in addition to the Tafel
slope.11 The exchange current density is more often used as an
activity parameter for the HER than for the OER. As we stated
earlier, the kinetics of the HER is facile beyond the defined
overpotential of the catalyst, so almost all reported catalysts
have similar kinetics in the HER. This means that the exchange
current density is directly correlated to the onset overpotential
in the HER. Hence, it can be used there as an activity
parameter. In contrast, the OER case is different, as the kinetics
differs from one catalyst to another one and is strongly pH-
dependent. A classic example of this kind can be the
comparison of the RuO2/IrO226,38,41,43,126−128 and Ni−
Fe98,129−132 systems in alkaline media. In this case the onset
overpotential of IrO2/RuO2 is lower than that of Ni−Fe but the
Tafel slope is lower for the latter one. This implies that though
the driving force to start the reaction on IrO2/RuO2 is lower,
the rate of charge transfer/electron transfer is lower than for
the Ni−Fe system in alkaline media. This is one of the reasons
why people have adopted the overpotential at fixed current
density (e.g., 10 mA/cm2) as an additional activity parameter
rather than the exchange current density (j0) or the onset
overpotential for the OER.11 Hence, hereby we can conclude
that for the HER the Tafel slope and the onset overpotential
and/or exchange current density can be taken as activity
parameters. For the OER, the Tafel slope and the overpotential
at a defined current density can be taken as activity parameters.
2.3. Stability. The stability of an electrocatalyst is usually
tested by subjecting it to CV cycling at a higher scan rate, which
is otherwise known as the accelerated degradation test, and to
chronoamperometric or chronopotentiometric analyses. In the
case of the HER, the accelerated degradation test is carried out
for several thousands of cycles as the polarization starts from 0
V vs NHE. In the case of the OER, the number of cycles
reported in accelerated degradation test ranges from 250 to
1000. Beyond 1000 cycles, it is rare to see such a report on an
OER catalyst with extreme stability. After the accelerated
degradation test, the shift in onset overpotential (η0) (cathodic
for HER and anodic for OER) and the overpotential at a
defined current density of 10 mA/cm2 (η10) are measured as
indicative parameters of stability, with a smaller increase in
overpotential indicating a higher stability. Stability under
constant exposure to a fixed potential (chronoamperometry)
or a fixed current density (chronopotentiometry) is examined
for durations of several minutes to hours. It has now been
widely accepted that a stable current density (e.g., 10 mA/cm2)
for more than 12 h by chronoamperometry or a negligible
increase in overpotential at a current density of 10 mA/cm2 for
more than 12 h by chronopotentiometry is enough to recognize
an efficient electrocatalyst for both the OER and HER. As
highlighted in the overpotential case, for high-performance
materials and catalysts with strong redox peaks, other current
densities such as 50 or 100 mA/cm2 and their corresponding
potentials can also be used to run chronopotentiometric and
chronoamperometric analyses for long times.17,27
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2.4. Faradaic Efficiency. Faradaic efficiency is another
quantitative parameter used for both the HER and OER. It can
be defined as the efficiency of an electrocatalyst to transfer
electrons provided by the external circuit across the interface to
the electroactive species to effect the electrode reaction (in our
case, either the HER or OER). There are two methods to find
the Faradaic efficiency.8 The first one is the electrochemical
method using a rotating ring disc electrode (RRDE), which is
applicable to the OER only. The catalytically active material is
coated on the disc of the RRDE without disturbing the ring.
The commonly used RRDE is the one with a glassy carbon
(GC) disc and Pt ring. Prior to that, the collection efficiency of
the RRDE must be known or to be determined experimentally
by studying the conventional ferrous/ferric redox system’s
response at various rotation rates. The potential at the disk is
then swept over the same experimental potential window of the
OER, while at the same time the potential at the Pt ring is set at
a constant potential for the oxygen reduction reaction (ORR).
The ORR potential set at the Pt ring is varied depending on the
pH of the electrolyte solution. Equation 10 is used to calculate
the Faradaic efficiency (FE) of an OER catalyst:133−135
IR nD
FE =
IDnR NCL (10)
where IR and ID are the current at the ring and disc,
respectively, nR and nD are the numbers of electrons transferred
at the ring and disc, respectively, and NCL is the collection
efficiency of the RRDE used. This is an extremely useful
technique to find the true activity of an OER catalyst that has
the following possibilities of losing its Faradaic efficiency: an
OER catalyst with one or more strong redox peaks within the
potential window of the OER (almost all Ni-, Co-, and Fe-
based catalysts), an electrocatalyst that can facilitate other
unwanted side reactions, and an electrocatalyst that heats up
during the electrocatalysis process.
The second method of determining the Faradaic efficiency is
common for both the HER and OER. In this case, the quantity
of gas (H2/O2) evolved is calculated by integration from the
chronoamperometric or chronopotentiometric analysis. Then
the practically obtained gas (H2/O2) quantity is calculated, for
which any one of the following three methods can be
employed.8 The first method is the conventional water gas
displacement method, and the second is gas chromatography.
The third method is a spectroscopic technique applicable only
to the OER in which the evolved oxygen is excited from the
triplet state to the singlet state and allowed to relax by
fluorescence. The intensity of the fluorescence is a direct
measure of the quantity of oxygen evolved. However, the
method for determining the practically evolved gas quantity can
be chosen depending on the nature of the catalyst and the
availability of resources to do such studies. The ratio of the
quantities of gas determined by the practical method and the
theoretical method is the Faradaic efficiency of the catalyst
under study.8 The selection from among these methods is also
determined mainly by the demands of the catalyst used.
2.5. Turnover Frequency (TOF). The TOF is another
quantitative parameter used to evaluate an electrocatalyst at a
defined overpotential. The TOF of the catalyst is defined as the
number of moles of O2/H2 evolved per unit time. Equation 11
is used to calculate the TOF for an electrocatalytic gas
evolution reaction:
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INA
TOF =
AFn Γ (11)
where I is the current, NA is the Avogadro constant, A is the
geometrical surface area, n is the number of electrons
transferred, and Γ is the surface or total concentration of
catalyst in terms of number of atoms. There are several
methods available to determine the surface or total
concentration catalyst in terms of number of atoms. The
redox peak in the cyclic voltammogram can be used to find the
surface concentration after activation of the catalyst by CV
cycling.133−135 By the Avogadro’s number method, the total
concentration of atoms can be calculated using the average
particle diameter of the catalyst.17 Another method is the
assumption of a monolayer.27 If the catalyst surface is flat and
smooth or the catalyst has a sheet morphology, this assumption
can be made. However, we are aware that each of these
methods has its own drawbacks. The first method may cause
potential error when there is more than one element in the
catalyst or if the catalyst is not fully activated. The second
method does not reflect the exact catalytic property of the
catalyst as it also includes the atoms in the core of the particle,
which actually do not participate in the catalytic cycle. The
third method may lead to potential error when the material is
not completely flat, is prone to destruction under harsh
electrochemical conditions, or does not have a sheet
morphology. Hence, it is advisible to adopt a method
appropriate for the catalyst and its nature.
2.6. Mass and Specific Activities. The mass and specific
activities of an electrocatalyst are two other quantitative active
parameters used to define the catalytic activity of an
electrocatalyst. The current normalized by the catalyst loading
is the mass activity, which is expressed in amperes per gram (A/
g).136 On the other hand, the current normalized by the
electrochemical surface area (ECSA) or the Brunauer−
Emmett−Teller (BET) surface area is the specific activity. As
in the case of the TOF, the mass and specific activities of an
electrocatalyst should be given at a defined overpotential. More
insights about mass and specific activities are described in detail
in section 3.1. Among the six parameters discussed to describe
the catalytic activity of an electrocatalyst, the overpotential,
Tafel slope, and stability parameters are the mandatory ones.
3. METHODS OF NORMALIZING THE
EXPERIMENTALLY OBSERVED CURRENT AND THE
ASSOCIATED MERITS AND DEMERITS
Though the geometrical-surface-normalized current density has
now been widely used, it has its own merits and demerits in
quantifying the activity of an electrocatalyst. A good survey of
such normalization methods was briefly discussed by Fabbri et
al. in their recent review article on oxide-based OER catalysts.11
3.1. Normalization of the Current by the Geometrical
Surface Area. It is not good to have the current density
normalized by the geometrical area of the substrate electrode
(in units of A/cm2geo), as this does not reflect the intrinsic
catalytic property of the material. Moreover, it does not care
about the catalyst loading, giving different potentials for the
same current density with the varying catalyst loading. In other
words, if the coverage of the loaded catalyst is 100% and
sufficient to form a monolayer, then the geometrical area of the
substrate electrode can be used to normalize the current. In
cases where the loading is low (in which there will be many
catalytically inactive substrate electrode sites) or very high (in
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Table 1. Merits and Demerits of Various Current Normalization Methods Used in Electrocatalysis of Water Splitting
normalization
method merits demerits
geometrical widely accepted and used does not reflect the intrinsic catalytic property of the catalyst
surface area method
fair comparison with existing may vary depending on catalyst loading and its optimization
literature reports is easy
good for planar electrodes ceometrical area of the substrate electrode is not equal to the actual surface area of the catalyst participating in catalysis
such as foils and deposited
thin films
ECSA can reflect the intrinsic difficulties in determining the ECSA
catalytic property of the
catalyst
loading-sensitive large experimental inaccuracies between one method and other, such as CV and EIS studies
comparison with existing reports would be tedious
BET surface ease of determining the BET does not reflect the intrinsic catalytic property
area surface area
most suitable for porous leads to large errors because not all gas adsorption sites are electrochemically active
materials and catalysts
loading-sensitive not suitable for planar and thin film electrodes
catalyst directly cares about the direct comparison with theory and experiment is not feasible
loading loading regardless of type
of catalyst
suitable when same material does not reflect the intrinsic catalytic property of the material
is used at different loadings
comparison of catalysts of varying particle size (e.g., mono- and polydispersed catalysts), density (e.g., metals and metal
aerogels), morphology (e.g., catalysts with spherical, rod, wire, and sheet structures), and topography (e.g., catalysts with
smooth and rough surfaces) is not possible
comparison with existing reports is also not possible

which only the surface layer participates in the electrode
reaction, thereby excluding the catalyst present under the
surface layer), the geometrical area of the substrate electrode is
not equal to the actual surface area of the catalyst participating
in catalysis. In such cases, normalization by the geometrical
surface area will lead to large errors while quantifying the
catalytic activity of an electrocatalyst. However, this is the
conventional and widely accepted method for current normal-
ization. Hence, to get information on the optimum catalyst
loading, knowledge about the catalyst morphology (if a
nanomaterial) and the wettability of the catalyst are needed.
Beyond everything, an experimental study of the effect of
loading can also reveal information about the minimum catalyst
loading to form a near-monolayer catalytically active surface.
The increase in catalyst loading will not affect the potential at a
fixed current density beyond a certain amount of loading that is
actually the minimum amount of catalyst required to form the
monolayer. However, care must be taken while doing such a
study because if the increase in catalyst loading from one trial to
another is large, then the actual optimum loading may slip in
between somewhere. Moreover, if the loading difference is
large, the catalyst resistance will drastically increase, which will
in turn lead to an increase in the overpotential beyond certain
loading limits instead of a steady potential at a fixed current
density. This may lead to potential error in determining the
optimum catalyst loading to form a monolayer. Having
discussed all such difficulties, we can conclude here that the
geometrical surface area can be used normalize the
experimentally observed current when a planar electrode is
used to catalyze the electrode reaction.
3.2. Normalization of the Current by the Electro-
chemical Surface Area (ECSA) and the Brunauer−
Emmett−Teller (BET) Surface Area. It is better to use the
ECSA (or roughness factor)-normalized current density, as it is
more sensitive to the catalyst loading and will vary with the
same. The current normalized by the ECSA (in units of A/
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cm2ECSA) will reflect the intrinsic catalytic property of the
catalyst, unlike the one normalized by the geometrical surface
area. The current density obtained by this method is often
called the specific activity.136 However, the ECSAs determined
by cyclic voltammetry and impedance analysis differ from one
another significantly, which may lead to potential error.
Recently, people have been using the BET surface area of the
catalyst. However, this is also lacking in experimental accuracy.
This is mainly due to the fact that all of the sites in the BET
surface area determined by gas adsorption and desorption need
not be electrocatalytically active. The experimental incongruity
becomes large when the catalyst is composed of more than one
element.
3.3. Normalization of the Current by the Catalyst
Loading. Fabbri et al.11 recently justified why the current
normalized by the catalyst loading is a more reliable activity
parameter than the current normalized in other ways. The
loading-normalized current density (in units of A/g) is
otherwise known as the mass activity. Though it has lesser
experimental inaccuracy than the others, it has more
disadvantages than the other two methods explained above:
direct comparative evaluation of the activity with the theoretical
activity is not possible, the intrinsic catalytic property of the
material is not soundly represented by this parameter, and it
does not allow a fair comparison of catalysts of varying particle
size (e.g., mono- and polydispersed catalysts), density (e.g.,
metals and metal aerogels), morphology (e.g., catalysts with
spherical, rod, wire, and sheet structures), and topography (e.g.,
catalysts with smooth and rough surfaces). To have a better
clarification of the merits and demerits of these methods, we
have summarized them in Table 1.
Having reviewed the advantages and disadvantages of each of
these normalization methods, we can hereby come to a
conclusion that depending on the nature of the catalyst, any
one of these methods can be chosed for normalization of the
current. However, to enable fair comparison with earlier
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Figure 2. (A, B) LSVs for the HER on various transition metal phosphide catalysts with current normalization by geometrical surface area and ECSA,
respectively. (C) Plots of average TOF vs E for various transition metal phoshides. (D−F) Volcano plots for various transition metal phosphides
using different activity parameters such as geometrical-area-normalized current, ECSA-normalized current, and average TOF per surface site.
Reproduced with permission from ref 143. Copyright 2015 Royal Society of Chemistry.
reports, it is essential to have data on the current density
normalized to the geometrical surface area. Otherwise, it is
better to provide all of them together, and the same will help us
to come to semiquantitative conclusion on the reliability of
these methods.
4. BOND ENERGETICS OF INTERMEDIATES:
THEORETICAL INSIGHT FROM DENSITY
FUNCTIONAL THEORY (DFT) CALCULATIONS
For an electrocatalyst to be efficient, the bond strengths of the
intermediates should be neither too high nor too low. In case of
the HER, the intermediate is the H-adsorbed active site after
electrochemical discharge of a proton. Although all of the Pt-
group metals have been predicted to be highly active toward
the HER, the actual activity is in the order Pt > Pd > Ni.137−142
This is mainly because of the increased reluctance shown
toward desorption of Hads from the catalytic site by Pd and Ni.
The high metal−Hads bond strength ultimately results in
catalytic poisoning.137−142 As the standard redox potential for
hydrogen evolution is zero, the associated standard free energy
of hydrogen adsorption is should also be zero.
The efficiencies of a set of HER catalysts are usually
determined by calculating the standard free energies of H
adsorption through DFT calculations and plotting them against
a parameter such as the exchange current density (j0), the
current density at a defined overpotential, or the TOF (Sabatier
volcano plot). The catalysts that are placed at or near the
summit of the plot are said to be highly active for HER
electrocatalysis. Such an analysis of the activity trends of various
transition metal phosphides (viz., Ni2P, FeP, Fe2P, CoP, Co2P,
MoP, MoP/S, Fe0.25C0.75P, Fe0.75Co0.25P, and Fe0.5Co0.5P) in
comparison with Pt nanoparticles (NPs) and Ti foil was
performed by Kibsgaard and co-workers143 using a combined
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experimental and theoretical approach (Figure 2). In this
particular report, the HER activities of these catalysts were
benchmarked by plotting the free energy of H adsorption
against the current normalized by both geometrical surface area
and ECSA and also against the TOF.
According to this study, an optimal free energy of H
adsorption is predicted for Fe0.5Co0.5P when the activity
parameters such as the current normalized by ECSA and the
TOF were plotted against it. However, the Volcano plot
obtained by plotting the current normalized by the geometrical
surface area against the H adsorption free energy showed a
slightly controversial activity trend and placed Fe0.5Co0.5P just
below MoP/S and Fe0.25Co0.75P. This is mainly believed to be
an effect of the contribution of non-Faradaic capacitive current
to the catalytic current. The same group also revealed the
reason behind the exceptional HER activity trends observed
with these FeP-based catalysts from their dependence of the
free energy of H adsorption on the increasing fraction of
monolayer H coverage, as shown in Figure 3. From Figure 3,
one can notice that the free energy of H adsorption decreases
for FeP and Fe0.5Co0.5P beyond a certain fraction of H coverage
on these catalytic surfaces and approaches a negative free
energy of H adsorption at high H coverages. This indicates that
beyond a certain amount of H adsorbed via the electrochemical
discharge of protons, these catalytic surfaces turn into H2
donors simultaneously. The exceptional activity observed with
these catalysts is attributed to this particular behavior.
Later, a similar combined experimental−theoretical work on
revealing the activity trends of CoP catalysts for the HER
depending on the Fe dopant content was reported by Tang and
co-workers.144 Interestingly, they too ended up with the same
conclusion that the Fe0.5Co0.5P is the catalyst with Pt-like HER
activity in acid with a low overpotential of 37 mV at a current
density of 10 mA/cm2. The scheme of the free energy of H
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Figure 3. Plots of free energy of H adsorption on various metal
phosphide catalysts vs increasing fraction of H monolayer coverage.
Reproduced with permission from ref 143. Copyright 2015 Royal
Society of Chemistry.
adsorption with respect to reaction coordinate (Figure 4)
shows that Fe0.5Co0.5P has an optimal free energy of H
adsorption very close to that of Pt.
Figure 4. Scheme of free energy of H adsorption with corresponding
reaction coordinate. Reproduced from ref 144. Copyright 2016
American Chemical Society.
Although both of these reports say that Fe0.5Co0.5P is a better
nonprecious catalysts with Pt-like HER activity, it is not the
bestthere is still room to improve the catalytic behavior.
From Figure 3 we can see that only FeP and Fe0.5Co0.5P show
such a reduction in the free energy of H adsorption, whereas
the other catalysts do not show such a trend on the same. This
could lead to the question of what makes them almost equally
active as FeP and Fe0.5Co0.5P. The answer lies in the higher
negative free energy of H adsorption at lower H coverage and
lower positive free energy of H adsorption at higher H coverage
on these surfaces. This higher negative free energy of H
adsorption at low H coverage shows its readiness to adsorb
hydrogen, and the lower positive free energy of H adsorption
the ease of H2 delivery from these catalytic surfaces and at the
same time, its ability to achieve full Hads coverage as seen with
Pt. This is the reason why these FeP based systems have been
showing parallel activity to that of Pt in catalyzing HER.
Examples of this kind of catalyst are MoP and MoP/S, as
shown in Figure 3. This inference leads us to believe that the
better transition metal phosphide catalysts are still hidden and
that changing the stoichiometric compositions among all of
these known metal phosphides could lead to better HER
catalysts. To carry out such worthy studies, combined
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theoretical and experimental studies on these catalysts such as
the above-said reports are highly desired.143,144
In the case of the OER, the reaction proceeds through
adsorption of water/hydroxide on the catalytic site (S−OH/S−
OH 2) followed by oxidation of the same along with
deprotonation to form the metal oxide (SO). Formation of
the hydroperoxide intermediate (S−O−OH) then occurs by
coordination of one more water molecule/hydroxide ion at the
same site, and this is followed by deprotonation and reductive
elimination of O2 from the active site, making it ready for the
next catalytic cycle. These are the common elementary steps in
all of the proposed pathways for the OER mechanism in acidic
and alkaline media.11,13,14,116 We can see from this that the
OER is associated with a series of elementary steps and that
during each step the chemical environment around the active
site is changing. If any one of these intermediates is not favored
by its standard free energy of bonding, then the catalyst will not
be able to catalyze the OER. On the other hand, if the bond
strength is too high for any one of these intermediates, then
catalyst poisoning occurs, resulting in a very high overpotential
for the OER. In 2007, Rossmeisl et al.145 presented a good
theoretical survey of the efficiency of the OER activities of
oxides of Ir, Ru, and Ti in which they defined the theoretical
OER activity of the same by plotting their oxygen binding
energies against −ΔG (the negative of the change in the
standard free energy) associated with each of the above-said
elementary steps of the OER. That plot also contained a
horizontal dashed line indicating the thermodynamic over-
potential for the OER (1.23 eV). A material with high activity
has to stay on the horizontal line, but it will not be seen becaue
of the kinetic hindrances experienced by the catalysts in the real
system, which will fetch them an additional potential (the
overpotential). Moreover, the plot also says that regardless of
the nature of the binding of oxygen to the active site, the
activity is always limited by the oxide (SO*) and peroxide
(S−O−O*) formation steps. However, catalysts with lower
oxygen binding energies will stay closer to the theoretical
horizontal line of the OER (where RuOx is placed just above
IrOx as it binds more strongly to oxygen than RuOx does). In
the report of Man et al.,14 similar interpretations were made for
various other binary metal oxides, including the three studied
by Rossmeisl and co-workers along with some perovskites as
OER catalysts. Here the difference in the standard free energies
of two subsequent steps, namely, hydroxide coordination and
oxidation of the same with deprotonation (ΔGO* − ΔGHO*)
was plotted against the theoretical oxygen overpotential. It
should be noted that the standard free energy associated with
the formation of hydroperoxide from the oxide intermediate
was not included here. This could lead to potential errors in
predicting the catalytic activities of some catalysts with slow
kinetics of hydroperoxide formation. As far as this work is being
considered, the catalysts placed at the top of the plots, such as
Co3O4, RuO2, IrO2, NiO, SrCoO3, LaNiO3, and SrNiO3, are
the ones with the optimum oxygen bonding energies to catalyze
the OER efficiently. From the above discussion, we can now
conclude here that the catalytic surface with high oxygen
binding energy would have the peroxide formation step as the
limiting step and the surface that binds oxygen weakly will have
the hydroxide coordination and oxide formation steps as the
limiting steps. Therefore, an OER catalyst should neither bond
too strongly nor too weakly to oxygen, as we have seen in the
case of the HER.
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5. EFFECT OF HETEROATOMS (S, SE, AND P) IN
WATER SPLITTING
A brief and nice highlight on the effect of P doping in metal
lattices on the electrocatalytic HER has recently been given by
Shi and Zhang.8 In this section of the review, we will also
elaborate the effect of other heteroatoms such as S and Se not
only in the HER but also in the OER.
As highlighted by Shi and Zhang,8 the polarization-induced
partial negative charges localized on P centers in a metal
phosphide structure with a P-terminated surface attracts
protons as a base and make their discharge easier, promoting
the HER easily. As a consequence of this, it is obvious to expect
that metal phosphides with higher P content should show
higher HER catalytic activities. Interestingly, among the
reported phosphides of Co, Ni, and Fe, the polymorphs with
higher P content are reported to be the highly active ones.
Between CoP and Co2P, CoP is the more active one (Figure
5a).146 Similarly, among Ni2P, Ni5P4, and Ni12P5, Ni5P4 with
the highest P content is the most active one (Figure 5b).147
Besides trapping the protons by acting as a base, these P centers
have recently been found to enhance the hydrogen desorption
at high Hads coverage. A DFT study carried out by Wang and
Figure 5. (a) P-content-dependent HER activities in NixPy.
Reproduced with permission from ref 147. Copyright 2015 Royal
Society of Chemistry. (b) P-content-dependent HER activities in
CoxP. Reproduced from ref 146. Copyright 2015 American Chemical
Society.
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co-workers148 on P-terminated MoP surfaces focusing the
Gibbs free energy of hydrogen adsorption (ΔG°H) revealed that
at lower Hads coverage ΔGH° is sufficiently negative (−0.34 eV)
to accelerate the adsorption of hydrogen. However, when the
surface becomes fully covered by Hads, ΔG°H becomes positive
and accelerates the desorption of hydrogen, as observed earlier
in the cases of MoS2 with more S on the edges. This is in
agreement with the earlier reports of Kibsgaard et al.143 and
Tang et al.144 In the cases of S- and Se-doped metal lattices, a
similar mechanism should be responsible for the enhanced
HER catalytic property. However, the increased electro-
negativity of S and the relatively higher strength of the S−H
bond (∼360 kJmol−1) do not allow many of the sulfides of Fe,
Co, and Ni to act as efficient HER catalysts. However, a few
selected sulfides such as Ni3S2, CoS, CoS2, FeS2, and Co9S8 are
reported to be good in catalyzing the HER in acid. When the
bond strength is considered as an influencing factor in
enhancing the hydrogen desorption from the catalytic site,
the selenides stand a step ahead of both sulfides and
phosphides, as the strengths of E−H bonds (E = S, P, Se)
are in the order S−H (363 kJ/mol) > P−H (322 kJ/mol) >
Se−H (276 kJ/mol).149 Moreover, like phosphides, both
sulfides and selenides can trap protons by acting as bases to
promote the discharge step faster.
The story on the influences of these heteroatoms in the OER
is different from the one we described above for the HER.
Unlike the HER, these heteroatoms do not have any direct
influence in enhancing the OER kinetics of these materials. In a
report by Subbaraman et al.,150 the trends in the electrocatalytic
OER activities of these 3d M2+ ions with oxide environments
are described, and it is stated that Ni2+ is more active than other
divalent cations that appear just before in the series. This is
mainly attributed to the increased 3d−2p repulsion between
the metal d-band center and the coordinated oxygen’s p-band
centers. However, when we have electronegative ligands (S2−,
Se2−, and P3−) in the vicinity of catalytically active metal sites,
there could be two effects. One of these is that the localized
negative charges on these heteroatoms (S and P only) will
actually deactivate the catalyst from coordinating with the
hydroxide ligand as a result of the increased 3p−2p repulsion.
This will increase the overpotential considerably. However,
after a tiresome coordination with hydroxide ligands, the
oxidation coupled with deprotonation followed by peroxide
formation will be supported because the deprotonation will
increase the electron population on the metal center and
thereby feed these electronegative heteroatoms. Similarly, the
formation of peroxide by coordination of an additional
hydroxide ligand happens just above the surface layers of
these heteroatoms and therefore is not affected during the
coordination processes. After formation of the peroxide
intermediate, the delivery of the dioxygen molecule is actually
accelerated by the enhanced 3p−2p repulsion between the
heteroatoms and the peroxide entity. In the case of Se in place
of S and P, we think that the coordination step with hydroxide
will be less affected because both the metal centers and the
ligand centers have 3d subshells as the outermost orbitals.
However, because of the negative charge localized on Se sites
and the cumulative 3d−2p repulsion between the metal d-band
center and Se d-band center, the delivery of the dioxygen
molecule may become faster.
The facts discussed above on the OER performance of group
VIII metal (Fe, Co, and Ni) sulfides, selenides, and phosphides
are in resonance with the experimental reports. These are the
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reasons why the selenides are better OER catalysts than the
phosphides and sulfides. In the HER, the selenides and
phosphides are better than the sulfides as a result of the
strengths of the E−H bonds (E = S, Se, P) described above.
Hence, we conclude here by saying that an efficient water
splitting catalyst should be designed by considering the bond
energies of the intermediates formed and the electronic
structure requirements of each element in the catalyst.
6. OTHER REQUIREMENTS FOR A GOOD WATER
SPLITTING CATALYST
In addition to the key thermodynamic and kinetic requirements
of an electrocatalyst discussed above, it is important to highlight
some other essential requirements for an electrocatalyst to be
economically affordable in large-scale water electrolysis.
The first of these is the availability of resources of the
catalytic material from which the catalyst can be formulated, as
we can no longer rely on noble metals (Pt, Ir, and Ru) to do
this simple water electrolysis. The second one concerns health
and environmental hazards. The catalyst should at least be less
harmful to persons working with it and to the environment in
which it is applied. Except for oxides and hydroxides of Fe, Co,
and Ni, other compounds are potentially harmful. The third
one is the conductivity of the catalyst. Although heteroatom
doping of the metal lattice is fruitful in enhancing the catalytic
activity, doping beyond certain limits will turn the metal
surfaces into semiconducting and even insulating ones, which is
not acceptable in electrocatalytic water splitting because it will
drastically increase the Ohmic drop. The fourth one is the need
for a high surface area of the catalyst, which would allow the
amount of catalyst used to be reduced. The wettability is
another parameter to be considered while formulating a water
splitting catalyst, as higher wettability lowers the Ohmic drop
caused by the formation of gas bubbles on the catalyst surface.
Another serious problem in dealing with these Fe-, Co-, and Ni-
based catalysts is the current selectivity, as they tend to have
strong redox reactions within the potential window of the OER.
In such cases we should be aware of where the applied current
is being spent. A good electrocatalyst for water oxidation should
have more current selectivity toward the OER rather than its
own redox reactions. To know this, the Faradaic efficiency
determination by the RRDE experiment can be used. The final
thing we should worry about is the corrosion resistance. Since
the medium of water electrolysis is going to be either highly
acidic or highly basic, the material that is supposed to catalyze
the HER and OER should have very high corrosion resistance.
With the sulfides, selenides, and phosphides of Fe, Co, and Ni,
this problem is well documented in the literature and patents,
as the oxides of these heteroatoms (S, Se, and P) are well-
known corrosion inhibitors and resistors.151−159
The above discussion certainly implies the advantageous use
of the sulfides, selenides, and phosphides of group VIII 3d
metals in water electrolysis. In the following sections, the
synthetic strategies applied in designing such catalysts and their
subsequent applications in water electrolysis are highlighted in
detail.
7. SYNTHETIC STRATEGIES EMPLOYED IN GROUP VIII
3D METAL (FE, CO, AND NI) SULFIDE, SELENIDE,
AND PHOSPHIDE NANOSTRUCTURES
7.1. Synthesis of Metal (Fe, Co, and Ni) Sulfides. The
synthesis of metal sulfides has been achieved by following one
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of the procedures with a few necessary modification from one
material to another. The simple method of synthesizing metal
sulfides is coprecipitation, in which the metal precursor salt is
placed in a solvent that dissolves both the metal ion and the
sulfide precursors. In this method, the reaction temperature and
the pH should be carefully monitored to get reasonable yield.
The main disadvantage of this method is that it requires
additives such as surfactants, scaffolds, ligands, and chelating
agents to control the size and shape of the synthesized metal
sulfide nanostructure. Moreover, these additive are hard to
remove after the synthesis. There are no reports on the
preparation of MxSy (M = Fe, Co, Ni) nanostructures by this
coprecipitation method for electrocatalytic water splitting
applications.
The most common method of all time used to prepare metal
sulfide nanostructures alone or with some three-dimensional
(3D) matrix support is the solvothermal method. The common
sulfide sources used in this method are thiourea (TU,
(NH2)2CS) and thioacetamide (TAA, CH3(CS)NH2).160,161
Among the sulfides of Fe, Co, and Ni, the sulfide
nanostructures of Co have been relatively reported more than
other two metal sulfides. Di Giovanni et al.162 prepared FeS
nanoparticles by solvothermal decomposition of Fe2S2(CO)6 at
230 °C for the HER under neutral conditions. Other available
reports describe Fe-based sulfides with Co as a dopant. Shen
and co-workers reported the formation of Fe0.5Co0.5S@
mesoporous N-doped graphitic carbon as an efficient ORR
and OER catalyst under alkaline conditions by a solvothermal
route where TU was used as the S source.163 Apart from these,
Faber et al.164 recently reported pyrite-type FeS2 for the HER
obtained by a two-step procedure that includes the formation of
a metallic thin film on a desired substrate by electron beam
evaporation followed by thermal sulfidization taking elemental
S as the source directly. Co-based sulfides with varying S
content such as CoS, CoS2, Co3S4, and Co9S8 have been
prepared by solvothermal methods and reported with different
morphologies. You et al.165 compared the HER electrocatalytic
activities of hollow nanoprisms of CoS prepared by microwave
(MW) and solvothermal methods taking TU as the S source.
Kornienko et al.166 showed the HER electrocatalytic activity of
amorphous CoS with some O content in CoS2-like small
amorphous clusters of CoS. Aslan and co-workers prepared
CoS nanoparticles and anchored them on carbon nanotubes
(CNTs) by a solvothermal method for the HER under alkaline
conditions.167 Wang’s group recently published an interesting
report on the design of CoS@CTs@CP, an efficient 3D
electrocatalyst for overall water splitting that comprises carbon
tubes (CTs), carbon paper (CP), and CoS sheets (Figure 6).168
Besides CoS, pyrite-type CoS2 is the next best documented
Co-based sulfide nanocatalyst for water splitting. Faber et al.169
synthesized pyrite-type CoS2 by electron beam evaporation of
the metal target followed by thermal sulfidization and applied
them to the HER. These pyrite CoS2 began to draw attention
in mid-2014 and have been reported frequently with modified
morphologies and support materials such as graphene oxide
(GO), CNTs, N-doped CNTs (NCNTs), etc. The following
are some significant reports about them. It was Faber and co-
workers who reported the HER activity of CoS2 for the first
time.169 Soon after that, Zhang’s group reported pyrite CoS2
prepared by a solvothermal route as a versatile catalyst for the
HER over a wide pH range of 0−14.170 In the same year, Peng
et al.171 fabricated CoS2 nanosheets on graphene@CNT as a
flexible electrode for the HER. Then a similar report by
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Figure 6. (a, b) SEM images of CP/CTs/Co−S. (c, d) TEM images,
(e) SAED pattern, and (f) elemental mapping of CT/Co−S.
Reproduced from ref 168. Copyright 2016 American Chemical
Society.
Ganesan et al.172 with S- and N-doped graphene as a support
for CoS2 for use in the ORR and OER was published later in
2015. Other than these two sulfides of Co, Co3S4 on N-doped
CNTs was prepared by Wang and co-workers by a simple anion
exchange method taking Co(OH)2/NCNTs as the starting
material, and this material was applied to the OER.173 Feng et
al.174 proposed method for the formulation of Co9S8 armored
with C that utilizes thiocyanuric acid as the S source and
thermal decomposition at 700 °C under an atmosphere of N2.
Very recently, Liang et al. published an interesting report on
CoS and Zn-doped CoS for total water splitting where these
catalysts were grown on a Ti mesh.175
Like the sulfides of Fe and Co, Ni-based sulfides with good
electrocatalytic properties toward water splitting have been
reported. NiS and Ni3S2 are the most common Ni-based
sulfides applied for water splitting. The exceptional OER
performance of Ni3S2 grown on Ni foam with low overpotential
was first reported by Zhou et al.176 in 2013. They synthesized
this material by a simple solvothermal sulfurization of Ni foam
taking S directly as the sulfur source. In 2015, Tang et al.177
showed the HER performance of Ni3S2 nanosheets grown on
Ni foam by a hydrothermal method for a pH range of 0−14.
Then the same Ni3S2 in the form of a nanorod (NR) array on
the same Ni foam for use in total water splitting was reported
by Ouyang et al. later in 2015.178 In the last two reports of
Ni3S2 preparation, TU was used as the S source, and the
solvothermal treatment was kept constant in all three methods.
In another report by Tang et al.,179 NiS hierarchical arrays
grown on carbon cloth (CC) for efficient HER electrocatalysis
were obtained adapting a solvothermal route of synthesis.
Another interesting report by Yang and co-workers achieved
highly efficient and stable water splitting catalysis with Fe-
doped NiS nanaoarrays prepared by a solvothermal route.180
Similarly, the electrocatalytic properties of NiS for the HER and
OER individually and also for bifunctional catalytic activity
were reported. Unlike Ni3S2, the bifunctional activity of NiS in
1 M KOH was first reported in 2015 by Zhu et al.181 following
similar hydrothermal route of sulfidizing Ni foam. Later in
2015, Li et al. reported the atomic layer deposition of NiS on a
silica substrate for the OER under alkaline conditions.182 Very
recently, Mabayoje et al.183 comparatively reported the role of
the anion in nickel sulfide and selenide toward the OER.
Apart from the individual binary metal sulfides, it is common
to see reports on sulfides of alloys of Fe, Co, and Ni. The
sulfide of Ni−Co alloy is the most often reported alloy sulfide
of this kind. The first report of the preparation of NiCo2S4@
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Review
graphene by a solvothermal approach using TU as the S source
was published by Liu and co-workers in 2013, and they applied
this material to the ORR and OER under alkaline conditions.184
Recently Liu et al.185 reported the electrodeposition of Ni−
Co−S and applied it to total water splitting. In a couple of
recent reports by Sun and co-workers, the sulfides of Ni and Co
have been fabricated into nanowire arrays via a solvothermal
route for application in total water splitting electrocataly-
sis.186,187 Ansovini et al.188 recently reported the formulation of
a 3D Co9S8−NixSy/Ni foam electrode for the HER by a
solvothermal method. The sulfide of Co−Fe alloy on N-doped
mesoporous carbon for the ORR and OER was recently
reported by Shen et al.163 Wang et al.189 reported the
advantages of Co-doped FeS2 nanosheet/CNT arrays for
HER application. Similarly, Long et al.190 reported the
fabrication of ultrathin Fe−Ni−S nanosheets by a topotactic
sulfidization of Fe−Ni layered double hydroxides and examined
their HER properties under acidic conditions. Apart from these,
the sulfides of these three metals (Fe, Co, Ni) are also often
alloyed with other metals to improve their electrocatalytic
properties. One such catalyst, Ni−Mo−S on carbon fiber cloth
synthesized by a solvothermal method for the HER under
neutral conditions, was reported by Miao et al.191
For a better comparative overview of latest synthetic
methodologies of these metal sulfides, we have tabulated the
materials, precursors, and methods in Table 2.
7.2. Synthesis of Metal (Fe, Co, and Ni) Selenides. The
synthesis of metal selenides resembles the synthesis of metal
sulfides in many ways. The most common method of forming
metal selenide nanostructures is the solvothermal route. The Se
sources used for metal selenide synthesis are selenourea (SU),
selenium metal powder, sodium hydrogen selenide (NaHSe)
derived from the reaction of NaBH4 and crude Se powder, and
sodium selenide (Na2Se) in some cases, particularly when
aprotic solvents are used as the medium of synthesis.192 Unlike
the sulfides, the numbers of reports on the selenides of these
three metals are uneven. The most reported one is CoSe2 for
both the OER and HER. The lone report on NiSe nanowires
(NWs) was published by Tang et al.193 in 2015, where the NiSe
NWs were solvothermally grown on Ni foam and applied for
water splitting under strongly alkaline conditions (1 M KOH).
NaHSe derived from the reaction of crude Se powder and
sodium borohydride was used as the Se source during the
solvothermal treatment of surface-etched-clean Ni foam. In the
case of Fe, there has been no report for either the HER or
OER. However, very recently Wang and co-workers reported
that the OER activity of NiSe was drastically increased when Fe
was introduced into the system, with a decrease in the
overpotential of >100 mV.194 This indicates that although the
catalysts with Fe alone have not been shown to date to possess
any significant OER activity, their incorporation into the lattices
of active catalysts composed of Ni and Co may reduce the
overpotential and increase the activity. In that report, the Ni to
Fe ratio was maintained at 3:1 during the Ni−Fe ultrathin
precursor sheet formation and also while it was selenized with
NaHSe by a hydrothermal route.
Apart from the above two reports, the electrocatalysis by
selenides of group VIII 3d transition metals is mainly occupied
by CoSe2. Cobalt diselenide has been reported in both
amorphous and crystalline forms with various morphologies
and supports. Some of the important findings on the synthesis
of this CoSe2 are briefly summarized below. Other than these
there are two recent interesting reports on Ni3Se2 films and
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Table 2. Methodologies and Precursors Used To Form the Sulfides of Fe, Co, and Ni
method and reaction
s. no. material and morphology metal precursor source of sulfur conditions ref
1 iron sulfide nanoparticles Fe2S2(CO)6 Fe2S2(CO)6 solvothermal heating at 230 °C 162
2 Co0.5Fe0.5S@N-MC cobalt(II) acetate and iron(III) nitrate thiourea self-assembly by F127 163
surfactant and annealing at
900 °C in Ar atmosphere
3 FeS2, CoS2, NiS2 films high-purity Fe, Co, and Ni metals sulfur powder electron beam evaporation and 164
thermal sulfidation
4 hollow cobalt sulfide nanoprisms cobalt acetate hydroxide thioacetamide microwave heating for 15 min 165
5 CoSx film CoCl2·6H2O thiourea electrodeposition at pH 7 166
6 CoS@CNT CoCl2·6H2O thioacetamide solvothermal method at 140 °C 167
for 24 h, N2 atmosphere
7 CoS@CNT@CFP sheets Co(NO3)2·6H2O thiourea electrodeposition for 8 min 168
8 CoS2 micro- and nanowires Co(NO3)2·6H2O and (Co(OH)(CO3)0.5·xH2O sulfur powder thermal sulfidation at 500 °C 169
for 1 h
9 CoS2 pyramids@Ti foil CoCl2·6H2O thiourea hydrothermal method at 180 170
°C for 15 h
10 CoS nanosheets@graphene@CNT Co(Ac)2·4H2O CS2 and thiourea hydrothermal method 171
combined with vacuum
filtration
11 CoS nanoparticles@N- and S-doped graphene Co(TU)4(NO3)2 complex Co(TU)4(NO3)2 solid-state thermolysis at 400, 172
oxide complex 500, and 600 °C
12 Co3S4@NCNTs CoCl2·6H2O Na2S and solvothermal method at 160 °C 173
thioacetamide for 15 h
13 Co9S8 nanoparticles@C Co(NO3)2·6H2O trithiocyanuric acid annealing at 700 °C in N2 174
atmosphere for 3 h
14 Zn0.76Co0.24 S/CoS2 nanowires@Ti mesh ZnCo2O4 nanowires sulfur powder annealing at 400 °C for 2 h 175
15 Ni3S2 nanorods@Ni foam nickel foam thioacetamide hydrothermal method at 180 176
°C 4 h
16 Ni3S2 nanosheets@Ni foam Ni(NO3)2·6H2O thiourea hydrothermal method at 120 177
°C 10 h
17 Ni3S2 nanorod arrays@nickel foam nickel foam thiourea hydrothermal method at 160 178
°C for 6 h
18 NiS2 nanosheets@CC Ni(NO3)2·6H2O sulfur powder hydrothermal method at 100 179
°C for 10 h
19 iron-doped nickel disulfide nanoarray@Ti NiFe LDH sulfur powder annealing at 400 °C for 60 min 180
under Ar atmosphere
20 nickel sulfide microsphere film@Ni foam nickel foam sulfur powder annealing at 300 °C with a rate 181
of 8 °C min−1 under Ar
atmosphere
21 NiSx films bis(N,N′-di-tert- butylacetamidinato)nickel(II) hydrogen sulfide vapor-phase atomic layer 182
deposition
22 NiS film NiCl2 thiourea electrodeposition 183
23 NiCo2S4 nanoparticles@graphene Ni(CH3COO)2·4H2O and Co(CH3COO)2·4H2O thiourea solvothermal method at 200 °C 184
for 6 h
24 NiCoS nanosheet films Ni(CH3COO)2·4H2O and Co(CH3COO)2·4H2O thiourea electrodeposition 185
25 CoS nanosheets@Ti mesh CoCl2·6H2O thiourea electrodeposition 186
26 NiCo2S4 nanowires@CC NiCl2·6H2O and CoCl2·6H2O sulfur powder annealing at 300 °C for 2 h 187
27 Co9S8−NixSy@Ni foam Co(NO3)2·6H2O and nickel foam thiourea annealing of cobalt thiourea 188
complex on Ni foam at 300
°C for 5 min
28 Fe1−xCoxS2/CNT Fe(NO3)3 and Co(Ac)2 thioacetamide 90 °C in an oil bath for 24 h. 189
29 iron−nickel sulfide nanosheets FeNi LDH thioacetamide hydrothermal method at 120 190
°C for 6 h
30 Ni−Mo−S nanosheets@CC Na2MoO4·2H2O and NiSO4·6H2O L-cysteine hydrothermal method at 200 191
°C for 24 h

NiSe2 nanowires fabricated via electrodeposition and solvo-
thermal routes by Sun and co-workers for application in total
water splitting.195,196 Like the other two selenides (NiSe NWs
and Ni−Fe−Se nanosheets), the synthesis of CoSe2 is also
achieved by the solvothermal method. It was Xu and co-
workers who in 2013 reported the exceptional HER activity of
CoSe2 nanobelts to which Ni/NiO was anchored by electro-
deposition on a glassy carbon electrode (GCE).197 Soon after
in 2014, the same was reported as CoSe2 NPs grown on carbon
fiber paper (CFP) by Kong et al.,198 who utilized thermal-
pyrolysis-assisted cobalt oxide NP formation on CFP followed
by selenization under a Se vapor atmosphere. The HER
8080
performance shown by this CoSe2 NPs/CFP catalyst was better
than the previous report. In 2015, more attention was paid to
synthesizing CoSe2 in various forms using various methods with
the ultimate aim of total water splitting. In this regard, for the
first time Liu et al.199 reported the bifunctional catalytic activity
of CoSe2 as electrodeposited amorphous thin films on Ti foils
for full water splitting. Before this, Carim and co-workers had
already reported the HER activity of electrodeposited CoSe
amorphous thin films in 2014.200 Then the attention was
deflected toward crystalline CoSe2. Zhang et al.201 reported the
HER activity of polymorphic CoSe2 with mixed orthorhombic
and cubic phases. Recently, Liao et al.202 reported the OER
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activity of coral-like CoSe2 nanostructures prepared by a
solvothermal route. As expected, the CoSe2 was then
composited with various other active catalysts such as MoS2
and Ni−Fe LDH and synergistically enhancing compounds and
substrates such as CeO2, TiO2, and graphene to improve the
catalytic activity of CoSe2. A clever thing done by Hou and co-
workers was the synthesis of a CoSe2/Ni−Fe LDH on
graphene composite, which resulted in better bifunctional
water splitting catalytic activity than any other report.121
Similarly, Gao et al.105 synergistically improved the HER
performance of CoSe2/MoS2 by making a composite of them.
With a different synthetic route involving microwave
irradiation, Ullah et al.203 reported the same CoSe2 but as a
composite with graphene and TiO2 with improved HER
performance. Zheng and his group members showed the effect
of CeO2 on the OER catalysis led by CoSe2 with a nanobelt
morphology.204 As a step ahead in the HER catalysis by CoSe2,
Liu et al.205 formed a 3D HER catalyst by simple hydrothermal
growth of CoSe2 on carbon cloth (Figure 7).
Figure 7. (a) XRD patterns of the precursor and selenized product
scratched down from CC. (b, c) SEM images of Co(OH)F NW/CC.
(d) TEM image of a Co(OH)F NW. (e, f) SEM images of CoSe2
NW/CC. (g) TEM image of a CoSe2 NW. (h) HRTEM image and (i)
SAED pattern of a CoSe2 NW. (j) STEM image and EDX elemental
mapping of cobalt and selenium for a CoSe2 NW. (k) SEM image of a
CoSe2 MP. Reproduced from ref 205. Copyright 2015 American
Chemical Society.
We have summarized the methods and materials used for the
synthesis of these metal selenides in Table 3.
7.3. Synthesis of Metal (Fe, Co, and Ni) Phosphides.
Although there are two good surveys on the synthesis of
transition metal phosphides and their applications to the HER,
it would be better to have a consolidated review of the OER
activities of Fe, Co, and Ni phosphides in addition to the
sulfides and selenides of the same. The synthesis of metal
phosphide nanostructures is much more difficult than that of
simple sulfides and selenides and is almost always done at high
temperature in an inert atmosphere. The metal phosphide
syntheses mainly fall into three categories. In the high-
temperature liquid-phase synthesis, the most common P
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source, trioctylphosphine (TOP), is used along with
trioctylphosphine oxide (TOPO) as a structure-directing
agent in various molar ratios. In the high-temperature solid-
state synthesis, the desired metal precursor is reacted with
sodium hypophosphite (Na2HPO2), commercially known as
hypo, as the source of P under highly oxygen-free conditions.
Other than hypo, elemental phosphorus (preferably red
phosphorus) and ammonium hydrogen phosphate
((NH4)2HPO4) are also used as P sources.8,10 However, with
the latter two P sources, the reaction temperature needs to be
2-fold higher than that required for the solution-phase synthesis
using TOP. The inert atmospheres used to date for the
synthesis of these metal phosphide nanostructures are Ar, H2,
N2, and mixtures of H2 and N2 under either static or flowing
conditions. Similarly, in all of the liquid-phase syntheses the
common metal precursors used are the acetate or acetylacet-
onate complexes of the respective metal ions or the nitrates and
chlorides of the metals with a phase-transfer catalyst (PTC)
such as tetraoctylammonium bromide (TOAB).206,207 In the
case of the high-temperature solid−gas-phase reaction, the
nitrates are the most common metal precursors used. Unlike
the sulfides and selenides, the phosphides of Fe, Co, and Ni
have been equally explored in terms of synthesis and their
subsequent applications to water splitting. In the case of Fe, the
phosphides reported to date are FeP, FeP2, and Fe2P. Among
these, FeP is the more frequently reported one. As mentioned
in the earlier discussion on the effects of heteroatoms in water
splitting, the higher P content in FeP helps it to be more active
than Fe2P. Moreover, where bifunctionality is concerned,
among the available reports on the phosphides of Fe there is
only one report by Yan et al.,208 who grew ZnO NWs on CFP,
which were then doped with Fe3+ by hydrolysis followed by
phosphidization at 300 °C with hypo in an Ar atmosphere.
Similarly, there is a lone report by Xiong et al.209 on the OER
catalytic activity of FeP NRs supported on CFP obtained
through a set of hydrothermal and gas-phase phosphidization
reactions. Almost all of the other reported FeP materials in
various morphologies and crystalline forms are devoted only to
HER catalysis. Some of their synthesis sequences are briefly
summarized below. FeP has been reported as nanowires,
nanotubes, nanosheets, thin films, and nanocrystals and as a
composite with N-doped CNTs for HER applications. The first
report on HER electrocatalysis on FeP was published by Xu
and co-workers, who synthesized FeP nanoporous nanosheets
by an anion exchange method.210 Du and co-workers proposed
an interesting method of preparing FeP NRs by a simple hard-
template method using anodized aluminum oxide (AAO) as the
desired hard template, onto which the Fe3+ precursor was
loaded through a sequence of soaking and drying processes
followed by phosphidization with hypo in an alumina boat at
350 °C.211 Later, Liang et al.212 obtained nanoarrays (NAs) of
FeP NRs on CC by a solvothermal treatment to form the
Fe2O3/CC precursor, which was then phosphidized using hypo
at relatively lower temperature than other methods (Figure 8).
Using a similar synthetic route, Tian and co-workers obtained
3D FeP NP thin films on CC that showed better HER
performance than other phosphides in both acidic and neutral
electrolytes.213 In a similar report by Yang et al.,214 the same
CC was used once again for the formation of rugae-like FeP
and FeP2 nanocrystal (NC) arrays, which were used later for
HER electrocatalysis in acid. Jiang and co-workers chose a Ti
plate instead of CC as the substrate for the FeP NW array.215
The synthesis was a two-step process involving initial
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Table 3. Methodologies and Precursors Used for the Synthesis of Selenides of Fe, Co, and Ni
source of
s. no. material and morphology metal precursor selenium method and reaction conditions ref
1 MoS2/CoSe2 Co(OAc)2·H2O and (NH4)2MoS4 Na2SeO3 hydrothermal method at 200 °C 105
for 10 h
2 Co0.85Se/NiFe LDH Co(NO3)2·6H2O, Ni(NO3)2·6H2O, and Fe(NO3)3·9H2O Na2SeO3 hydrothermal method at 150 °C 121
nanosheets for 48 h
3 NiSe nanowire film@Ni foam nickel foam Se powder hydrothermal method at 140 °C 193
for 12 h
4 (Ni0.75Fe0.25)Se2@CFC Ni(NO3)2·6H2O and Fe(NO3)3·9H2O Se powder hydrothermal method at 180 °C 194
for 24 h
5 Ni3Se2 film@Cu foam Ni(CH3COO)2·4H2O SeO2 electrodeposition 195
6 NiSe2 nanoparticle film NiCl2·6H2O SeO2 electrodeposition 196
7 Ni/NiO/CoSe2 nanocomposite Co(Ac)2·H2O and nickel(II) 2,4- pentanedionate Na2SeO3 hydrothermal method at 180 °C 197
for 16 h
8 CoSe2 Nanoparticles@CFP Co(NO3)2·6H2O Se powder thermal selenization in Ar 198
atmosphere
9 CoSe film@Ti mesh Co(Ac)2·4H2O SeO2 electrodeposition 199
10 amorphous cobalt selenide Co(Ac)2·4H2O SeO2 electrodeposition 200
films@Ti foil
11 polymorphic CoSe2 CoCl2 SeO2 electrodeposition 201
12 3D coral-like CoSe Co(NO3)2·6H2O Se powder hydrothermal method at 180 °C 202
for 15 h
13 CoSe2/graphene−TiO2 CoCl2 Se powder microwave heating for 15 min 203
heterostructure
14 CeO2/CoSe2 nanobelts Co(Ac)2·H2O and Ce(CH3COO)2 Na2SeO3 polyol reduction method at 278 204
°C for 1 h
15 CoSe2 nanowires Co(NO3)2·6H2O Se powder hydrothermal method at 140 °C 205
for 10 h

phosphidization under an atmosphere of N2 with hypo at 350

Figure 8. (a, b) SEM images of (a) Fe2O3 NAs/CC and (b) FeP NAs/
CC. (c) TEM and (d) HRTEM images of FeP nanorods. (e) SAED
pattern recorded from the FeP nanorod. (f) STEM image and EDX
elemental mapping of C, P, and Fe for the FeP NAs/CC. Reproduced
from ref 212. Copyright 2014 American Chemical Society.
hydrothermal growth of FeOOH on the Ti plate followed by its
chemical conversion to an FeP NW array on the Ti plate at low
temperature. As expected, Liu and co-workers composited N-
doped CNTs to FeP by growing the Fe2O3/NCNT precursor
composite first via a hydrothermal route followed by
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°C and applied these composites to the HER.216
The phosphides of Co have been studied more than those of
Fe in both the HER and OER. The phosphides of Co known to
date are CoP and Co2P. As seen in the case of FexP, CoP with
the higher P content is reported to be a better catalyst for the
HER and OER than Co2P. Moreover, the number of reports on
CoP is 3-fold higher than that on Co2P. Co2P has been
reported as nanoneedles and NWs and as a composite with
CNTs and NCNTs for OER and HER applications. The
synthesis of Co2P resembles the synthesis of FexP. One such
recent report with a significantly different synthetic route was
made by Dutta and co-workers, who synthesized Co2P
nanoneedles by a liquid-phase alkylamine-assisted synthesis
but instead of TOP as the P source, PH3 gas produced ex-situ
was purged into the reaction vessel at 230 °C. This method
provided the significant advantage of avoiding the strong
possibility of explosion by other methods in the case when a
little bit of O2 is present inside the reaction chamber.217 In the
case of CoP, there is a cluster of reports on their synthesis and
subsequent applications to the HER and OER. The synthesis of
CoP can be done by any of the above-seen methods for the
synthesis of FexP, viz., liquid-phase metal ion reduction and
phosphidization, high-temperature solid−gas-phase reaction, or
anion exchange reaction. Like the contribution made by Sun
and co-workers in the case of sulfide and selenide catalysts of
these three metals, they have done an enormous amount of
work on cobalt phosphide too by various methodologies and
subsequently used them for both HER and OER applications.
Among them, fabrication of self-supported nanoporous CoP
nanowire arrays,218 CoP nanowire arrays for sensing and
photcatalytic HER,219 templated-assisted synthesis of CoP
nanotubes,220 CoP nanowire arrays on Ti mesh,221 3D
interconnected CoP nanowire arrays,222 and a combined
experimental−theoretical study of CoP with varying Fe dopant
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contents are the significant works.144 Popczun et al.223 reported
the HER activity under acidic conditions of CoP NPs prepared
by the first method mentioned above. Subsequently, a number
of reports appeared in literature with either a significant
improvement in the catalytic activity or an improvement
resulting in a relatively easier synthetic route. CoP has been
reported with a branched starlike morphology by Popczun et
al.,224 as hollow polyhedra by Liu and Li,225 as urchinlike NCs
by Yang et al.,226 as porous NR bundles by Niu et al.,227 as
nanosheets on a Ti foil substrate by Pu et al.,228 as self-
supported mesoporous NRs by Zhu et al.,229 as surface-oxidized
NRs by Chang et al.,230 again as NRs by Huang et al.,231 as
nanoporous NWs by Gu et al.,232 with a mixed morphology by
Jiang et al.233 and as CoOOH-covered CoP NPs by Ryu et
al.234 Apart from various morphologies, as expected CoP was
composited with carbonaceous materials such as CNTs by Liu
et al.235 and with GO by Ma et al.236 via hydrothermal
deposition of CoP on GO. One other important study was
reported by Hou et al.,237 who decorated the CNTs with
ultrafine CoP NPs and applied them as a highly active
bifunctional water splitting catalyst. Beyond this, an interesting
report on CoP@C core−shell nanostructures was first made by
Wang’s group, who applied them to HER electrocatalysis.238
Like the FeP case, CoP was also grown on CC by Li et al.239
through the two-step universal process of growing metal
phosphides on CC.
The phosphides of Ni are quite different from those of Fe
and Co. Unlike the latter, the phosphides of Ni have been
reported beyond the mono- and dimetallic centers. The nickel
phosphides reported to date are NiP, Ni2P, Ni5P4, Ni12P5, and
NiP2. The P content and its direct influence on the catalytic
performance in the HER is well-explained in the very recent
review of metal phosphide synthesis for HER applications by
Shi and Zhang.8 Moreover, the evolution of nickel phosphides
with varying P content led Kucernak and Sundaram240 to make
a linear relationship between the P content and the catalytic
activity of the metal phosphide toward the HER in acidic
media. As observed with Fe and Co, the nickel phosphide with
high P content (NiP) was found to be a better HER catalyst
than the others. However, such a direct correlation between the
P content and the OER activity of metal phosphides cannot be
made because the mechanism of the OER is much more
complicated than that of the HER. Syntheses of nickel
phosphides were also done by any one of the three known
methods of phosphidization as explained for Co and Fe
phosphides. Nickel phosphides with various P contents were
obtained simply by changing the molar ratio of the metal ion
precursor to the source of P, as was done by Kucernak and
Sundaram.240 Among the known nickel phosphides, Ni2P is the
most frequently reported one with various morphologies such
as metallic nanosheets by Li and co-workers,241 urchinlike
crystals on Ni foam by You and co-workers,242 nanoaggregates
by Li and co-workers,243 W-doped Ni2P microspheres by Jin
and co-workers,111 nanosheets of Ni foam by Shi and co-
workers,244 monodispersed NCs with different phases by Pan
and co-workers,147 nanoflakes (NFs) on graphene/Ni foam
hybrid electrode for the HER from pH 0 to 14 by Han and co-
workers,245 and NRs on Ni foam by Wang and co-workers.246
The second most reported nickel phosphide is NiP. NiP has
been reported by Yu et al.247 as carbon-coated porous
nanoplates that were applied in the OER, and Wang and co-
workers reported the one-step formation of NiP nanosheet
arrays on Ni foam for efficient HER in acidic electrolyte.248
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Review
Very recently, Zhuo et al.249 reported the effect of Se doping
onto the NCs of NiP and NiP2 on their HER activities. As an
interesting advancement in the nickel phosphide research, Jiang
and co-workers reported the exceptional HER performance of
NiP2 under both acidic and alkaline conditions.250 The higher P
content in NiP2 fetches an additional corrosion resistance under
harsh alkaline conditions and improves the HER performance
of the same. Similarly, the Ni5P4 NCs were found to be highly
stable while catalyzing the HER under both acidic and alkaline
conditions because of the increased P content, as reported by
Laursen and co-workers.251 As a step ahead and above, the
same Ni5P4 was later applied to full water splitting by
Ledendecker and co-workers because it holds better stability
in alkali than other phosphides of Ni.252 Huang and co-workers
showed the catalytic and photocatalytic HER performance of
Ni12P5 NPs.253
The methodologies and materials applied to the synthesis of
the phosphides of Fe, Co, and Ni are summarized in Table 4.
Beyond the monometallic phosphides, studies of phosphides
of mixed metals and their electrocatalytic performance toward
water splitting have recently also started to appear in the
literature. The first such mixed metallic phosphide of Ni and
Co was reported by Feng and co-workers, who prepared quasi-
hollow Ni−Co−P nanocubes and applied them to the HER in
alkaline solution.254 A little later, a ternary array of Ni−Co−P
nanosheets was synthesized by Li and co-workers, who applied
it to total water splitting under alkaline conditions.255 The
advantage of making such bimetallic phosphides is that it helps
to achieve better durability performance during both the HER
and OER as reported by Li et al.255
Having briefly discussed the synthetic strategies for the
sulfides, selenides, and phosphides of Fe, Co, and Ni, we can
come to the conclusion that there is still room to improve the
synthetic routes of these sulfides, selenides, and phosphides to
reduce the associated experimental, environmental, and health
hazards by minimizing the utilization of more toxic precursors,
avoiding high-temperature reactions and explosive reaction
conditions, and minimizing the waste from solution-based
syntheses. We have also seen that the phosphides of Fe, Co,
and Ni have been found to be better catalysts than the sulfides
and selenides of the same. Now it is time to find simplified,
easier, one-step, quick synthetic strategies to make the efficient
metal phosphides affordable for industrial-level large-scale H2
production more conveniently. Beyond the extensive contribu-
tions made by Sun and his group members to this particular
field of electrocatalysis of water splitting using sulfides,
selenides, and phosphides of Fe, Co, and Ni, they have newly
reported two other catalysts, namely, a Ni−Mo hollow nanorod
array for total water splitting256 and amorphous NiB alloy NPs
grown on Ni foam for total water splitting as well.257 These
reports have basically made us aware that there is still room to
improve the catalytic efficiencies of these catalysts. From the
above discussion, it is quite obvious to expect a review summary
on Co-catalyst-based materials for the electrocatalysis of water
splitting from Sun and his group members, and the same has
appeared very recently in the literature.258 This particular
review nicely corroborates the activity trends of various Co
catalysts such as its oxides, sulfides, selenides, and phosphides
for both the HER and OER in acidic, basic, and neutral
environments. However, it should be noted here that Sun’s
review is centered around only the Co-based catalysts and does
not cover Ni- and Fe-based ones completely. This has been
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ACS Catal. 2016, 6, 8069−8097
 Table 4. Methodologies and Precursors Used in the Synthesis of Metal (Fe, Co, and Ni) Phosphides
s. no. material and morphology metal precursor source of phosphorus method and reaction conditions ref
1 iron phosphide nanotubes Fe(NO3)3·9H2O NaH2PO2 heated at 300 °C for 30 min under Ar flow 208
2 FeP nanorods@CP FeCl3·6H2O red phosphorus phosphorization treatment in P vapor at 500 °C for 209
ACS Catalysis

30 min
3 FeP nanosheets Fe18S25−TETAH trioctylphosphine anion exchange reaction by diffusion at >300 °C 210
4 FeP nanorods FeCl2 NaH2PO2 heated at 350 °C for 2 h under Ar flow 211
5 FeP nanorod arrays FeCl3·6H2O NaH2PO2 heated at 300 °C for 2 h under Ar flow 212
6 FeP nanoparticle film@CC Fe(NO3)3·9H2O NaH2PO2 heated at 300 °C for 2 h under Ar flow 213
7 rugae-like FeP nanocrystal@CC FeSO4 NaH2PO2 phosphidation at 500 °C 214
8 3D FeP nanowires FeCl3 NaH2PO2 heated at 300 °C for 2 h in a static Ar atmosphere 215
9 FeP@NCNT FeCl3·6H2O NaH2PO2 Calcined at 350 °C under N2 flow for 2 h 216
10 surface-oxidized Co2P nanoneedles CoCl2·6H2O Ca3P2 solvothermal method at 230 °C for 30 min 217
11 3D CoP nanowires@CC Co(NO3)2·6H2O NaH2PO2 heated at 300 °C for 1 h in a static Ar atmosphere 218
12 CoP nanowires Co(Ac)2 NaH2PO2 heated at 300 °C for 2 h 219
13 CoP nanotubes CoCl2·6H2O NaH2PO2 heated at 300 °C for 2 h in a static Ar atmosphere 220
14 CoP@Ti mesh Co(NO3)2·6H2O NaH2PO2 heated at 300 °C for 2 h in a static Ar atmosphere 221
15 CoP nanoparticles@CC CoCl2·6H2O NaH2PO2 heated at 300 °C for 2 h in Ar flow 222
17 CoP nanoparticles Co2(CO)8 trioctylphosphine solvothermal method at 320 °C for 1 h 223
18 branched CoP nanostructures cobalt(II) acetylacetonate trioctylphosphine and trioctylphosphine heated at 120 °C for 1 h under vacuum 224
oxide
19 CoP hollow polyhedra Co(NO3)2·6H2O NaH2PO2·H2O heated at 250 °C for 2 h in a static N2 atmosphere 225
20 urchinlike CoP nanocrystals Co(NO3)2·6H2O NaH2PO2 heated at 300 °C for 150 min in a static N2 226

8084
atmosphere
21 CoP nanorod arrays@Ti Co(NO3)2·6H2O NaH2PO2 heated at 300 °C for 2 h in a static Ar atmosphere 227
22 CoP nanosheet arrays@Ti plate Co(NO3)2·6H2O NaH2PO2 heated at 300 °C for 1 h in a static Ar atmosphere 228
23 CoP nanorod arrays@Ni foam CoCl2 NaH2PO2 electrodeposition 229
24 surface-oxidized CoP nanorods CoCl2·6H2O NaH2PO2·H2O heated at 300 °C for 2 h in a static N2 atmosphere 230
25 Co2P nanorods Co(Ac)2·4H2O trioctylphosphine solvothermal method at 120 °C for 30 min in N2 231
flow
27 CoP nanoparticles@C cobalt(II) acetylacetonate trioctylphosphine solvothermal method at 300 °C 234
28 CNTs decorated with CoP Co(Ac)2 NaH2PO2 heated at 300 °C for 2 h 235
nanocrystals
29 CoP nanoparticles@RGO Co(Ac)2·4H2O NaH2PO2 heated at 300 °C for 2 h 236
30 CoP nanoparticles@CNT Co(Ac)2 NaH2PO2 heated at 300 °C for 2 h in Ar flow 237
31 CoP@C core−shell nanocables cobalt(II) acetylacetonate triphenylphosphine heated in a sealed tube at 400 °C for 100 min 238
32 nickel phosphide NiSO4 NaH2PO2 electrodeposition 240
33 Ni2P nanosheets NiCl2·6H2O NaH2PO2 heated at 380 °C for 15 h 241
34 urchinlike Ni2P@Ni foam Ni foam NaH2PO2·H2O heated at 400 °C for 2 h in a static Ar atmosphere 242
35 NixPy Ni(NO3)2·6H2O NaH2PO2·H2O heated at 275−475 °C for 2 h in a static Ar 243
atmosphere
36 Ni2P nanosheets@Ni foam Ni foam trioctylphosphine Solvothermal method at 320 °C for 2 h 244
37 Ni2P nanoflakes@graphene/Ni foam Ni foam KH2PO4 Chemical vapor deposition process 245
38 Ni5P4−Ni2P nanosheet array Ni foam red phosphorus heated at 500 °C for 6 h in N2 flow 246
39 carbon-coated nickel phosphide potassium tetracyanidonickelate(II) and NiCl2·xH2O NaH2PO2 heated at 300 °C for 2 h in a static Ar atmosphere 247
nanoplates
Review

40 Ni foam red phosphorus 248

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Ni2P nanorods@Ni foam hydrothermal method at 200 °C for 48 h
ACS Catalysis Review

rectified in the present review, which includes updated

249
250
251
252
253

111
144
ref literature reports.

solvothermal method at 390 °C for for 30 min under

heated at 500 °C for 30 min in Ar flow atmosphere
heated at 300 °C for 1 h in a static Ar atmosphere
8. APPLICATIONS OF GROUP VIII 3D METAL (FE, CO,
AND NI) SULFIDE, SELENIDE, AND PHOSPHIDE
heated at 550 °C for 1 h in inert atmosphere

solvothermal method at 80−90 °C for 2 h

NANOSTRUCTURES IN WATER SPLITTING
method and reaction conditions

solvothermal method at 390 °C for 1·5 h

heated at 300 °C for 2 h under Ar flow

Before the discussion of the applications of sulfide, selenide,
and phosphide nanostructures of Fe, Co, and Ni, it would be
useful to elaborate the most common problems that are faced
during the application of nanostructured catalysts in water
splitting and some recent trends of fabricating electrodes using
these nanostructured catalysts for water splitting.
8.1. Common Problems Encountered with Nano-
structured Catalysts in Water Splitting. One of the
major problems encountered with nanostructured catalysts is
achieving reasonable stability without compromising the
N2

catalytic activity. The sources of stability failure can include

the binder used to tether the nanostructured catalysts to the
substrate/current collector, the pH at which electrolysis is
carried out, high surface energy of the nanomaterials, a decrease
source of phosphorus

in conductivity due to overoxidation of the catalyst (in the case

of the OER), and the effect of loading on the conductivity.
8.1.1. Binders Used To Tether the Nanostructured
trioctylphosphine oxide

Catalysts and Associated Demerits in Water Splitting. In

triphenylphosphine

general, the binder is chosen on the basis of the medium in

red phosphorus

red phosphorus

which the electrolysis is carried out. Since the most reactive

NaH2PO2

NaH2PO2

HER and OER catalysts are found to catalyze these

Na2PO2

electrochemical reactions at either extremely low pH (strongly

acidic) or extremely high pH (strongly alkaline), the most
obvious choice is to go with a binder that can offer excellent
FeCl3·6H2O, Fe(NO3)3·9H2O, CoCl2·6H2O, and Co(NO3)2·6H2O

proton transfer in acidic solutions and good hydroxide

conductivity in alkaline conditions. The common commercial
binder used for this purpose is Nafion, which is actually a
perfluorinated alkyl sulfonate ionomer that is available at
various concentrations ranging from 5% to 40% as a solution in
water or a methanol/propanol mixture. The combination of the
very high fluorine content in the carbon backbone and its high
metal precursor

hydrophobicity with the sufficiently high polarity and hydro-

philicity of the sulfonate functional group helps the protons to
get transferred from the aqueous solutions to the hydrophobic
electrode surfaces easily. As a consequence of these advantages,
Nafion has been widely used as a binder for the HER and OER
under acidic conditions. However, when the electrolysis is
performed under alkaline conditions, this proton transfer
Ni(NO3)2·6H2O
Ni(NO3)2·6H2O

ionomer fails to deliver the same efficiency as it did in the

Ni(acac)2·xH2O

Ni(Ac)2·4H2O

acidic medium. As a result, the resistance of the catalyst−

electrolyte interface is considerably increased, which leads to a
Ni foil

NiSO4

drastic degradation in the catalytic activity and affects the

stability of the nanostructured-catalyst-modified electrodes.
However, the same 5 wt % Nafion solution with additives
such as propyl alcohol or isopropyl alcohol in water in the
volume ratio of 0.5:2.0:7.5 is being used as a binder for many
material and morphology

nanostructured catalysts in alkaline water electrolysis. In this

W-doped NixP microspheres
FexCo1−xP nanowire array

case, the hydroxide conductivity is believed to occur via the

water channels available on the thin film formed while drying
nanocrystalline Ni5P4

Ni12P5 nanoparticles
Ni2P NP films@Ti

this binder solution with the desired catalyst on the substrate

Table 4. continued

electrode surface. Although this modification makes the Nafion

Se-doped NiP2

Ni5P4 Films

applicable in alkaline water electrolysis, the serious problem

associated with it is the hydration of the thin films formed
during drying upon prolonged exposure to strongly acidic and
alkaline conditions. This results in a gradual increase in the
s. no.

thickness of the catalyst layer on the substrate electrode, leading

41
42
43
44
45

46
47

to increased catalyst resistance, which in turn decreases the

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ACS Catalysis
catalytic activity and affects stability of the catalyst directly. To
overcome this problem, attention has now been diverted
toward some anion exchange ionomers made up of some
indole-based polymers and ionic liquids. However, these are
quite expensive, and the efforts that have been made to reduce
the overall expenses associated with water electrolysis by
making these nanostructured catalysts would become mean-
ingless if we must rely on a costly anion exchange ionomer to
attain reasonable stability with our catalysts. Other than these, it
is quite common to see reports with some other binders such as
poly(tetrafluoroethylene) (PTFE), poly(vinyl pyrrolidine)
(PVP), poly(vinyl alcohol) (PVA), N-methylpyrrolidone
(NMP), and dimethylformamide (DMF). However, except
for DMF the other binders listed above are nonconductive and
require a conductive additive such as carbon black in equal
proportion to the catalyst material. This could lead to wrong
interpretation in assessing the catalytic activity of the desired
catalyst by either partially masking the active sites in the catalyst
or additionally contributing to the overall activity. Though
DMF does not require any such conductive additive, the
stability of the catalyst-modified surface is poor compared with
other binders, particularly when it is subjected to the
accelerated degradation test and long-term galvanostatic or
potentiostatic electrolysis. Very recently, in this concern of
overcoming the problems associated with the binders, we have
exploited the use of DNA molecular self-assemblies, which are
cheaper than these anion and proton exchange ionomers, by
anchoring of the ultrasmall Pt NPs for the HER under acidic
conditions and IrO2 NPs for the OER under alkaline
conditions.17,259 These Pt NP-anchored DNA molecular self-
assemblies have shown extreme stability and increased catalytic
performance over a commercial Pt/C catalyst under identical
experimental conditions.17 The mechanism of binding with
DNA molecular self-assemblies is mainly dependent on the
electrostatic interactions between the DNA molecules and
various charged and polarized entities during polarization of the
electrode in both the anodic and cathodic directions; apart from
these, the catalyst resistance is not increased by the conductivity
associated with the DNA as a consequence of free electron
movements by resonance among the purine and pyrimidine
bases in their backboned. This study now has opened up
pathways utilizing other biomolecules with charged and
polarized entities, such as amino acids, peptides, proteins, and
polysaccharides, as binders for other materials in the future.
8.1.2. pH of the Medium of Water Electrolysis. The
medium of water electrolysis plays a crucial role in water
electrolysis, as elaborated earlier under various categories. Here
the effect of the pH of the water electrolysis solution on the
stability of the nanostructured catalyst is discussed. We have
seen that at under strongly acidic or alkaline conditions, non-
noble-metal catalysts such as the ones considered in this review
are highly prone to corrosion, which affects the stability
directly. To overcome this issue, many catalysts have now been
designed to be active at neutral pH. In this regard, the metal
phosphides, sulfides, and selenides have more advantages than
the metals, metal oxides, and metal hydroxides, as the oxides of
S, Se, and P are highly resistive toward corrosion. Hence, these
materials find very limited stability problems due to the
solution pH of water electrolysis.
8.1.3. High Surface Energy and Overoxidation of the
Catalyst Surface. These are two other serious problems that
reduce the stability of catalysts for water electrolysis. It is
known that the nanomaterials have higher surface energies than
8086
Review
their counterparts, and when they are exposed to such a high
applied electric potential field, there is a fair chance of
agglomeration with nearby particles. This will ultimately reduce
the overall number of available active sites compared with the
initial stage of the catalytic process. Besides agglomeration,
there are chances for overoxidation of the nanomaterial surface
due to these higher surface energies in cases where the
agglomeration of nearby particles is restricted by high dilution
of the catalyst concentration. As a consequence of over-
oxidation of the catalyst surface, the resistance associated with
the catalyst will also increase, which will ultimately result in
reduced catalytic activity. Efforts should be made to avoid all of
the above problems associated with nanostructured catalysts by
optimizing the experimental conditions with care.
8.2. Recent Trends in Electrode Fabrication with
Nanostructured Catalysts for Prolonged Water Electrol-
ysis. All of the stability problems elaborated in the previous
section can be overcome by simple and brilliant electrode
fabrication methods. The most stable nanostructured-catalyst-
modified interfaces that have recently been reported make use
of one of the following two methods: electrochemical
deposition or hydrothermal/solvothermal growth of nano-
structured catalysts on the desired substrate materials.
8.2.1. Electrochemical-Deposition-Assisted Improvement
in the Stability of Nanostructured Catalysts. Obviously, it is
more advantageous to support the catalysts on the desired
current collectors by electrochemical deposition than to
prepare the same by other methods and depend on suitable
binders. However, this method is not always suitable for all
kinds of materials. It is most reported for metal-, metal oxide-,
and metal hydroxide-based nanostructures. Additionally, there
are reports for sulfides and selenides too. The common
substrates employed are metal foils such as Ti and Cu, metals
such as Ni in the form of Ni mesh and Ni foam, indium-doped
tin oxide (ITO), fluorine-doped tin oxide (FTO), carbon fiber
paper, and carbon cloth. Depending on the material, any of the
above substrates can be used for electrodeposition. For
example, in photoelectrocatalytic water splitting, ITO and
FTO are the most obvious choices of substrates. The major
advantages of this method are the ability to monitor the
quantity of deposited catalyst and the control over the catalyst
film thickness. The disadvantages are the inefficiency in
producing nanomaterials with various other morphologies and
the requirement for sophisticated instruments such as electro-
chemical workstations.
8.2.2. Hydrothermal- or Solvothermal-Growth-Assisted
Improvement in the Stability of Nanostructured Catalysts.
This method has recently been explored by materials scientists,
and it is suitable for almost all sort of materials. In this method,
the substrate on which the catalysts must be grown is taken
along in the hydrothermal/solvothermal vessel after necessary
pretreatments. The most common substrates are Ti foil, Ni
foam, carbon fiber paper, and carbon cloth. These methods
offer the advantage of preparing catalysts with various
morphologies of a hierarchical nature, which enables some
special studies such as morphology- and shape-selective
catalytic studies. The main disadvantage of this method is the
lack of control over the quantity of the catalyst grown on the
desired substrate. Both methods are efficient in fabricating
highly stable 3D catalyst electrodes and should be chosen
according to the material of interest.
8.3. Sulfides of Fe, Co, and Ni in Water Splitting.
Having discussed the methods of evaluating an electrocatalyst
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ACS Catalysis
for water splitting and the synthesis of the catalyst materials, we
now proceed to a discussion of benchmarking all of the
reported sulfides of Fe, Co, and Ni with respect to the
overpotential at 10 mA/cm2 (η10) and Tafel slope values under
two categories, viz., metal sulfides for the HER and metal
sulfides for the OER. The activity parameters for total water
splitting catalysts are split up and included along with other
catalysts used for the HER and OER. The same trend will be
followed for the selenides and phosphides too. As far as total
water splitting is concerned, no Fe-based sulfides have been
reported to date. There are only few reports on total water
splitting by these metal (Fe, Co, and Ni) sulfides. The report by
Wang et al.168 on CoS supported on CTs that in turn were
grown on CC is the only one on the total water splitting activity
of a Co-based sulfide. However, the literature says that the Ni-
based sulfides are better bifunctional catalysts than the Fe- and
Co-based ones. NiS microspheres grown on Ni foam and Ni3S2
nanosheets grown on Ni foam are good in catalyzing both the
HER and OER under alkaline conditions.171 However, a
significant advancement in the bifunctional activity of these
sulfides is achieved when they are present as bimetallic sulfides.
The electrodeposited Ni−Co−S reported by Liu et al.185 and
the Ni-promoted formation of CoS2 NW arrays on CC as
reported by Fang et al.186 are examples of this kind.
8.3.1. Activity Trends of Metal (Fe, Co, Ni) Sulfides in the
Electrocatalytic HER. The available reports on the sulfides of
Fe, Co, and Ni clearly reveals that they have been employed
more for the HER than for the OER and total water splitting. It
has been highlighted in the synthesis section that to date there
have been no reports on Fe-based sulfides except the one on
FeS for the HER by Di Giovanni et al.162 and the one on pyrite-
type FeS2 for the HER by Faber et al.164 On the other hand,
literature reports on Co-based sulfides are more abundant than
for both Fe and Ni. Interestingly, almost 80% of the available
reports on Co-based sulfides were studied for the HER, and the
reports for the OER and total water splitting are limited.
Among the various Co-based sulfides such as CoS, CoS2, Co3S4,
and Co9S8, CoS and pyrite-type CoS2 are the ones frequently
reported for the HER. In the case of Ni-based sulfides, there are
only two reports for the HER, namely, the report on NiS2 by
Faber et al.164 and the report on Ni3S2 by Tang et al.187 Apart
from these, there are reports on the HER activities of bimetallic
sulfides such as Co−Fe−S, Co−Ni−S, Fe−Ni−S, and Ni−Co−
S. To have a comparative view of the catalytic activities of these
sulfides toward the HER, they have been benchmarked with
respect to their overpotential at 10 mA/cm2 and Tafel slope, as
shown in Figure 9. More information on the electrochemical
conditions under which these data were acquired and others are
provided in Table 5. From Figure 9 it is clear that the FeNiS
catalyst reported by Long and co-workers is the best catalyst
with the lowest HER η10 of 105 mV. In Table 5, other catalysts
are listed in order of increasing η10.
Since there had been a serious discussion of the selection of
activity parameters to evaluate an electrocatalyst’s efficiency for
water splitting, it is fruitful to arrive at a conclusion whether the
use of η10 with the Tafel slope as the primary activity parameter
is good for evaluating catalysts. Figure 9 clearly reveals that the
overpotential has nothing to do with the kinetics of the
electrocatalytic water splitting process, as we can see that some
catalysts with low η10 have larger Tafel slopes than some
catalysts with relatively larger η10, such as CoS|P/CNT reported
by Liu and co-workers,260 which showed an overpotential of
480 mV at 10 mA/cm2 with a Tafel slope of 55 mV/dec. This
8087
Review
Figure 9. Benchmarking the metal (Fe, Co, Ni) sulfides with respect
to the HER overpotential at 10 mA/cm2 and the corresponding trend
in the Tafel slopes.
primarily indicates that the thermodynamic activity parameter
(i.e., the overpotential) does not affect or only slightly affects
the kinetic activity parameter (i.e., the Tafel slope). Similar
trends are also observed with selenide- and phosphide-based
catalysts for both the HER and OER, as discussed in the
subsequent sections.
8.3.2. Activity Trends of Metal (Fe, Co, Ni) Sulfides in the
Electrocatalytic OER. Although the sulfides of Fe, Co, and Ni
have been devoted more toward the HER, there are also reports
available on the OER catalytic performance of these sulfides,
particularly the sulfides of Co and Ni. There is no data on the
OER and total water splitting activities of Fe-based sulfides
alone. However, Fe has been reported by Shen and co-
workers163 as a bimetallic sulfide with Co as Co−Fe−S on N-
doped mesoporous carbon for the OER along with the ORR.
The story with Co-based sulfides is different from that of Fe-
based sulfides. Though Co-based sulfides have also been much
devoted to the HER, there are reports on their OER and total
water splitting activities. Another thing to be noticed here is
that wherever a Co-based sulfide is applied to the OER or total
water splitting, it is always applied with a substrate material
such as a carbon nanostructure or Ti foil. Among the reported
catalysts are Co3S4 on N-doped CNT by Wang et al.,173 CoS
nanosheets grown on Ti by Liu et al.,262 and CoS2 grown on N-
and S-codoped GO by Ganesan et al.172 In the case of Ni, there
is a lone report on Ni3S2 nanosheets grown on Ni foam that
showed a low overpotential for the OER under alkaline
conditions. Other than these, bimetallic NiCo2S4@graphene
has been reported by Liu et al.184 for the OER and ORR under
alkaline conditions. As for the HER, as a comparative measure
the plots of η10 and the Tafel slope are shown in Figure 10, and
the data are listed in Table 6.
As we have seen for the HER, the activity trends of these
metal sulfide catalysts benchmarked with respect to η10 and the
Tafel slope follow an irregular trend in terms of kinetics. This
again implies the same conclusion that the Tafel slope
(kinetics) has no direct relation to the overpotential
(thermodynamics) of a water splitting catalyst.
8.4. Selenides of Fe, Co, and Ni in Water Splitting. The
irregularities seen in the trends of selenides of Fe, Co, and Ni
are more vigorous for both the OER and HER than those
observed with the sulfides. This indicates the strong influence
of a ligand with an ionic radius comparable to that of the central
metal atom, which belongs to the 3d series of the periodic table
with 4s shells. However, the best correlations among these
metal selenides are given for a comparative evaluation of the
HER and OER activity trends via the benchmarking plots of η10
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ACS Catalysis Review

Table 5. Benchmarking the Metal (Fe, Co, Ni) Sulfides with Respect to the HER Overpotential at 10 mA/cm2 (η10)
s. no. catalyst electrolyte η10 (mV) Tafel slope (mV/dec)a ref
1 A-FeNiS 0.5 M H2SO4 105 40 190
2 B-FeNiS 0.5 M H2SO4 117 48 190
3 CoS2 0.5 M H2SO4 128 52 192
4 Ni2.3%CoS2/CC 1 M KOH 136 106 235
5 Co3S4/NCNTs 0.5 M H2SO4 140 70 189
6 NiCoS/CC NSs 1 M KOH 140 96 177
7 CoS2 NS/RGO/CNT 0.5 M H2SO4 142 51 171
8 (Fe0.48Co0.52)S2 0.5 M H2SO4 143 47.5 164
9 NiS/Ni Foam 1 M KOH 150 83 181
10 Ni2.3%CoS2/CC 1 M KOH 150 106 186
11 Fe0.9Co0.1S2/CNT 0.5 M H2SO4 160 46 190
12 Co3S4 0.5 M H2SO4 160 79 173
13 Co9S8−NixSy/NiF 1 M KOH 163 88 188
14 (Co0.59Ni0.41)S2 0.5 M H2SO4 170 50.4 170
15 CoS2/Ti (pH 0.3) 0.5 M H2SO4 190 72 170
16 NiCo2S4 NA/CC 1 M KOH ∼190 141 187
17 Ni3S2@Ni 1 M KOH 195 107 178
18 Fe0.07Ni0.91S2 0.5 M H2SO4 196 58.7 164
19 NiMoS/C 1:1 pH 7 200 85.3 191
20 Zn0.76Co0.24S/CoS on Ti mesh 1 M KOH ∼200 164 175
21 B-NiS 0.5 M H2SO4 202 − 190
22 FeS2 0.5 M H2SO4 217 56.4 164
23 NiS2 0.5 M H2SO4 230 48.8 164
24 NixSy/NiF 1 M KOH 230 87 188
25 MW-CoS (nanoprism) 0.5 M H2SO4 230 76 175
26 ST-CoS (nanoprism) 0.5 M H2SO4 240 90 175
27 NiS on CC pH 7 243 69 179
28 CoS2/Ti (pH 13.37) 0.5 M H2SO4 244 133 183
29 Fe0.1NiS2 NA/Ti 1 M KOH ∼250 108 180
30 Ni3S2−Ni 1 M KOH 270 141 178
31 Co9S8/C phosphate buffer 280 − 174
32 CoS2 NS/RGO 0.5 M H2SO4 280 82 171
33 3D G/CoSx 1 M PBS 330 93 176
34 Co9S8 (all pH) phosphate buffer 340 − 174
35 FeS (pH 7) 0.1 M phosphate buffer 350 150 162
36 Co9S8-700 phosphate buffer 370 − 174
37 CoS|P/CNT 0.5 M H2SO4 480 55 260
a
Dashes indicate that the corresponding data are not available in the respective reports cited here.

selenides for the HER. However, there are some bifunctional

Figure 10. Benchmarking the metal (Fe, Co, Ni) sulfides with respect
to the OER overpotential at 10 mA/cm2 and the corresponding trend
in the Tafel slopes.
and Tafel slope in Figures 11 and 12 and the data in Tables 7
and 8, respectively.
8.4.1. Activity Trends of Metal (Fe, Co, Ni) Selenides in the
Electrocatalytic HER. As we highlighted in the synthetic
methodologies part, there are no reports on Ni- and Fe-based
8088
water splitting bi- and trimetallic selenides. On the other hand,
the most reported Co-based selenide, CoSe2 with various
morphologies and substrate materials, has itself shown different
trends in the HER catalytic performance. The same can be seen
when they are benchmarked with respect to η10 and Tafel slope,
as shown in Figure 11.
As all of them are the same material, it is hard to make a
conclusion about the trend of the HER activity of 3d group VIII
metal (Fe, Co, and Ni) selenides. However, the Co0.13Ni0.87Se2/
Ti is the one with the lowest overpotential of 64 mV at 10 mA/
cm2 for the HER among all other selenide-based HER catalysts,
as reported by Liu and co-workers.262 The selenides of the
group VIII 3d metals that have been reported to date are listed
in Table 7 in increasing order of η10 along with the
experimental conditions under which the evaluations were
made. As observed with the sulfides, the selenides show similar
trends in the correlation between the thermodynamic activity
parameter (the overpotential) and the kinetic activity parameter
(the Tafel slope). This once again emphasizes the independ-
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Table 6. Benchmarking the Metal (Fe, Co, Ni) Sulfides with Respect to the OER Overpotential at 10 mA/cm2 (η10)
s. no. catalyst electrolyte η10 (mV) Tafel slope (mV/dec)a ref
1 Fe0.1NiS2 NA/Ti 1 M KOH ∼205 43 180
2 Ni2.3%CoS2/CC 1 M KOH 297 117 262
3 NiS/Ni foam 1 M KOH 300 89 179
4 Zn0.76Co0.24S/CoS on Ti mesh 1 M KOH ∼300 79 175
5 Ni2.3%CoS2/CC 1 M KOH ∼300 119 186
6 Ni3S2@Ni 0.1 M KOH 330 163 178
7 NiCoS/CC NSs 1 M KOH 330 109 177
8 NiCo2S4 NA/CC 1 M KOH 340 89 187
9 NiCo2S4@N/S-RGO 0.1 M KOH 355 − 184
10 CoS2/N−S GO 1 M KOH 370 − 172
11 ALD NiSx 1 M KOH 372 41 182
12 Co3S4 0.1 M KOH 375 − 184
13 Ni3S2−Ni 0.1 M KOH 410 330 178
14 CP/CNT/CoS 1 M KOH 450 − 168
15 Ni3S4 0.1 M KOH 555 − 184
a
Dashes indicate that the corresponding data are not available in the respective reports cited here.

expected, as similar irregular trend in the Tafel slopes is seen

Figure 11. Benchmarking the metal (Fe, Co, Ni) selenides with
respect to the HER overpotential at 10 mA/cm 2 and the
corresponding trend in the Tafel slopes.
Figure 12. Benchmarking the metal (Fe, Co, Ni) selenides with
respect to the OER overpotential at 10 mA/cm 2 and the
corresponding trend in the Tafel slopes.
ence of the overpotential from the nature of the HER kinetics
and vice versa.
8.4.2. Activity Trends of Metal (Fe, Co, Ni) Selenides in the
Electrocatalytic OER. As with the HER catalysis, the OER
catalysis by these metal selenides is mainly occupied by CoSe2
and other Co-based sulfides. Some of the significant works
include the CoSe oxohalides reported by Rabbani et al.,263 the
coral-like 3D CoSe2 crystals reported by Liao et al.,202 and the
CeO2-doped CoSe2 reported by Zheng et al.204 For NiSe2 there
is a report by Tang et al.193 As we did for the HER,
benchmarking plots of the activity parameters (i.e., η10 and the
Tafel slope) of these selenides are provided in Figure 12, and
other relevant data on the same are included in Table 8. As
8089
when these selenide-based catalysts are queued according to
increasing overpotential. This too emphasizes again the
independence of the overpotential from the nature of the
HER kinetics and vice versa.
8.5. The Phosphides of Fe, Co, and Ni in Water
Splitting. Similar to the sulfides and selenides, the Activity
trends of the phosphides of Fe, Co, and Ni are comparative
evaluated by plotting the overpotential against the phosphide
catalysts in the increasing overpotential order as shown in
Figure 13 and Figure 14 and the experimental conditions under
which the evaluation were made are listed in Table 9 and Table
10 for HER and OER respectively.
8.5.1. Activity Trends of Metal (Fe, Co, Ni) Phosphides in
the Electrocatalytic HER. Unlike the selenides, the phosphides
of Fe, Co, and Ni have been equally reported for the HER.
Where the HER is concerned, the maximum number of reports
(∼40) have been published using the phosphides. The sulfides
come second, and the number of selenide-based HER catalysts
is minor compared with the sulfides and phosphides. The plots
of η10 and the Tafel slope for the metal phosphides for the HER
are shown in Figure 13, and Table 9 provides the experimental
details under which the measurements of the HER activities of
these phosphide catalysts were made. From Figure 13 and
Table 9 an interesting observation can be made: lower HER
overpotentials at 10 mA/cm2 were shown predominantly by the
Fe-based phosphides compared with the Co- and Ni-based
phosphides. This is in sharp contrast to the HER activity trends
of the sulfides and selenides of Fe, Co, and Ni. For the sulfides
and selenides, either Co or Ni or a mixture of Co and Ni
occupied the top position in the table of HER and OER activity
trends, in accordance with the activity trends of 3d metal oxides
and hydroxides predicted by Subbaraman and co-workers
earlier.150
However, there are some specific phosphides of Ni and Co
with specific P contents, such as Ni5P4, NiP2, and CoP, that
showed good HER performance comparable to that of the Fe-
based phosphides. As observed with the sulfides and selenides,
the phosphide catalysts ranked by the overpotential at 10 mA/
cm2 show an irregular trend in the Tafel slopes, as catalysts with
low overpotentials were found to show higher Tafel slopes and
vice versa. This indicates to us that the phosphides are not
exceptions and that they too have independent thermody-
DOI: 10.1021/acscatal.6b02479
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ACS Catalysis Review

Table 7. Benchmarking the Metal (Fe, Co, Ni) Selenides with Respect to the HER Overpotential at 10 mA/cm2 (η10)
s. no. catalyst electrolyte η10 (mV) Tafel slope (mV/dec) ref
1 Co0.13Ni0.87Se2/Ti 1 M KOH 64 63 262
2 MoS2/CoSe2 0.5 M H2SO4 68 36 105
3 electrodeposited Ni3Se2 1 M KOH 70 82 195
4 NiSe/NF 1 M KOH 96 120 193
5 Ni3Se2/CF 1 M KOH 100 98 196
6 Ni/NiO/CoSe2 0.5 M H2SO4 100 39 197
7 NiPSe (1.93:0.07) 0.5 M H2SO4 100 43 249
8 CoSe2−NW/CC 0.5 M H2SO4 130 32 205
9 CoSe2/CP 0.5 M H2SO4 137 40 198
10 NiPSe(0.09:1.91) 0.5 M H2SO4 170 44 249
11 NiSe2 0.5 M H2SO4 175 33 249
12 CoSe2-MP/CC 0.5 M H2SO4 193 50 205
13 EG/CoSe-NiFe-LDH 1 M KOH 260 −a 121
14 Co0.13Ni0.87Se2/Ti 1 M KOH 270 94 262
15 CoPSe/MWCNT/GCE 0.5 M H2SO4 370 46 117
a
Dash indicates that the corresponding data are not available in the respective reports cited here.

Table 8. Benchmarking the Metal (Fe, Co, Ni) Selenides with Respect to the OER Overpotential at 10 mA/cm2 (η10)
s. no. catalyst electrolyte η10 (mV) Tafel slope (mV/dec) ref
1 EG/CoSe-NiFe-LDH 1 M KOH 250 57 121
2 coral-like CoSe2 1 M KOH 290 40 172
3 electrodeposited Ni3Se2 1 M KOH 290 82 195
4 CoSe2/Ti mesh 1 M KOH 292 69 199
5 Ni3Se2/CF 1 M KOH ∼300 80 196
6 CeO2/CoSe2 1 M KOH 310 44 204
7 CoSe2 NPs 1 M KOH 350 49 172
8 NiSe/NF 1 M KOH 400 −a 193
9 Mn3O4−CoSe2 0.1 M KOH 450 49 185
a
Dash indicates that the corresponding data are not available in the respective reports cited here.

namics and kinetics of water splitting. However, the shape of

Figure 13. Benchmarking the metal (Fe, Co, Ni) phosphides with
respect to the HER overpotential at 10 mA/cm 2 and the
corresponding trend in the Tafel slopes.
Figure 14. Benchmarking the metal (Fe, Co, Ni) phosphides with
respect to the OER overpotential at 10 mA/cm 2 and the
corresponding trend in the Tafel slopes.
8090
the Tafel slope line in Figure 13 is showing merely a linear
relation between the overpotential and the Tafel slope values,
unlike the sulfides and selenides.
8.5.2. Activity Trends of Metal (Fe, Co, Ni) Phosphides in
the Electrocatalytic OER. Application of phosphides of Fe, Co,
and Ni to the OER is new, and there are relatively few reports
compared with the number of reports available on the same for
HER applications. However, here we have made similar
comparative evaluation of the available reports on the metal
phosphides for OER applications via the benchmarking plots of
η10 and the Tafel slope shown in Figure 14 along with Table 10
carrying information on the experimental conditions under
which the results on the OER activities of these metal
phosphides were acquired. As expected, there is an irregular
trend in the Tafel slopes when these catalysts are queued in
increasing order of their overpotentials at 10 mA/cm2. Hence,
the same conclusion of the independence of the kinetics of an
electrocatalyst from the thermodynamics of the catalyst can be
drawn.
8.6. Activity Trends of Metal (Fe, Co, Ni) Phospho-
sulfides and Phosphoselenides in Electrocatalytic HER
and OER. Beyond the sulfides, selenides, and phosphides alone
as electrocatalysts, people have now moved forward in
combining the effects of two different ligands such as P and
S and P and Se together with a single metal among Fe, Co, and
Ni. The reports where such kinds of materials have been
employed for the HER, OER, and total water splitting to date
are summarized here. Pyrite-structured CoPS for the HER was
DOI: 10.1021/acscatal.6b02479
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ACS Catalysis Review

Table 9. Benchmarking the Metal (Fe, Co, Ni) Phosphides with Respect to the HER Overpotential at 10 mA/cm2 (η10)
s. no. catalyst electrolyte η10 (mV) Tafel slope (mV/dec)a ref
1 Ni5P4 0.5 M H2SO4 24 27 251
2 FeP/CC nanocrystal (300 °C) 0.5 M H2SO4 34 29.2 214
3 Fe0.5Co0.5P/CC 0.5 M H2SO4 39 30 222
4 NixPy 0.5 M H2SO4 40 46.1 213
5 CoP NPs/CC 0.5 M H2SO4 48 70 221
6 Ni5P4 1 M NaOH 50 14 251
7 CoP MNA 0.5 M H2SO4 54 51 229
8 Ni2P−G@NiF 0.5 M H2SO4 55 30 245
9 FeP NAS/CC 0.5 M H2SO4 58 45 212
10 nanoporous CoP pH 0−14 67 51 218
11 CoP/Ti mesh 1 M KOH 72 65 221
12 NiP2−NS/CC 0.5 M H2SO4 75 51 250
13 3D CoP NWs on Ti 0.5 M H2SO4 ∼80 65 222
14 CoP-NBAs/Ti 0.5 M H2SO4 90 40 227
15 CoP/NCNT 0.5 M H2SO4 92 49 236
16 CoP branched NS on Ti Foil 0.5 M H2SO4 98 − 224
17 Ni2P/Ni/NF H2 sat. 1 M KOH 98 72 242
18 Ni2P−G@NiF 1 M KOH 100 30 245
19 CoP NWs 0.5 M H2SO4 110 54 233
20 FeP/NCNT 0.5 M H2SO4 113 59 162
21 NiP2−NS/CC 1 M KOH 110 64 250
22 CoP@NPC 0.5 M H2SO4 120 69 115
23 Ni5P4−Ni2P NS 0.5 M H2SO4 120 79.1 246
24 CoP/CNT 0.5 M H2SO4 123 54 140
25 CoP/C 0.1 M KOH 130 − 234
26 CoP NTs 0.5 M H2SO4 130 60 220
27 Ni2P-NRs-Ni N2 sat. 0.5 M H2SO4 130 106.1 248
28 Fe2P/NGR 0.5 M H2SO4 138 − 211
29 NiCoP hollow NCs 1 M KOH 145 60.6 254
30 Co2P/NCNT 0.5 M H2SO4 148 62 236
31 Ni2P/NF H2 sat. 1 M KOH 150 93 242
32 CoP hollow polyhedra 0.5 M H2SO4 159 59 225
33 Ni2P−G@NiF 1 M KPi 160 40 245
34 CoP NSs 0.5 M H2SO4 164 61 233
35 CoP/CNT 0.5 M H2SO4 165 68 236
36 CoP 0.5 M H2SO4 168 46 226
37 CoP@C Ar sat 0.5 M H2SO4 170 61 238
38 Co2P/CNT 0.5 M H2SO4 195 74 236
39 CoP NPs 0.5 M H2SO4 221 87 233
40 CoP/RGO (0.30) 0.5 M H2SO4 240 104.8 236
41 CoP 0.5 M H2SO4 383 90 236
42 Co2P 0.5 M H2SO4 406 101 236
a
Dashes indicate that the corresponding data are not available in the respective reports cited here.

Table 10. Benchmarking the Metal (Fe, Co, Ni) Phosphides with Respect to the OER Overpotential at 10 mA/cm2 (η10)
s. no. catalyst electrolyte η10 (mV) Tafel slope (mV/dec)a ref.
1 Ni2P/Ni/NF O2 sat. 1 M KOH 205 − 242
2 Ni2P/NF O2 sat. 1 M KOH 220 − 242
3 Ni2P 1 M KOH 300 64 248
4 Co2P NPs 1 M KOH 310 50 222
5 CoP/Ti mesh 1 M KOH 310 87 221
6 CoP MNA 1 M KOH 310 65 229
7 Ni5P4 1 M KOH 330 − 252
8 CoP/C 0.1 M KOH 358 66 234
9 CP@FeP 1 M KOH 365 63.6 209
10 CoP hollow polyhedra 1 M KOH 400 57 225
a
Dashes indicate that the corresponding data are not available in the respective reports cited here.

8091 DOI: 10.1021/acscatal.6b02479

ACS Catal. 2016, 6, 8069−8097
ACS Catalysis
very recently reported by Liu and co-workers.261 Similarly, Xiao
and co-workers reported exceptional HER performance of Co−
P−Se NPs.117 Another interesting report was recently
published by Zhuo and co-workers on the HER activity of
Se-doped pyrite-type NiP2.250 These catalysts are included with
the sulfide and selenide benchmarking plots (Figures 9 and 11)
for comparative evaluation, and the respective experimental
details are included in Tables 5 and 7, respectively. These kinds
of materials are quite promising and can offer new pathways to
increase the catalytic activities of these sulfides and selenides.
Having seen a detailed comparative evaluation by means
benchmarking plots and the trends observed with the Tafel
slopes, it is now essential to compare the best HER catalysts
among the sulfides, selenides, and phosphides as well as the
best OER catalysts among the sulfides, selenides, and
phosphides. Such comparative plots are provided in Figure
15, from which we can conclude that the phosphides of Fe, Co,
Figure 15. Benchmarking plots of the best-ever metal (Fe, Co, Ni)
sulfide, selenide, and phosphide (a) HER and (b) OER catalysts
according to their overpotentials at 10 mA/cm2.
and Ni are better catalysts than the sulfides and selenides of the
same for both the HER and OER. This offers us new pathway
to modify the catalytic properties of these materials by tuning
the heteroatom (S, Se, P) content and/or mixing them with a
single metal atom among Fe, Co, and Ni or with a bi- or
trimetallic alloy of the same. With the given comparative view,
the knowledge of the activity trends of the Fe-, Co-, and Ni-
based sulfide, selenide, and phosphide catalysts is now clearly
exposed. Hence, we can recommend that beyond only the
overpotential and the Tafel slope, other activity parameters
such as mass activity, specific activity and TOF are to be
determined to elucidate the real catalytic efficiency of an
electrocatalyst for water splitting. Careful investigation of
Tables 5, 7, and 9 reveals that the anomaly observed in the
Tafel slope values with respect to the overpotentials is mainly
due to the pH of the medium of electrolysis. It is clear that all
8092
Review
of the lower values of Tafel slopes (approximately up to 55
mV/dec) were seen when the studies were carried in acidic
solution. This again indicates that although there are potential
catalysts being developed for the HER in alkaline media, there
is no catalyst with better kinetics than observed in acidic HER
electrocatalysis. One more thing that needs to be emphasized
here in the benchmarking of catalysts is that the lowest
overpotential is shown by fabricated electrodes such as
nanoarrays on various supports such as Ti mesh, CC, CF, Ni
foam, and carbon paper. In these cases the catalyst loading is
normally 5−10-fold higher than for the normal nanocatalysts
used in other studies, which leads us to misunderstand that they
are better than the other studies when actually they are not.
This again emphasizes the conclusion that the mass-normalized
current density would be better than the geometrical-area- or
ECSA-normalized current density for a fair comparison of
different catalysts. Having reviewed intensively the current
perspectives in electrochemical water splitting catalysis, we
recommend that the following activity parameters be
compulsorily incorporated in future reports of any such
electrocatalysts for the OER and HER: overpotential at a
defined current density normalized by the geometrical area and
the mass of loaded catalyst, the Tafel slope, the exchange
current density (for the HER), the mass activity, and the
loading.
9. SUMMARY AND OUTLOOK
The increasing pressure due to the faster depletion of
conventional fossil fuels and the negative impacts of the same
on the environment have urged the research community to find
alternative and viable sources of energy to enlighten the
decendants of humankind in the near future. As per the recent
studies of energy consumption and the availability of sources,
by 2015 the world will require 30 TW of power from new and
nonconventional energy sources.1 Though energies harvested
from solar, wind, tide, and other similar natural and endless
resources seem to be the most promising future ways of energy
generation, the major problem associated with those resources
is that they are seasonal and hence require large-scale energy
storage systems beyond the incapable batteries and super-
capacitors. One such indirect way of large-scale energy storage
is water splitting.
As we are aware that conventional combustion engines
running on conventional carbon fuels are badly contaminating
the environment, which is considered as the most serious threat
for humankind in the near future, people have now diverted
their attention to new zero-carbon-emitting and/or less-carbon-
emitting engines such as fuel cells. Fuel cell technology is a
greener available way of generating electrical energy from
various sources such as hydrogen, oxygen, methanol, glycerol,
borohydride, formic acid, and more as fuels. Among them, the
fuel cell that uses H2 and O2 as fuel is the greenest way to
produce electrical energy via a simple electrochemical redox
reaction between them that produces water as the byproduct.
The efficiency of these fuel cells can be as high as possible if the
H2 supplied is the purest. The conventional coal reforming
technology for H2 production is certainly not the one that gives
the purest H2. The H2 obtained by coal reformation contains a
considerable quantity of CO which is a serious threat to the
cathodes of fuel cells, as it will poison them by making strong
carbonyl coordination compounds with Pt atoms on the
catalyst’s surface, thereby reducing the number of active sites
available for the desired electrochemical reaction. Great
DOI: 10.1021/acscatal.6b02479
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ACS Catalysis
attention has now been given to water electrolysis for the
production of H2 in the purest form. However, there are several
thermodynamic and kinetic barriers in splitting water electro-
chemically, and they cause a huge energy loss in this process,
which increases the overpotentials of the HER and OER at the
cathode and anode further. Hence, both the HER and OER
need catalysts.
In earlier days, for HER the Pt electrode was used as the
state-of-the-art electrocatalyst, and it is still so used. Similarly,
for the OER either Ir or Ru and their compounds are used as
the state-of-the-art catalysts. However, we know that they are
noble, expensive, and less abundant metals. Hence, we cannot
afford such expensive materials for simple water electrolysis,
during which there are potential chances for losing the
materials by corrosion as the OER is the process that can
occur at very high anodic overpotential compared with the
HER. To avoid such pitfalls, people have started looking at the
3d transition metal oxides and hydroxides for OER electro-
catalysis and the chalcogenides of W, Mo, Ta, and Ti for HER
electrocatalysis. Very recently, people have found that the
sulfides, selenides, and phosphides of 3d transition metals,
particularly the group VIII metals (Fe, Co, Ni), can catalyze
both the HER and OER at all pH with almost the same kinetics.
The advantages of these 3d-transition-metal-based catalysts are
that they highly abundant, cheap, efficient, and easy to design in
a desired shape and structure depending on the needs for
electrolysis.
Hence, to make use of these advantages, we should be aware
of the activity trends and mechanisms of the OER and HER on
the surfaces of these group VIII 3d metal (Fe, Co, Ni)-based
sulfide, selenide, and phosphide catalysts. In this review, we
have made such a comparative measurement of group VIII 3d
metal (Fe, Co, Ni)-based sulfide, selenide, and phosphide
catalysts to enable those who are working on increasing the
efficiencies of these catalysts for H2 production by water
electrolysis with little loss in electrical energy via designing
catalysts with low overpotentials for both the HER and OER.
This comparative review enables researchers to acquire
knowledge of the trends in the activities of these catalysts
toward the HER and OER and helps them to formulate new
highly efficient water splitting catalysts for the sake of our
global future energy requirements.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: skundu@cecri.res.in and subrata_kundu2004@yahoo.
co.in. Fax: +91 4565-227651. Tel: +91 4565-241487.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We acknowledge Dr. Vijayamohanan K. Pillai, Director, CSIR-
CECRI, Karaikudi, India, for his continuous support and
encouragement. S.A., S.R.E., and K.S. acknowledge CSIR, New
Delhi, and K.K. acknowledges UGC, New Delhi, for the
afforded funding through the Senior and Junior Research
Fellowship (SRF and JRF) schemes. We also acknowledge The
Royal Society of Chemistry and The American Chemical
Society for the licenses given to reproduce figures from their
publications.
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Review
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8097 DOI: 10.1021/acscatal.6b02479

ACS Catal. 2016, 6, 8069−8097