Advanced Energy Materials - 2019 - Sultan - Single Atoms and Clusters Based Nanomaterials For Hydrogen Evolution Oxygen

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Review
Electrocatalysts www.advenergymat.de
Single Atoms and Clusters Based Nanomaterials

for Hydrogen Evolution, Oxygen Evolution Reactions,
and Full Water Splitting
Siraj Sultan, Jitendra N. Tiwari,* Aditya Narayan Singh, Shynggys Zhumagali,
Miran Ha, Chang Woo Myung, Pandiarajan Thangavel, and Kwang S. Kim*
demand is around 15 terawatts (TW), and

The sustainable and scalable production of hydrogen through hydrogen evo- the solar sun can provide higher than
lution reaction (HER) and oxygen through oxygen evolution reaction (OER) 50 TW energy in the light irradiance form.
Since other renewable energy resource
in water splitting demands efficient and robust electrocatalysts. Currently,
are limited and less than our present and
state-of-the-art electrocatalysts of Pt and IrO2/RuO2 exhibit the benchmark foreseeable future social requirements,
catalytic activity toward HER and OER, respectively. However, expanding their the sun represents the most plentiful
practical application is hindered by their exorbitant price and scarcity. There- source of energy that can provide enough
fore, the development of alternative effective electrocatalysts for water split- power which is higher than the human-
ting is crucial. In the last few decades, substantial effort has been devoted to ity’s needs. The existing technologies and
photovoltaic devices are converting light
the development of alternative HER/OER and water splitting catalysts based
energy of sun into an electrical energy,
on various transition metals (including Fe, Co, Ni, Mo, and atomic Pt) which however, in each day the sun only shines
show promising catalytic activities and durability. In this review, after a brief to a few hours, and due to shadowing the
introduction and basic mechanism of HER/OER, the authors systematically light from sun is distributed unevenly
discuss the recent progress in design, synthesis, and application of single across the earth’s surface. Additionally, the
energy from sun rays is scattered over the
atom and cluster-based HER/OER and water splitting catalysts. Moreover,
entire earth surface and fairly decreases
the crucial factors that can tune the activity of catalysts toward HER/OER and their power on the basis of area. Therefore,
water splitting such as morphology, crystal defects, hybridization of metals due to the diffuse and intermittent nature
with nonmetals, heteroatom doping, alloying, and formation of metals inside of the sun’s energy, alternative methods
graphitic layered materials are discussed. Finally, the existing challenges and and devices for concentrating and storing
future perspectives for improving the performance of electrocatalysts for of this light energy are necessitated.
Water splitting is considered to be a
water splitting are addressed.
promising approach which can resolve the
looming energy and environmental crisis
because it produces clean hydrogen energy
1. Introduction with zero CO2 emission.[3,4] Water splitting, a combination of
two half-cell reactions being hydrogen evolution reaction (HER)
The continuous growth in global energy demand, the rapid at a cathode and oxygen evolution reaction (OER) at an anode
consumption of conventional coals, oils, and fossil fuels and to produce hydrogen and oxygen gases that can be recombined
its associated environmental issues are prompting intense and converted into electricity at the point of usage in a fuel cell,
research interest in developing alternative energy systems.[1,2] provides a promising and environmental friendly pathway for
In particular, geopolitical anxieties and rising threats in climate conversion and storage of these clean renewable energy.[5] But,
variation inspire movement toward renewable, stable, ecof- in practice the water-splitting requires a larger thermodynamic
riendly, and benign energy sources. The current global energy potential due to some kinetic barriers happening at both HER
and OER sides.[5] This large thermodynamic equilibrium poten-
tial can be overcome by decorating the surface of the electrode
S. Sultan, Prof. J. N. Tiwari, A. N. Singh, S. Zhumagali, with some active catalytic materials. Currently, benchmark
M. Ha, Dr. C. W. Myung, P. Thangavel, Prof. K. S. Kim commercial Pt/C is used for HER, and benchmark IrO2/RuO2
Center for Superfunctional Materials
Department of Chemistry electrocatalysts for OER.[6,7] However, their rocketing price and
Ulsan National Institute of Science and Technology (UNIST) scarcity are major obstacles toward their practical implemen-
50 UNIST-gil, Ulsan 44919, South Korea tation.[6–8] Therefore, it is highly desirable to explore low cost,
E-mail: jitendra@unist.ac.kr; kimks@unist.ac.kr efficient, and stable catalysts especially designed from earth-
The ORCID identification number(s) for the author(s) of this article abundant metals for both photo and nonphoto water splitting.
can be found under https://doi.org/10.1002/aenm.201900624. In this regard, the research and development of earth-abundant
DOI: 10.1002/aenm.201900624 materials for HER/OER and whole water splitting catalysts
Adv. Energy Mater. 2019, 9, 1900624 1900624 (1 of 48) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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www.advancedsciencenews.com www.advenergymat.de
have attracted considerable interest in the past few decades,

with a variety of active catalysts being explored and developed. Siraj Sultan received his M.Sc.
The electrocatalysts for water splitting such as transition metal and M. Phil. in Chemistry
selenides, sulfides, nitrides, phosphides, carbides, and transi- from the Institute of Chemical
tion metals inside graphatic layers have been reported.[7,9] At Sciences, University of
present, fabulous breakthroughs have been attained regarding Peshawar, Pakistan. He is
the synthesis and design of advanced non-noble metal-based currently pursuing a Ph.D.
catalysts for HER, OER, and whole water splitting,[7,9] which degree under the supervision
has inspired the review of this broad research area. Although of Prof. Kwang S. Kim at the
numerous outstanding review papers relevant to OER or HER School of Natural Science,
or whole water splitting are available,[3,5,7,9c] a comprehensive Department of Chemistry,
review paper which covers wide-ranging earth-abundant metals UNIST, South Korea. His
and nonmetals based catalyst in cluster and atom forms for research interest focuses on
HER, OER, and whole water splitting is still not available. the synthesis and design of novel materials for electro-
In this review, we briefly introduce history and basic chemical catalysis.
mechanism of electrochemical HER/OER as well as general
parameters for scientific assessment of the catalytic activity of Jitendra N. Tiwari received
electrocatalysts. Moreover, we also discuss the critical problem his Ph.D. degree in electro-
and their solution during electrochemical measurement of chemistry from the Materials
HER/OER and whole water splitting by providing experimental Science and Engineering,
results in support of our discussions. Then, based on the recent National Chiao Tung
progress in the field, we systematically discuss the performance University (NCTU), Taiwan
of earth abundant metal based catalysts in form of single atoms, in 2009, where he worked on
single atoms + nanoclusters and nanoclusters under various synthesis of highly durable
pH values for HER/OER and whole water splitting, which are catalysts for electrochemical
depicted in Figure 1. We also address the density functional devices. After a short period
theory (DFT) calculation in support of HER/OER performance of postdoctoral research
of the reported catalysts. At last, we point out the current sci- experiences at the Institute
entific challenges that exist in the development of earth abun- of Nanotechnology, NCTU, Taiwan, he continued to work
dant metal based catalysts for HER/OER and whole water split- as a senior research scientist at Department of Chemistry,
ting. More significantly, we believe that this comprehensive POSTECH. Currently, he is a research assistant professor
review paper can offer a fresh and new impetus to design of at the Department of Chemistry, Ulsan National Institute
stable and high-performance earth abundant metals and non- of Science and Technology. He focuses on the development
metals catalysts, and can guide the researchers to exploit the of carbon-based hybrid materials and their applications in
established catalysts in appropriate water splitting and fuel cell energy storage and conversion.
technologies.
Water splitting can be divided into two half-cell reactions: Kwang S. Kim received his
cathodic HER and anodic OER. Figure 2 exemplifies the gen- Ph.D. degree from University
eral scheme of whole water splitting in a typical electrolysis of California, Berkeley. He was
cell in which water is first oxidizing to molecular oxygen at an a postdoctoral fellow at IBM
anode (OER). The resulting protons and electrons from water and a visiting professor or
oxidation reaction are transferring into cathode compartment scientist at Rutgers University,
through the applied membrane and an external circuit, respec- MIT, and Columbia University.
tively. Finally, the protons combine with electrons at cathode He was a professor in
and generate H2 (HER). Both HER and OER are critical for the Department of Chemistry,
whole efficiency of water electrolysis. At standard condition, the Pohang University of Science
change in Gibbs free energy (ΔG) for water electrolysis reaction and Technology. Currently, he
is 237.2 kJ mol−1, corresponding to a cell voltage of 1.23 V.[5] is a distinguished professor
However, in practice the water-splitting requires a larger voltage in Department of Chemistry and the director of the Center
than 1.23 V due to some kinetic barriers happening at both OER for Superfunctional Materials at Ulsan National Institute
and HER sides. This large thermodynamic equilibrium poten- of Science and Technology (UNIST). His research interest
tial can be overcome by decorating the surface of the electrode includes design and development of functional nanomate-
with some active catalytic materials. Generally, for water split- rials and nanodevices.
ting the electrocatalysts provide the following three main func-
tions: i) stabilizing the charge transfers (electrons and holes)
and hampering them from recombination; ii) offering active and sustainable energy conversion is the designing of scalable
adsorption sites for oxygen and hydrogen molecules; and and robust electrocatalysts, which can drive the splitting of
(iii) reducing the activation energies for oxidation and reduc- water with excellent efficiency and durability. In general, pro-
tion of water. The main challenge in hydrogen fuel for clean spective electrocatalysts based on earth-abundant metals for
the given j (in mA cm−2), the Φ value will be denoted as Φj,

and the η value as ηj. Since the minimum theoretical value
for the whole water splitting is 1.23 eV, ηj = Φj − 1.23 V. When
j = 0, the η becomes onset potential (ηo) at which the j starts
to deviate from the baseline (i.e., 0). The benchmark j is usu-
ally set to 10 mA cm−2 (to be denoted as “j10”),[10] and so the
benchmark Φ and η at j10 is denoted as “Φ10” and “η10”. Often
the j values are chosen as 20 mA cm−2 (j20) or 100 mA cm−2
(j100), for which Φ20/η20 and Φ20/η20 will be used. The exchange
current density (je) calculated from the equation (η = ζ log j/jo)
where “ζ” is the Tafel slope, and so je is defined as the j in the
absence of overpotential (i.e., for ηj = 0). The onset potential
is the potential at which catalytic j starts to deviate from the
baseline (the starting point for HER or OER), while the η is the
potential at which hydrogen or oxygen bubble formation starts.
It has been proposed that the intrinsic catalytic activity of
the HER/OER catalyst is strongly correlated with H-adsorption
Gibbs free energy (ΔGH*) and OH/O/OOH-adsorption free
energies (ΔGOH*, ΔGO*, ΔGOOH*) for the binding strength of
reaction intermediates where * denotes the active site on the
surface of the catalyst.[3,9e,f ] Plotting the je for HER with respect
to structural parameters such as ΔGH* and the η for OER
with respect to the adsorbed oxygen reduction free energy of
Figure 1. Overview of electrocatalysts for HER/OER and whole water
(ΔGO* ‒ ΔGOH*) for various metal oxides give triangular shapes
splitting discussed in this review. (NC: N-doped carbon, NG: N-doped
graphene, DG: defected graphene). known as volcano plots (Figure 3),[3,9e,f ] which reveals that nei-
ther strong nor weak interaction between reactant species and
catalytic site helps in effective electrocatalytic activity. The vol-
water splitting would have the following characteristic features: cano plots for HER/OER reflect the general explanatory para-
1) high efficiency like noble metal-based materials; 2) good cata- digm of the Sabatier principle in catalysis, which states that
lytic activity over a vast pH range; 3) high durability with stable the high catalytic activity can be achieved from the catalyst
activity; 4) ecofriendliness; 5) low cost and abundant sources; when its surface has an optimal binding energy for the gen-
6) abilities to integrate both OER and HER in a cell. erated intermediates species.[11,12]An active catalyst will bind
To achieve efficient electrocatalysts for water splitting, it is intermediate species neither too strongly nor too weakly. If the
essential to understand fundamental theoretical and experi- reactant intermediates are weakly bound to the active sites, the
mental concepts of the reactions on catalyst surface. The perfor- catalyst surface will be unable to activate the active sites for
mance of electrocatalyst for HER/OER/whole-water-splitting is a proper reaction, while if they are bound very strongly, they
evaluated from overpotential (η) or applied potential (Φ) which will occupy and block most of the active catalytic sites, which
is required to obtain a current density (j) for the electrode. For forbids effective reactions.[11,12] In specific case of HER, this
general paradigm can be guided from computation of ΔGH*
on the catalyst surface, which is the most common and reason-
able descriptor for determining HER activities for a variety of
metals, nonmetals, and alloys. In 1957, Parsons for the first
time demonstrated that the catalyst surface having ΔGH* near
to zero will be very active for HER catalysis.[13] It can be seen
from Figure 3a that the metals of (Pt, Rh, Re, and Ir) which
are located near the apex of HER volcano plot have the optimal
binding energy for hydrogen atoms. In the case of OER, the
theoretical overpotential (ηthe) versus the (ΔGO* ‒ ΔGOH*) in
volcano plot shows a good consistency with the electrocatalytic
activity for water oxidation.[9f ] The metal oxides located at the
bottom of the volcano plot (Figure 3b) such as ReO2, NbO2,
VO2, CrO2, and SnO2 exhibit high η for water oxidation due to
their weak or strong binding interaction with OER intermediate
species (O*, OH*, and HOO*). The metal oxides at or near the
apex of OER volcano plot such as IrO2, RuO2, NiOx, Co3O4,
and PtO2 (Figure 3b) have optimal binding strengths with OER
intermediate species and satisfy small ηthe for water oxidation
reactions.[7,9f ] However, most of the efficient HER/OER mate-
Figure 2. Schematic of electrolysis cell for whole water splitting. rials which are located at or near the apex of HER/OER volcano
Figure 3. Volcano plots for a) hydrogen evolution reaction. Reproduced with permission.[3,9e] Copyright 2018 Springer Nature and Copyright 1972,
Elsevier, Inc. b) oxygen evolution reaction. Reproduced with permission.[9f ] Copyright 2011, John Wiley and Sons.
plots are expensive noble metals/metal oxides, which limits 1.1. Basic Mechanistic Principles of Water Splitting Reactions
their widespread industrial applications.[6,7] Therefore, most of
the research efforts for finding and designing efficient HER/ 1.1.1. HER
OER electrocatalysts are diverting toward Ni, Co, and Fe based
materials which are next to noble metals in the volcano plots. HER is a two electron transfer reaction taking place on the
The volcano plots are providing valuable guidelines for electrode surface via two steps (Figure 4).[5a] The first step
understanding and designing efficient electrocatalysts in view of in HER is discharging of protons (H+) to form an absorbed
controlling the adsorption energy on catalyst surface for HER/ hydrogen intermediate (Hads) by coupling with an electron on
OER intermediates. However, in addition to material selection the active surface of an electrode, which is called the Volmer or
for fabricating efficient electrocatalysts, the rational design of discharging reaction. In acidic solutions, the source of proton
catalysts in terms of structure and morphology can be used to
improve the catalytic performance of HER and OER. The syn-
thesized catalyst would have the following characteristic feature
for better performance: 1) large surface area and high density
of active sites,[5a] 2) high catalytic activity and a large number of
active sites,[5c,14] 3) improved electrical contact to active sites,[9c]
4) increased open spaces and porosity among adjacent nano-
structures of the catalyst for efficient charge transport and elec-
trolyte permeation into the deep portion of catalyst surface,[15]
and 5) increased crystal and topological defects which increase
the electron density and conductivity of the materials.[14,16]
In this review, we first describe the basic mechanistic study
of HER/OER. Then we make a comprehensive survey on the
discovery and recent progress of earth-abundant transition
metals (including Ni, Co, Fe, Mo) based catalyst in cluster and
atom forms and their performance for HER/OER and full water
splitting in terms of η10, ζ, turnover frequency (TOF), and Fara-
daic efficiency at benchmark j10. Critical factors determining the
OER/HER and whole water splitting performance are summa-
rized, such as morphology, crystal defects, strain engineering
for metal with nonmetal, heteroatom doping, alloy effect for
metals, and formation of metals in graphitic carbon structures.
With experimental results, we also discuss the theoretical cal-
culations concerning the active catalytic sites and the origins of
the activity based on free energy change for adsorption on the
catalyst surface. Finally, we describe the current challenges and
Figure 4. HER mechanisms on the catalyst surface: If the theoretical ζ
provide a summary and future perspective for designing inex-
is ≈29 mV dec−1, the possible HER mechanism on the catalyst surface
pensive and effective catalysts for water splitting. This review will be Volmer–Tafel. The HER mechanism will be Volmer–Heyrovsky, the
aims at providing valuable guidelines in designing and fabri- ζ is ≈38 mV dec−1. In HER the * denotes the active sites of catalyst; H*
cating high-performance electrocatalysts for water splitting. denotes the adsorbed hydrogen to the active site of the catalyst.
is hydronium cation; while in the case of alkaline electrolytes OOH*  * + O2 + ( H+ + e − )

the source of proton is water molecule.[5a] In the second step, (4)
∆G4 = ∆GO2 − ∆GOOH* − eU + KTln H+ 
the H2 gas formation in both acidic and basic electrolytes may
occur through two different reaction mechanisms, depending
on the Hads coverage on the electrode surface.[17] If the coverage The proposed reaction mechanism for OER in basic
surface of Hads is low, single Hads would be preferably joining conditions
with a H+ and an electron concurrently to form a molecule of
H2, known as Volmer Heyrovsky or atom + ion reaction.[5c,18] OH− + *  OH* + e − (5)
In the case of large coverage surface of Hads, two adjacent Hads
on the electrode surface will recombine with each other to gen-
OH* + OH−  O* + H2O + e − (6)
erate molecular H2, known as Volmer Tafel or combination
reaction.[5c,17] ΔGH* has been suggested to be a good descriptor
for determining the HER rate. If ΔGH* is negative for the cata- O* + OH−  OOH* + e − (7)
lyst, the H* will bind more favorably with the surface of an elec-
trode and make the initial step (Volmer step) very easy; however,
OOH* + OH−  * + O2 + H2O + e − (8)
with more negative ΔGH*, the subsequent Heyrovsky or Tafel
step will be difficult. On the other hand, if a catalyst has a large
positive ΔGH*, the entire reaction will be slow due to repulsive where * indicates the active site of catalyst, and OH*, O*, and
interactions between electrode surface and proton. Thus, the OOH* denote adsorbed intermediates species, which are same
active catalyst for HER needs to have ΔGH* close to zero. in both acidic and basic pH. Therefore, the free energy changes
The theoretical ζ has been derived from the Butler–Volmer during OER in both acidic and basic solutions are calculated by
equation for three different cases[18] i) if the discharge reac- the same equations (Equations (1)–(4)). The OER η (ηOER) is
tion (Volmer reaction) is fast and H2 molecules are produced measured as the difference of the maximum value among ΔG1
by a rate determining combination (Tafel) reaction, the slope of through ΔG4 and the equilibrium potential (1.23 V), shown in
2.3RT/2F (ζ = 29 mV dec−1 at 25 °C) should be observed; ii) if the following equation
the discharge reaction is fast and H2 molecules are produced
by rate determining atom + ion (Heyrovsky) reaction, the slope η OER = max( ∆G1 , ∆G2 , ∆G3 , ∆G4 ) / e − 1.23 V (9)
should be 4.6RT/3F (ζ = 38 mV dec−1 at 25 °C); iii) If the dis-
charging of H+ is slow, the H2 is evolved either by a rate deter- According to DFT calculations, the ηOER is effected by
mining atom+ion reaction or combination reaction, where the the energy barriers of ΔGOH*, ΔGO*, ΔGOOH*, and ΔGO2
ζ should be 4.6RT/F (ζ = 116 mV dec−1 at 25 °C). The detailed (Figure 5a).[9f,20,21] For example, the work of Man et al.[9f ] revealed
HERs with theoretical ζ are summarized in Figure 4. that in the case of ideal catalyst the standard free energy (at pH = 0,
T = 298.15 K, potential U = 0 versus standard hydrogen elec-
trode) of each OER is equivalent to 1.23 eV (ΔGOOH* − ΔGOH* =
1.1.2. OER 2.46/2 = 1.23, red line in Figure 5a). However, in a real cata-
lyst, e.g., LaMnO3, the energy difference between ΔGOOH* and
OER is a sluggish reaction in water splitting which generates ΔGOH* is 3.22 eV instead of 2.46 eV (blue line in Figure 5a),[9f ]
oxygen gas through several electron/proton complex reac- indicating that the conversion of OH* → O*→ OOH* inter-
tion pathways. OER consists of four elementary steps, which mediates is the main obstacle in OER. Thus, the ηOER can be
strongly depend on the pH of the reaction medium.[3,19] In reduced by designing a catalyst which can decrease the ΔG
acidic pH, the reaction operates via oxidation of two water related to the OOH* formation in water oxidation reactions.
molecules to make one oxygen molecule with four proton-cou-
pled electron transfer steps. While in basic pH, the hydroxyl
groups take the lead and are converted into O2 and water mole- 1.1.3. Key Points for Electrocatalytic HER and OER Testing
cules with four electron transfer steps. The reactions for OER
in acidic and basic pH are summarized as follows. Counter Electrode: Electrocatalysts for HER and OER are usu-
The proposed reaction mechanism for OER in acidic condi- ally evaluated via three-electrode system, in which a counter
tions with free energies equations electrode, a reference electrode, and a working electrode loaded
with catalyst are immersed in the required electrolyte. Since Pt
H2 O + *  OH* + (H+ + e − ) is considered as a stable and inert metal for most of the oxi-
(1)
∆G1 = ∆GOH* − ∆GH2O − eU + KTln H+  dation and reduction reactions, it has been frequently applied
as a counter electrode in different electrochemical tests. How-
ever, the Pt can be oxidized and dissolved in both acidic and
OH*  O* + ( H+ + e − ) basic electrolytes at certain electrochemical circumstances.[23]
(2)
∆G2 = ∆GO* − ∆GOH* − eU + KTln H+  For example, the chloride of the acidic solution can increase
the electrochemical dissolution/leaching of Pt due to the pro-
duction of some stable chloride complexes (such as PtCl3−,
O* + H2O  OOH* + ( H+ + e − ) (3) PtCl42−, and PtCl62−). This dissolution of Pt from counter elec-
∆G3 = ∆GOOH* − ∆GO* − eU + KTln H+  trode in an electrolyte and its deposition on the catalyst occur
Figure 5. a) Standard free energy diagram for ideal and real OER electrocatalysts. The red and blue arrows represent the standard free energies for ideal
(2.46 eV) and real (LaMnO3: 3.22 eV) electrocatalysts, Reproduced the data with permission.[9f ] Copyright 2011, John Wiley and Sons. b) OER linear
sweep voltammetry (LSV) curves for the proper selection of oxidation peak and onset potential (EG: exfoliated graphene, LDH: layer-double-hydroxide).
Reproduced with permission.[22] Copyright 2016, Royal Society of Chemistry.
mostly during cyclic voltammetry (CV) stability test in the HER can probably influence the electrochemical performance of
potential region. In this instance, we examined the effect of Pt the working electrode.[24] Additionally, if Ag/AgCl electrode is
wire as a counter electrode on the HER activity of our designed immersed for a long time in strong alkaline environment, the
catalyst (carbon tubes encapsulating 1:2 Fe:Co alloys, denotes OH− from solution can diffuse to RE that will convert the AgCl
as CT-Fe:2Co) in 0.1 m HClO4 electrolyte. In our experiment, to AgxO and will shift the Ag/AgCl electrode potential to the
we performed stability test for 7000 CV cycles (7 K CV cycles), mixed potential of Ag/AgCl/AgxO.[24] In this regard, the Hg/
in which CT-Fe:2Co loaded on glassy carbon was used as a HgO electrode (often made from plastic which is highly stable
working electrode and Pt wire and Ag/AgCl as a counter and in an alkaline environment) is highly recommended to be used
reference electrodes, respectively. We observed that the HER as a RE for HER/OER measurements in alkaline solution.
activity of CT-Fe:2Co hybrid was increased with increasing the The RE using for each HER/OER measurement must be
number of CV cycles (Figure 6). The high number of CV cycles calibrated in the respective solution (acid or base selected for
corresponds to high Pt loadings, leading to a benchmark HER electrochemical measurements). For calibration, the linear
activity. From the CV curve of CT-Fe:2Co catalyst, the hydrogen sweep voltammetry (LSV) curve with slow scan rate in the
adsorption–desorption peaks were observed during 5 K CV potential range of −0.1 to −0.4 V should be performed in
cycles (Figure 6g,h). On the other hand, such peaks were not hydrogen saturated solution with Pt wires as counter and
seen in the initial cycle (Figure 6a) and unclear until 4 K CV working electrodes as well as with a selected RE. The poten-
cycles (Figures 6a–e). The area of hydrogen adsorption–desorp- tial at which the current just crosses the zero in the LSV curve
tion region increases as the Pt content increases by increasing should be taken as a thermodynamic potential for the reversible
the number of CV cycles; this proportionality is consistent with hydrogen electrode (RHE).
HER activity. To confirm the presence of Pt deposition on CT- Working Electrode: The working electrodes play a significant
Fe:2Co, we performed the transmission electron microscopy role in the HER/OER kinetics and performance due to their dif-
(TEM) and TEM-energy-dispersive-spectrometer (TEM-EDS) ferent structural configuration, degree of wettability, access of
analysis after 7 K CV cycles, which showed that the Pt was electrolyte to a catalyst and electrical conductivity. On account of
deposited on the CT-Fe:2Co surface (Figures 7a–d). To prevent the structure and degree of wettability, the working electrodes
deposition or any side reaction of Pt on catalyst surface during are divided into the flat surface electrode and 3D electrode. The
HER stability test, the graphite rod should be used as a counter electrodes with flat surface, such as glassy carbon electrode
electrode. (GCE), indium doped tin oxide substrate (ITO) and Cu/Ti foil
Reference Electrode: As the reference electrode (RE) has allow only single-way for electrolyte penetration that limits the
a strong influence on the accuracy of the electrochemical electrocatalytic reactions only on the electrode surface, while
measurements, it must have a constant potential and should be the 3D electrodes, such as Ni foam (NF) and carbon paper/
independent of the nature and concentration of the electrolyte cloth (CP/CC) allow the electrolyte penetration from all pos-
during the whole HER/OER testing. Specifically, in the alka- sible direction of electrode and therefore utilizing the whole
line solution, the RE must not be contaminated by the electro- material in catalyzing reactions.[25]
lyte or other foreign species during the experiment. The most The above-mentioned electrodes have their own advantages
common RE documented for HER/OER measurements in the and disadvantages. The GCE is considered as an inert substrate
literature is saturated calomel electrode, Ag/AgCl and Hg/HgO that has negligible electrochemical activity, and has been widely
electrodes. Saturated calomel electrode and Ag/AgCl electrode applied for HER/OER measurements in the literature. The
are popular REs in acid solution but not fulfil the real condi- GCE which is inert to electrochemical measurements can be
tions as a RE at high pH values. For example, during long simply used to directly figure out the intrinsic catalytic activity
term measurements in alkaline solution, the Cl− ions from Ag/ of the catalyst because all the electrocatalytic features obtained
AgCl electrode can leach out and diffuse to the catalyst that from the electrode can be credited to the active material. But
Figure 6. Effect of Pt as a counter electrode on the HER performance CT-Fe:2Co monitored through CV cycles. a–h) 1st to 7 K CV cycles. g,h) Hydrogen
adsorption and desorption peaks, due to Pt deposition from counter electrode. i) HER performance corresponding to 1–7 K CV cycles.
GCE demands a binder for the catalyst attachment to the sur- species). In some Ni-based materials the oxidation peak reaches
face which increases the charge/mass transfer resistance, to or more than 10 mA cm−2 (i.e., j10), which gives a confusion
blocks the electrocatalytic active sites and therefore decreases in the selection of Φo and Φj=10. Note that the oxidation peak
the actual electrocatalytic performance of the catalyst. To avoid is the inactive potential region for oxygen generation (in this
the negative effect of nonconductive binders, the direct growth potential region no oxygen bubble formation occurs). Thus,
of catalyst on a self-supported 3D electrode (NF or CP/CC) the Φo and Φj in the LSV having an oxidation peak are selected
which can bring a strong electrochemical connection between after oxidation peak, respectively. For example, Hou et al. pre-
current collector and catalyst is a promising alternative. sented the oxidation peak (which reached to j = ≈100 mA cm−2
Electrochemical Tests: During electrochemical testing, the at Φ = 1.43 V) and the onset potential Φo = 1.47 V) in the OER
electrolyte will be saturated with high purity H2 gas for HER curve of the exfoliated-graphene/Co0.85Se/NiFe-layer-double-
and with O2 gas for OER, and then will be maintained over the hydroxide catalyst (Figure 5b).[22]
electrolyte surface during testing to establish standard condi-
tions. LSV curves are usually used to measure the HER and OER
performances of the electrocatalyst by measuring j (experimen- 2. Electrocatalysts for HER
tally observed catalytic current normalized to the geometrical
area of electrode) in milliampere (mA) as a function of applied In this section, we present the recent progress in HER electro-
potential. The performance of electrocatalyst for HER and OER catalyst based on earth-abundant metal (Ni, Co, Fe, and Mo) in
is evaluated from ηo (= Φo ‒ 1.23 V) and ηj (= Φj ‒ 1.23 V). To terms of their synthetic methods, morphology, activity, ζ, TOF,
avoid the background or capacitive current in LSV, the electro- and stability. We also focus our discussion on the theoretical
chemical test should be performed in a steady state condition understanding and the critical factors which boost the catalytic
at a low scan rate of 1 or 2 mV s−1. Moreover, in OER most of activity toward HER such as crystal defects, surface area, heter-
nickel-based materials give either a weak or a strong oxidation oatom doping, and alloy effect, etc. Finally, we make a summary
peak (the anodic peak before Φo originates from oxidation of Ni and future challenges for making a suitable catalyst for HER.
Figure 7. HAADF-STEM images of Pt-CT-Fe:2Co and the corresponding Fe-, Co-, Pt-elemental mappings after 7 K CV cycles. The EDX mapping shows
the presence of Pt.
2.1. Iron-Cluster-Based Electrocatalysts for HER of this catalyst would arise from the alloying effect of Fe and
Co and their encapsulation in conductive CNT, which reduces
2.1.1. Iron and Fe-Alloying with Other Transition Metals the charge transfer resistance during HER. Theerthagiri et al.
reported iron diselenide (FeSe2) nanorods on graphene oxide
Iron, titanium, and manganese are the most abundant transition (GO),[29] which showed η9.68 = 250 mV with ζ = 64 mV dec−1.
metals in the earth crust, among which iron is the most plen- Similarly, Guan et al. reported FeSe2 nanomesh on titanium
tiful and attractive metal due to its low toxicity, minor environ- foil, which displayed η10 = 175 mV with ζ = 51 mV dec−1 and
mental impact, and inexhaustible supply.[26,27] Iron in the form constant current in 24 h chronoamperometric response.[30]
of carbides, sulfides, and nitrides has been extensively applied Lan and co-workers synthesized alloy of Fe3C and Mo2C on
as effective electrocatalysts in oxygen reduction reaction (ORR) N and P codoped GO (Fe3C/Mo2C @ NP-GO), which showed
and fuel cell applications.[27] Researchers in the last few dec- η10 = 98 mV with ζ = 45.2 mV dec−1 and high stability in acid
ades explored that the OER activity of nickel oxide or hydroxide solution.[31]
can be drastically enhanced by doping it with metallic iron.[26,27]
Also iron in the form of phosphides and sulfides have shown
considerable HER activities. Nevertheless, studies of iron in 2.1.2. Iron Phosphides
single or alloy as electrocatalysts for HER are hardly reported.
Yet, Wang and coworkers reported iron oxide nanoparticles 3d-Transition metal phosphides (TMPs) have high electrical
(NPs) encapsulated in N-doped carbon matrix (Fe2O3 @ CN) and thermal conductivity and have been extensively applied as
as a HER electrocatalyst.[28] The Fe2O3 @ CN was synthesized catalysts for hydrodenitrogenation/hydrodesulfurization, and
from simple calcination of d-glucosamine hydrochloride, mela- as an anodic material for lithium ion batteries.[32,33] Recently,
mine and Fe(NO3)2·6H2O in N2 atmosphere. The TEM anal- TMPs such as CoP, Ni2P, Cu3P, WP, MoP, and FeP are found
ysis showed that the Fe2O3 NPs of ≈15 nm size were uniformly to be active and stable materials for HER.[34] Among all these
distributed in the N-doped carbon matrix. The as-synthesized 3d-TMPs, FeP is highly attractive because Fe is the most earth-
Fe2O3 @ CN exhibited η10 = 330 mV with ζ = 114 mV dec−1 and abundant and low-cost metallic element and FeP has been used
je (12.2 µA cm−2) in 1 m KOH solution. The HER activity of as HER electrocatalysts.[34,35] Guo et al. synthesized hierarchical
the Fe2O3 @ CN resulted from the strong interaction between hollow microspheres of FeP as a HER electrocatalyst.[34] This
Fe2O3 NPs and N-doped carbon. Yang et al. studied FeCo catalyst showed η10 = 144 mV with ζ = 58 mV dec−1 and rea-
alloy NPs encapsulated in N-doped graphene, which showed sonable stability for 1000 CV cycles. Most of FeP is facing the
η10 = 262 mV with ζ = 74 mV dec−1.[26] Deng et al. reported stability problem. To enhance the stability, it was coated with
FeCo alloy NPs in N-doped carbon nanotubes (CNTs), which some carbon layer or encapsulated inside graphitic carbon.
showed η10 = 110 mV with ζ = 74 mV dec−1.[27] The activity Zhu et al. reported hollow mesoporous FeP coated with carbon
(HMFeP @ C).[35a] This catalyst exhibited lower η10 (115 mV), high HER activity of this hybrid is attributed to the following
higher stability (constant j for 20 h) and similar ζ (56 mV dec−1). aspects: i) the hybrid nanostructure of FeP/VAGN provided a
The activity and stability are attributed to the cubic architectural large surface area with abundant accessible active sites for HER,
feature, porous nature, and synergistic effect of coated conduc- ii) the electrons rapidly transferred from FeP to the current col-
tive carbon. Zhang et al. used candle soot (CS) as a supporting lector due to close contact between FeP/VAGN and CC, iii) the
material for FeP NPs (FeP-CS).[35b] This FeP-CS electrocatalyst 3D morphology and suitable open space of VAGNs facilitated
exhibited η10 = 112 mV with ζ = 58 mV dec−1 and same perfor- the contact of electrolyte with electrode. Tang et al. developed
mance after 10 000 CV cycles. The HER activity and stability Fe0.5Co0.5P nanowire (NW) on conductive CC (Fe0.5Co0.5P/CC)
are attributed to: i) the metallic feature of FeP displaying high as an effective HER electrocatalyst.[41] This catalyst showed
conductivity and facilitating rapid electron transfer, ii) the elec- very small η10 = 37 mV with ζ = 30 mV dec−1 (followed the
tron transfer from metal to phosphorus which rendered large Volmer–Heyrovsky mechanism) and high stability. The superb
positive charge density on atomic Fe as an active site for HER, HER activity was elaborated from DFT calculations where the
iii) close contact between FeP and CS which afforded the syn- possible active sites in FexCo1−xP were investigated using CoP
ergistic effect for catalytic reactions, and iv) large surface area and Fe0.5Co0.5P models. For CoP the ΔGH* was −0.14 eV, repre-
provided by CS for the loading of FeP, which created more senting a proper binding of H on catalyst surface in the Volmer
active sites for HER. Liu et al. made a sandwich-like structure step which lowers the desorption rate of H2 in Heyrovsky step.
of FeP/reduced-graphene-oxide (rGO)/FeP NPs as a HER elec- In Fe0.5Co0.5P (ΔGH* = −0.106 eV) the strength of H+ adsorp-
trocatalyst.[36] This electrocatalyst displayed η10 = 101 mV with tion on catalyst surface weakened slightly and made it easy to
ζ = 55.2 mV dec−1, TOF of 1.11 s−1, and stability for 5000 CV desorb H2 from catalyst surface in the Heyrovsky step. The Fe
cycles. The high HER activity is attributed to sandwich-like substitution in CoP led to an optimal ΔGH*, due to which it
architecture, which enhanced electrical conductivity, accessi- showed inferior HER activity.
bility to electrolytes, and exposed active sites. Recently, Sung
and co-workers synthesized FeP NPs coated with carbon shell
(FeP/C),[37] which displayed η10 = 71 mV with ζ = 52 mV dec−1 2.1.3. Iron Sulfides
and high stability for 10 000 CV cycles with no obvious change
in performance. The high stability is ascribed to coated carbon Iron sulfide (FeS) materials have been extensively examined
shell, which protected FeP NPs from oxidation under HER. as catalysts for energy conversion and storage application due
Yan et al. synthesized hierarchical FeP films composed of FeP to low cost, earth abundance, large conductivity, mechanical
nanopetals by a bio-inspired hydrothermal and phosphorization and thermal stability.[42] Specifically, FeS based materials
approach.[38] In a typical synthesis process, first the FeO(OH) are presently under investigation for solar absorbers and as
film with uniform nanopetals in the presence of glycerol was electrocatalysts for batteries and ORR.[43,44] Recently, it was
produced by a bioinspired hydrothermal method. The FeO(OH) found that the FeS based materials can also be applied for
film was then transferred to Ti foil (electrode substrate), and HER application. For example, Konkena et al.[42] presented
heated at 80 °C to enhance the contact between Ti foil and natural ore of pentlandite having composition Fe4.5Ni4.5S8 as
FeO(OH) film. Finally, the FeO(OH) films were converted to a HER electrocatalyst, which displayed η10 = 280 mV with ζ =
FeP films using PH3 as a phosphorous source. The catalyst 72 mV dec−1 and long-term durability in 0.5 m H2SO4 solu-
showed high HER activity in both acidic and basic conditions tion. However, FeS based materials without modification
(η10 = 65 mV with ζ = 48.5 mV dec−1 in 0.5 m H2SO4 solu- have rarely shown HER activity due to its low surface area,
tion and η10 = 85 mV with ζ = 85 mV dec−1 in 1 m KOH). This small electronic affinity between sulfur and metal, and very
catalyst also displayed high stability in both acidic and basic few active catalytic sites. In this regard, a different synthetic
condition. The high HER activity was explained from DFT strategy has been used to improve the catalytic activity of
calculations that the ΔGH* for FeP at H coverage of 1/4 was FeS based materials by increasing their surface area, doping
0.09 eV, which allowed it a favorable surface for H adsorption/ them with other transition metals or changing their electronic
desorption. structure. Yu et al. synthesized hierarchically porous micro-
In the above-mentioned literature, the polymer (nafion) was flowers of 3D-nickel iron sulfide on Ni foam (Ni0.7Fe0.3S2/
used as a binder for the attachment of the FeP electrocata- NF) by hydrothermal and sulfurization method.[43] This cata-
lyst to the electrode substrate, which inhibits the electrolyte lyst displayed η10 = 155 mV with high stability in 1 m KOH
diffusion, increases the charge transfer resistance, and blocks solution. The HER activity was attributed to the synergistic
the active catalytic sites for HER.[39,40] Therefore, the HER effect of Fe and Ni alloy and the close contact of Ni0.7Fe0.3S2
activity of FeP can be further improved by growing it directly on with NF, which reduced the resistance for charge/mass
some 3D-conductive substrates such as NF or CC.[39–41] In this transportation during HER. Hu and his coworkers improved
regard, Luo group synthesized binder free FeP nanorod on CC the HER activity of FeS2 NPs by uniformly distributing and
by phosphidation reaction.[39] The catalyst showed η10 = 58 mV embedding them in conductive rGO.[44] The catalyst exhib-
with ζ = 45 mV dec−1 and large je (= 0.50 mA cm−2) in 0.5 m ited η10 = 139 mV with ζ = 66 mV dec−1 and high stability
H2SO4. Similarly, Wang et al. synthesized a hybrid nanostruc- in 0.5 m H2SO4 solution. The high HER activity of FeS2/rGO
ture of FeP and vertically aligned graphene networks on CC is ascribed to the strong interaction between FeS2 and rGO,
(FePNRs/VAGNs/CC) by electrodeposition and phosphidation and also protected the NPs from leaching during the long run
approach.[40] The catalyst displayed small η10 (53 mV) with HER operations. Suib group synthesized mesoporous FeS2 as
ζ = 42 mV dec−1 and high stability in 0.5 m H2SO4 solution. The an active HER electrocatalyst by sol–gel and low-temperature
sulfurization protocol.[45] This mesoporous FeS2 has larger ζ = 55 mV dec−1, and constant j during 40 h chronoampero-
BET surface area (128 m2 g−1) than that of commercial FeS2 metric test. The high HER activity is ascribed to the synergistic
(1 m2 g−1). This mesoporous FeS2 achieved η10 = 96 mV with effect of N–C and Co NPs. Wang et al. synthesized 3D-porous
ζ = 78 mV dec−1 and high stability for 24 h in basic solutions. electrode composed of CoOx NPs and CNTs which were sup-
The high HER activity of the mesoporous FeS2 is ascribed to ported on activated carbon fiber (denoted CoOx–CNT–CC)
mesoporous structure and high surface area which facilitated through impregnation and pyrolysis process.[52] The X-ray
the charge/mass transportation in HER. Li et al. fabricated photoelectron spectroscopy (XPS) analysis showed that the Co
ultrathin CuFeS2 nanosheets (NSs) with exposed (024) high in the as-synthesized CoOx–CNT–CC hybrid was composed of
index facets as a HER electrocatalyst.[46] The electrocatalyst Co(II) and Co(III) species. This CoOx–CNT–CC hybrid displayed
showed η10 = 88.7 mV, ζ = 47 mV dec−1, je = 0.35 mA cm−2, η20 = 99 mV with high durability for 70 h in 1 m KOH solu-
and high stability for 15 000 CV cycles in 0.5 m H2SO4 solution. The high HER activity and durability of CoOx–CNT–CC
tion. The HER activity of CuFeS2 NSs is ascribed to the high hybrid is contributed to its 3D structure with high surface
density of active S−2 sites on the exposed (024) index facets, area and well-developed pore structure and intimate contact
which is further confirmed from DFT calculations. The ΔGH* of CoOx–CNTs with a supporting substrate which facilitated
was calculated on three different facet planes of CuFeS2 NSs the charge/mass transfer and release of generated hydrogen
such as (112), (220), and (024). The ΔGH* on (220) and (112) molecules from the electrode surface during the HER reac-
planes are 0.19 and −0.26 eV, showing that both surfaces are tion. Similarly, Ma and co-workers used CC as a supporting
not highly favorable for HER due to their weak and strong material for the hollow shaped cobalt NPs.[50] This catalyst dis-
binding with H+, respectively. In (024) plane the ΔGH* is played η10 = 85 mV at neutral pH with small ζ = 38 mV dec−1,
0.1 eV, demonstrating a more favorable surface for H+ adsorp- high je = 1.53 mA cm−2, and long-term stability. The high HER
tion and H2 desorption compared to (112) and (220). Xiong activity is attributed to its unique structure and close contact of
et al. synthesized iron–cobalt–sulfide (FexCo1−xSy) alloy as a NPs with conductive substrate CC, which facilitated the faster
HER electrocatalyst by bottom-up engineering approach.[47] charge/mass transport. Zhang et al. used N and B codoped
They used two different optimization steps such as i) the ultrathin carbon cages for the encapsulation of Cobalt NPs
rational optimization of Fe, Co, and S in FexCo1−xSy for get- (Co@BCN).[51] This Co@BCN was synthesized by bottom-up
ting better HER activity by atomic layer deposition (ALD) strategy using metal organic framework (MOF) or zeolite imi-
method and ii) the geometrical optimization of CNTs on dazolate framework and H3BO3 as starting materials. The cata-
CC (CNTs/CC) as an electrode substrate for large surface lyst exhibited η10 = 96 mV with stability for 1000 CV cycles. The
achieved by chemical vapor deposition (CVD) technique. In high HER activity can originate from the synergistic effect of
the rational optimization, Fe0.54Co0.46S0.92 was the best com- cobalt NP and codoped B and N in the carbon shell, which is
position for the HER activity, which was then coated on the revealed from DFT calculations. For DFT calculations Co55@
optimized CNTs/CC electrode substrate (represented by C240, Co55@C234N6, Co55@B2C232N6 (Co55 cluster encapsulated
Fe0.54Co0.46S0.92/CNTs/CC) and applied as a electrocatalyst for in N/B Co-doped carbon cage), pure Co55 cluster and C240 cage
HER. This Fe0.54Co0.46S0.92/CNTs/CC hybrid exhibited very models were used. The more negative ΔGH* on Co55 cluster
small η10 (70 mV), and constant j during 72 h chronoampero- (≈−0.4 eV) represented their stronger interaction with H+, while
metric test in 1 m KOH solution. Kuo et al. synthesized cobalt- in C240 cage the more positive ΔGH* (≈1.31 eV) indicated their
doped iron pyrite modified with phosphide on Ti foil as an weak interaction with H+, which thus demonstrated low HER
electrode substrate (P/Co-FeS2/TF) by solvothermal, sulfuri- performance in both cases. In Co55@C240 the ΔGH* changed
zation, and phosphidation protocols.[48] This catalyst displayed from 1.31 to 0.35 eV, indicating more favorable sites to H+
η100 = 90 mV with ζ = 41.5 mV dec−1 and impressive stability and H2 adsorption/desorption compared to pure Co55 cluster
(no obvious changes in HER performance after 6-day chrono- and C240 cage. In N-doped Co55@C234N6 and N/B codoped
amperometric test). The superb HER activity of this catalyst is Co55@B2C232N6 the ΔGH* values changed dramatically to 0.23
attributed to the synergistic effect of Fe and Co alloy and the and 0.118 eV, respectively, indicating more active catalytic sur-
modification of their surface with phosphide which further face for HER compared to Co55@C240. Tong et al. synthesized
enhanced the catalytic sites for reactions. Co(OH)2 nanorods on 3D macroporous electrically conductive
network (MECN) as a HER electrocatalyst.[53] This catalyst dis-
played η10 = 69.2 mV with ζ = 61.9 mV dec−1, and moderate
2.2. Cobalt-Cluster-Based Electrocatalysts for HER stability in 1 m KOH solution. The superb HER activity of
this catalyst is ascribed to the synergistic effect of Co(OH)2
2.2.1. Cobalt and Co-Alloying with Other Transition Metals nanorods and MECN, which facilitated the charge/mass trans-
port during catalytic reactions.
Cobalt has been extensively applied for HER.[49,50] However, Co NPs in single form showed considerable HER activity.
cobalt in free atomic structure is not an active and stable cata- However, their activity and stability can be further improved
lyst for HER.[49,50] Therefore, for the stability and efficient HER, by alloying with Fe, Ni, Cu, Pd, and Pt.[54] Alloying of two dif-
some conductive materials such as graphene sheet or CNT ferent transition metals prompts favorable modifications in
are used to encapsulate or dope the cobalt in atomic or ionic intrinsic properties by changing the electron density around
form or to make their complex.[49–51] For example, Zhang and the Fermi level of the metallic sites, playing a critical role in
co-workers used N-doped carbon to support Co NPs.[49] The boosting the catalytic activity.[54] For example, Khalifah et al.
catalyst exhibited high HER activity with η10/100 = 138/212 mV, synthesized cobalt molybdenum nitride (CoMoN2) alloy as
HER electrocatalyst, which displayed η10 = 200 mV.[54a] This catalyst demonstrated high HER activity and stability in basic/
activity of CoMoN2 is ascribed to the synergistic effect of Co acidic ranges with η = 138/135 mV. This superb HER activity
and Mo. Recently, Zhang et al. made Co0.85Se alloy on gra- is attributed to high surface area (589 mg−1) and large con-
phene network.[54b] The catalyst exhibited η10 = 196 mV with ductivity (51 S cm−2 at 25 °C), which facilitated the charge and
ζ = 34.4 mV dec−1 and high stability for 20 h. The reasonable mass transport very efficiently between electrode and electro-
HER activity and stability is attributed to the synergistic effect lyte. Zhuang et al. fabricated encapsulated di-cobalt phosphide
of Co0.85Se nanocrystals and their strong interaction with con- NPs in N- and P-doped graphene (Co2P@NPG) as an electro-
ductive graphene network, which provided large conductivity catalyst for HER.[59] This catalyst exhibited high HER activity
and abundant active catalytic sites for charge transfer between giving η = 45 mV at j = 1 mA cm−2 with ζ = 58 mV dec−1,
electrode and electrolyte. Chen et al. synthesized PdCo alloy je = 0.21 mA cm−2 and high stability for 30 h in an acidic elec-
wrapped in N-doped Carbon (PdCo@NC) by calcining Pd- trolyte. The high HER activity and stability would originate
doped MOFs (PdxCo3[Co(CN)6]2) in N2 atmosphere.[55] This from the synergistic effect of N- and P-doped graphene layers
catalyst showed small η10 (80 mV) with small ζ = 31 mV dec−1 and encapsulated Co2P NPs. Similarly, Lin et al. designed
and long-term stability in 0.5 m H2SO4 solution. The high CoP nanorods supported on N- and P-doped carbon flakes for
HER activity and stability is attributed to the synergistic effect HER activity.[60] This hybrid catalyst displayed η10 = 135 mV,
of PdCo alloy and conductive N-doped C which boosted mass ζ = 67 mV dec−1, je = 1.37 µA cm−2, electrochemical double-layer
charge transfer, and the stability is due to PdCo alloy encapsu- capacitance (Cdl) of 9.25 mF cm−2 and high stability in 0.5 m
lated in carbon shell. Su et al. made RuCo alloy encapsulated H2SO4 solution. This high HER activity is attributed to active
in N-doped graphene layers (RuCo@NC).[56] This catalyst dis- and defects sites in the catalyst and the synergetic effect between
played very small η10/100 = 28/218 mV with ζ = 31 mV dec−1. To CoP and N- and P-doped graphene layers. Callejas et al. synthe-
investigate the superb HER activity of RuCo@NC electrocata- sized hollow Co2P NPs and checked their HER performance in
lyst, the DFT calculations were performed using models of pure acidic solutions.[61] This catalyst required cathodic η10 = 95 mV
graphene (C240), N-doped graphene (N-C239), Co encapsulated with ζ = 50 mV dec−1. Similarly, Yang et al. synthesized CoP
in N-doped graphene (Co239@N-C239), and RuCo alloy encap- encapsulated in N-doped porous carbon (CoP@NC) using a
sulated in N-doped graphene [Ru3Co (Ru3Co52@N-C239)]. The MOF derived method.[62] This catalyst exhibited remarkable
ΔGH* of pure graphene was highly positive (≈2.6 eV), which HER activity in acidic/basic media with η10 = 78/129 mV. This
reduced to ≈0.55 eV after doping with N atoms. In Co239@N- high HER activity is attributed to the synergistic effect between
C239 the ΔGH* was ≈0.48 eV, which reduced to ≈0.31 eV after N-doped graphitic carbon layer shells and CoP cores. The high
encapsulating Ru3Co alloy in N-doped graphene. Thus, the HER performance was further elaborated from DFT calcula-
introduction of Ru into Co core enhanced the electron transfer tions. The ΔGH* for N atom was highly positive (1.783 eV) as
efficiency from alloy core to N-doped graphene shell, improving compared with the adjacent C atoms (0.212 eV), indicating that
CH bond with lowering the ΔGH* for HER. Mahmood et al. the dopant N was not an active site for HER, but it activated the
synthesized the PtAgCo NSs as highly efficient electrocatalyst adjacent C atoms. Thus, the C adjacent to dopant N was the
for HER.[57] This catalyst delivered very high j = 705 mA cm−2 at active site for HER. Similarly, Bai et al. synthesized a hybrid
η = 400 mV with very small ζ = 27 mV dec−1 and high stability. of crystalline Co and amorphous CoP on NF (Co–CoP/NF).[63]
This high HER activity is due to the synergistic effect of three This hybrid exhibited η10 = 35 mV with ζ = 71 mV dec−1 in
combined metal alloy and the defective sites generated near to basic solution. The high HER activity is due to i) unique crystal-
Pt atoms which improved the mass/charge transferred during line and amorphous structure which helps in hydrogen adsorp-
the catalytic reaction. tion/desorption, ii) large electrochemical active surface area
(36.75 cm2) which provides more active sites, iii) porous struc-
ture, and iv) binder-free interaction between Co/CoP and NF
2.2.2. Cobalt Phosphides which reduces resistance between the electrode substrate and
the catalytic material. Chen et al. synthesized Mn-doped CoP
The electrochemical activity of transition metal based materials NSs on titania (TiO2) mesh (Mn–CoP/TiO2) as an effective 3D
is strongly correlated to the electric conductivity.[58] TMPs made electrocatalyst for hydrogen generation.[64] The Mn–CoP/TiO2
by alloying phosphorus and metal have metalloid features hybrid displayed η10 = 49/76 mV in acidic/basic solution with
with high conductivity and can be utilized in e lectrochemical high stability. The effect of Mn doping on HER activity was
applications.[59,60] Recently, it was discovered that the HER elaborated from DFT calculations. In Mn-CoP, the Mn atoms
proceeded through the same path as hydro-desulfurization, donated their valance electron to adjacent Co and P atoms,
where a hydrogen adsorption–desorption on the catalyst sur- and made weaker bond between CoH atoms with the ΔGH*
face was critical for getting fast and feasible kinetics.[32] Hence, close to zero. Ma et al. synthesized NPs of cobalt phosphide
phosphides based catalysts were utilized previously in the coated with N-doped carbon on N-doped graphene (CoP@NC/
hydrodesulfurization process, suggesting that it would also be NG) as acidic HER electrocatalyst.[65] This hybrid exhibited
an active catalyst toward HER.[32] Like different TMPs, cobalt η10 = 135 mV with ζ = 59.3 mV dec−1 and constant j during
phosphide (CoP) in different composition, structure, and mor- 14 h durability test. The high HER activity would arise from
phology has been studied for effective HER catalysis.[58–61] the following aspects: i) graphene sheet works as a conducting
Wang et al. synthesized hierarchically porous, N-doped gra- support for the well-dispersed CoP NPs growth; ii) dopant-
phitic carbon material supported with Janus-type nanocrys- N in carbon shell and graphene improves the conductivity of
tals of Co/CoP (HNDCM-Co/CoP).[58] The HNDCM-Co/CoP the catalyst and its interaction with hydrogen; iii) carbon shell
protects the NPs of CoP from degradation during the durability the density of exposed active catalytic sites and increasing
test. Similarly, Li and co-workers synthesized nanocrystals of conductivity. Liu and co-workers developed 3D hierarchical
cobalt molybdenum phosphide coated with N-doped carbon cobalt disulfide/molybdenum disulfide nanostructured on
shell (CoMoP@NC) as an electrocatalyst for HER.[66] This cata- CC (CoS2/MoS2/CC).[68] The catalyst exhibited η10 = 177 mV
lyst exhibited small η1/10 = 6/41 mV with ζ = 49.73 mV dec−1 in with ζ = 66 mV dec−1, and maintained their activity after
0.5 m H2SO4 solution. This superb HER activity was supported 1000 CV cycles test. The high HER activity of this hybrid can
from DFT calculations. The ΔGH* (1.832 eV) for pristine gra- be assigned to the synergistic effect between CoS2 and MoS2,
phene showed that the HER process on pristine graphene can more accessible electrochemical active sites due to alloying
hardly be proceeded due to its poor interaction with H. The effect and fast charge/mass transport because of conductive
ΔGH* for N–C was 1.181 eV, smaller than that of pristine gra- CC substrate. Wang et al. synthesized hybrid of Co3S4/CoP as
phene. The ΔGH* calculated for CoMoP was −0.555 eV, which electrocatalyst for HER, which exhibited onset η of 34 mV with
implies their strong interaction with atomic hydrogen but the ζ = 45 mV dec−1 and stability for 1000 CV cycles.[69] This high
difficulty in releasing H2. In the case of CoMoP@C the ΔGH* HER activity can be attributed to the synergistic effect between
was 0.103 eV, close to 0 eV, indicating that it is a highly active CoP and Co3S4. Zou et al. improved the HER activity of Co2.7S4
catalyst for HER. Moreover, its remarkable HER activity arose by doping it with zinc.[70] Zn0.3Co2.7S4 was synthesized by
from structural features of CoMoP@C such as i) its high BET MOF self-template strategy and thermal annealing. The cata-
surface area, ii) the synergistic effect between N–C and CoMoP, lyst exhibited η10 = 85/90/ 80 mV and η100 = 136/144/129 mV
and iii) the presence of the carbon-shell which makes a short in 1 m KOH/0.1 m phosphate-buffer/0.5 m H2SO4 solution.
path for charge transfer and intimate contact between electro- The calculated ΔGH* for Pt was 0.09 eV, while in the case of
lyte and active site of the catalyst. Han et al. fabricated NSs of Zn doped Co2.7S4 the ΔGH* was 0.32 eV, which indicated that
cobalt–nickel phosphide on NF (CoNiP/NF), which displayed a it had a moderate catalytic surface for the H+ adsorption and
good HER activity in acid, neutral and basic pH.[67] This catalyst H2 desorption. Jin et al. synthesized cobalt phosphosulfide
displayed η10 = 60/120/155 mV in acidic/neutral/basic solu- (CoPS) from cobalt-based nanostructured materials at 500 °C
tion. It showed ζ = 39 mV dec−1 and high stability in acid solu- in a thiophosphate atmosphere (produced from thermal evapo-
tion. The high HER activity and stability can be ascribed to its ration of elemental powders of sulfur and phosphorus) under
unique structure, high conductivity of NF, synergistic effect of argon.[71] The catalyst exhibited η10 = 48 mV with high dura-
CoNiP and NF, and close contact of CoNiP to NF which facili- bility (Figure 8a,b). Figure 8c indicates that the calculated ΔGH*
tated the faster charge/mass transport. for H+ adsorption at a Co site in CoPS is more favorable than
that of simple CoS2. Moreover, Figure 8c shows that after spon-
taneous H+ adsorption at open P sites the ΔGH* at the nearby
2.2.3. Cobalt Sulfides Co sites is negative, resulting in spontaneous reaction, which
can be ascribed to the reduction of Co3+ sites to Co2+ on H+
Cobalt sulfides are earth-abundant, low cost, highly electri- adsorption at an adjacent open P site, and then Co+2 turns back
cally conductive, thermally and mechanically stable, elec- to Co+3 after desorption of H2, whereas in the case of CoS2 no
trocatalytically high-active, and long-term durable in acidic such an analogous change was observed in ΔGH*. Chen et al.
environments, which makes them an interesting class of poten- studied the effect of nitrogen anion on the enhancement of
tial catalysts for HER.[68,69] However, their HER activity and HER activity of CoS2.[72] The porous NWs of CoS2 decorated
conductivity are still far from satisfactory than those of com- with N-anion on CC (N-CoS2 NW/CC) were synthesized from
mercial state-of-the-art catalyst due to a small number of active Co(OH)F/CC and thiourea powder (as a source of N and S)
surface sites.[69] Enhancing the conductivity and increasing in tube furnace at 500 °C in Ar atmosphere. For comparison,
the number of exposed active surface sites are effective ways CoS2 NW/CC was also synthesized. The N-CoS2 NW/CC deliv-
to increase their HER activity.[68,69] In this regard, many efforts ered j = 50 mA cm−2 at η = 152 mV which was much smaller
have been made to improve their HER activity by optimizing than η = 245 mV for CoS2 NW/CC, indicating that the N-atoms
Figure 8. a) LSV curve of CoPS film on graphite, CoPS NWs on graphite and CoPS nanoplates on carbon paper electrode. b) durability of the as-
synthesized catalysts. c) Free-energy diagram for adsorption and desorption of H+ and H2 on the Co site and P site of CoS and CoPS. Reproduced with
permission.[71] Copyright 2015, Springer Nature.
facilitated the synergistic regulation of the electronic struc- Ni2+δOδ(OH)2−δ growth on the 1T-MoS2 surface via the reaction
ture, active sites, and reaction dynamics of CoS2. To evaluate between NH4HCO3 and NiCl2 in 1T-MoS2 ethanol suspension.
the high HER activity of N-CoS2NW/CC compared to CoS2NW/ The optimized 1T-MoS2/Ni2+δOδ(OH)2−δ displayed high HER
CC, the Cdl measurements were performed. The N-CoS2 NW/ activity (η10 = 73 mV with ζ = 75 mV dec−1 and 30 h stability)
CC possessed enormously high Cdl of 565.5 mF cm−2, which compared to 1T-MoS2 in 1 m KOH solution. The high HER
was ≈1.9 times larger than that of simple CoS2 NW/CC hybrid activity of 1T-MoS2/Ni2+δOδ(OH)2−δ is ascribed to a bifunctional
(292.3 mF cm−2). The high HER activity of N-CoS2NW/CC mechanism, in which Ni2+δOδ(OH)2−δ promoted adsorption and
compared to CoS2 NW/CC was further confirmed from DFT dissociation of water molecules to provide H+ for H2 generation
calculations. The ΔGH* at a Co site in N-CoS2NW/CC was on the MoS2 surface. The modification of Ni-surface with het-
much smaller (≈0.5 eV) than that at a Co site in CoS2NW/CC eroatoms such as S, N, and P represents an interesting strategy
(≈3.1 eV), demonstrating that the H+ and H2 adsorption and to tune its structural, chemical, and electronic properties to
desorption on the CoS2 surface were optimized after incorpo- attain high catalytic and electrocatalytic performance.[77] In this
rating N atoms in CoS2. Liu et al. synthesized NPs of cobalt instance, Zhao and co-workers synthesized Ni NPs modified
phosphosulfide grown on CNTs (CoS/P/CNT) as a highly active with N atoms (Ni–N) through vapor phase-NH3-hydrothermal
HER electrocatalyst.[73] This catalyst exhibited small η10/100 = process. The optimized (Ni–N0.19) electrode exhibited high HER
48/109 mV with ζ = 55 mV dec−1 and je = 1.14 mA cm−2. This activity with η10 = 42 mV and large stability (η100) for 20 h in
high HER activity is ascribed to its unique structure such as 1 m KOH solution.[77a] To get more insight into the role of N
CoS/P anchored on CNTs so that electrons can quickly transfer on the HER activity of Ni–N0.19, the DFT calculations were
from applied external circuit to the NP/solution interface for performed, which revealed that the appropriate coverage of N
HER. atoms on Ni surface (Ni–N0.19) led to favorable ΔGH* kinetics
for H+ adsorption and the release of molecular hydrogen, while
high coverage of N (Ni–N0.59) weakened the H+ adsorption on
2.3. Nickel-Cluster-Based Electrocatalysts for HER the electrode surface and therefore decreased the HER activity.
In another study, an interface strategy of Ni3N and Ni on NF
2.3.1. Nickel and Ni-Alloying with Other Transition Metals was used to developing of an effective electrode for HER cata-
lyzing reactions.[77b] During synthesis, Ni was electrochemically
Nickel is the fourth most earth-abundant metal after Fe, Ti, deposited on NF, followed by heating in an ammonia environ-
and Zr which has been extensively used in hydrogenation and ment to make Ni3N/Ni/NF interfacial sites. The as-synthesized
reforming reactions.[74] Since the Ni element in the periodic Ni3N/Ni/NF exhibited enhanced HER activity with η10 = 12 mV
table has the same group with highly electrocatalytically active and 50 h stability at η10 in 1 m KOH solution. To understand
Pt, the electronic and structural parameters of Ni-based material the high HER activity of Ni3N/Ni/NF, the DFT calculations
and their relation with electrochemical HER have gained great were performed. The closed valves of ΔGH* to 0 eV at these
interest. Currently Raney Ni is used as an industrial catalyst for two positions of Ni3N/Ni (0.01 and −0.07 eV) indicated that the
electrochemical hydrogen production from alkaline solution unique geometrical and electronic structures of Ni3N/Ni inter-
which operates well at large current densities (500 mA cm−2).[75] facial sites provided large accommodation for H+ adsorption
Although Raney Ni has numerous advantages such as low cost, and also facilitated the desorption of molecular hydrogen from
high surface area and stability, it required large overpotential the electrode surface during the HER process.
(η500 = ≈300–500 mV) with ζ = ≈90–120 mV dec−1 in 30 wt% Ni as a HER catalyst in the above-mentioned structure and
KOH solutions.[75] Therefore, developing Ni-based electrocata- morphology showed considerable HER activity. However, the
lysts that generate hydrogen fuel at low overpotential is critical HER activity and stability can be further improved by alloying
for industrial scale applications. For efficient-catalyzing HER two different metals, as the bimetallic catalysts have often
reaction, the Ni-base catalysts could be designed in different distinct chemical and electronic properties compared to their
structure and morphology. Traditional HER activity of a spe- parent metals and may show superior performances.[74a,78]
cific metal can be improved by increasing the surface areas Among bimetallic alloys, Pt-based materials are the most
of the catalyst via designing highly porous nanostructures reported catalyst, however, high price and scarcity of Pt limit
(NS, NW, nanorod, or NP), introducing O-vacancies, utilizing their industrial scale applications.[74a,78] Therefore, significant
MoS2 NS, graphene, CNT or carbon fiber as support.[74b,76] For attention of alloying turned toward low-cost alternative metals
example, Zhang et al. reported NiO nanorods with abundant (Fe, Co, Ni, etc.), which has almost similar chemical and elec-
oxygen vacancies (denoted NiO NRs -Ov) as a HER electrocata- tronic properties to that of Pt for different reaction process.[74a]
lyst through a cation exchange approach.[76a] The experimental In fact, Ni has high alloying efficiency in different mass ratios
and DFT studies demonstrate that the electronic and chemical with many other transition metals, which makes it easier to
structure of NiO NRs was effectively modified with O-vacancy design composition-dependent wide-ranging Ni-bimetallic
engineering; as a result, the synthesized NiO NRs -Ov showed systems for HER catalytic reactions.[79] Feng et al. synthesized
η10 = 110 mV with ζ = 100 mV dec−1 and high stability in 1 m bimetallic cobalt−nickel nitrides derived from MOFs (CoxNiyN)
KOH solution. Zhang and Liang reported that the hybridiza- as a HER electrocatalyst, which displayed η10 = 102.6/92 mV
tion of 0D nickel hydr(oxy)oxide NPs (Ni2+δOδ(OH)2−δ) with in basic/acidic solution.[79a] Zhou et al. synthesized NiSe2 as
metallic 2D MoS2 NSs (1T-MoS2) can significantly improve a HER electrocatalyst from NF through simple acid treatment
the hydrogen production from alkaline HER reaction.[76b] The and selenization approach.[79b] The optimized NiSe2 showed
hybridized 1T-MoS2/Ni2+δOδ(OH)2−δ was synthesized by in situ η10 = 57 mV with ζ = 43 mV dec−1. The high HER activity
is attributed to NiSe2 porous structure which facilitated the increasing its P content.[82,83] Liu and coworkers demonstrated
charge/mass transport during HER reactions. that the high HER activity from NixPy can be achieved by simply
The HER is usually performed in acidic or basic solution, growing it in 3D-NF.[84] 3D-NF having porous hierarchical
among which HER in basic solution is more sluggish, as their structure and large specific surface area can significantly reduce
kinetics reactions are slowed by an additional water dissocia- the diffusion path length of ions and improve the electronic
tion.[80] Compared to a basic solution, the HER in neutral media and ionic conductivity during HER process. In Liu’s work, the
is more challenging because the main issue regarding the HER hybrid NS of Ni5P4 and Ni2P was obtained from simple phos-
in neutral pH along with high water dissociation energy is phidation of 3D-NF at 500 °C using the red phosphorus as a
reactant switching: hydroxyl ions are the reactants in alkaline phosphidation source and the N2 gas for inert atmosphere in
pH, whereas to achieve a considerable reaction rate in neutral tube furnace.[84] The catalyst generated η100 = 200 mV with high
solution, water must act as a reactant. Therefore, the HER in stability. The high HER activity of this catalyst is attributed to
neutral solution requires the electrocatalyst which can effec- the in situ derivation of Ni5P4–Ni2P and their 3D hierarchical
tively reduce the energy barrier for neutral water dissociation. porous structure which facilitated the charge/mass diffusion
If the HER process in neutral environments could be achieved, during HER. Another strategy for high HER activity from NixPy
it would be of great interest in the industrial-scale H2 produc- is the modification of its electronic structure by doping with
tion. The HER in neutral solution will utilize the active transi- p- or d-block metals so that the Hads energy and kinetic energy
tion metal-based catalysts that are unstable in acidic solution. barriers for H2 evolution might be reduced. Lado et al. reported
Additionally, water electrolyzer working in neutral solution will Al-doped Ni–P (AlNiP) which delivered η10 = 111 mV compared
potentially enable the direct usage of seawater into hydrogen to pure NiP (η10 = 175 mV).[85] The high HER activity of AlNiP
production without pH maintenance. In this instance, Sar- is attributed to Al doping which modified the density of states
gent group designed electrocatalyst composed of CrOx/Ni sites of NiP to reduce the energy barrier for HER kinetics. Simi-
doped onto Cu surface (denoted CrOx/Cu–Ni) that catalyzed larly, Li et al. designed Co–Ni–P NWs which delivered smaller
HER efficiently in neutral solution.[80] The Ni and CrOx sites η10 = 68 mV with ζ = 56.4 mV dec−1 and high stability.[86] The
in CrOx/Cu–Ni have strong binding energies for H+ and OH− high HER activity is attributed to the synergistic effect of Fe/Co
groups, respectively, accelerated efficiently the dissociation of and porous morphology of NW, which facilitated the charge/
water into H+ and OH−, which react later on the Cu surface to mass transport between electrolyte and catalyst as well as the
generate H2. As a result, the synthesized CrOx/Cu–Ni catalyst release of hydrogen gas bubble from the electrode surface.
exhibited η10 = 48 mV with ζ = 64 mV dec−1 and long term sta-
bility in neutral solution.
2.3.3. Nickel Sulfides
2.3.2. Nickel Phosphides Nickel sulfides exist in different crystalline phases such as
nickel sulfide (NiS), nickel disulfide (NiS2), and nickel sub-
In transition metal phosphides (TMPs), where P atoms sulfide (Ni3S2).[87] Among these three crystalline phases Ni3S2
doped into crystal lattices of TM, the P atoms are negatively has been widely investigated toward HER catalysis due to
charged due to its higher electronegativity than the central its high conductivity and electrochemical performances.[87]
metal atoms. The negatively charged P atoms in TMPs play a For example, Jiang et al. reported three crystalline phases
critical role in initial Volmer step (H+ adsorption on the catalyst (NiS, NiS2, and Ni3S2) as HER electrocatalysts.[87a] The HER
surface) of HER.[32,81] On the basis of this basic observation the activity of these three electrocatalysts in the basic solution was
TMPs having more P content will adsorb more H+ on the cata- in the order of NiS < NiS2 < Ni3S2. Feng et al. reported Ni3S2
lyst surface in the initial Volmer step. In the second step (Tafel NS on NF,[87b] which showed η10 = 170 mV with constant j in
or Volmer) which is dependent on the Hads availability on cata- 200 h chronoamperometric response. Recently, Tian et al. syn-
lyst surface (see the Introduction section for details), the cata- thesized hollow microspheres of Ni3S2 on NF, which displayed
lyst surface having more Hads will have a more facile Tafel or η10 = 77 mV, ζ = 67 mV dec−1 and constant j for 25 h in 1 m
Volmer step for H2 production. For example, Liu and his cow- KOH solution.[87c]
orkers compared the HER activities of Ni12P5, Ni2P, and Ni5P4 The Ni3S2 crystalline phase shows considerable HER activity.
nanocrystals in 0.5 m H2SO4 solution.[82] Among these catalysts, However, the HER activity of nickel-sulfide based catalysts can
the Ni5P4 (high P content of 44%) exhibited better HER activity be further improved by doping or alloying it with other tran-
than Ni12P5 and Ni2P. The high HER activity of this catalyst is sition metals.[88] In single metal sulfide, the hydrogen atoms
ascribed to active Ni+4 and P−5 in Ni5P4 NCs. Similarly, Wang are bonding too strongly with sulfur sites of the catalyst in the
et al. synthesized flower-like crystalline structures of Ni2P and Volmer step which makes the Tafel or Heyrovsky steps (forma-
Ni5P4 and compared their HER activity in 0.5 m acidic solution of H2 from 2Hads or H+ + Hads on catalyst surface and their
tion.[83] The HER activities of Ni5P4 in both acidic and basic desorption from catalyst surface) very difficult.[88a,c] In bimetallic
solutions (η10 = 35.4 and 47.1 mV, respectively) were much sulfides, the electron transfer from metal to metal sulfide can
better than that of Ni2P (η10 = 62.2 mV). The experimental optimize both Volmer and Tafel or Heyrovsky steps by changing
observation was supported by the DFT results that the Ni5P4 the density of electron distributions of electrocatalysts.[88a,b] For
has smaller ΔGH* (0.152 eV) compared to Ni2P (0.182 eV). The example, Feng et al. synthesized Ni3S2 nanotubes decorated
experimental and DFT studies of Liu et al. and Wang et al. with Cu nanodots on carbon fibers (CuNDs@Ni3S2NTs/CFs)
showed that the HER activity of NixPy can be enhanced with as a HER electrocatalyst.[88a] This hybrid showed η10 = 128 mV
with ζ = 76.2 mV dec−1 in alkaline solution, which was smaller electrocatalysts for HER catalyzing reactions.[91] Unfortunately,
than Ni3S2 NTs-CFs (η10 = 128 mV). The high HER activity of Mo in the zero-valence state is known to be an inactive catalyst,
CuNDs@Ni3S2NTs/CFs compared to Ni3S2 NTs-CFs is ascribed whereas they have many applications, once converted into oxide,
to the electron transfer from Cu to Ni3S2 which makes the nitride, phosphide, carbide, sulfide, or alloyed with other tran-
Ni3S2 more negatively charged. The higher electron density on sition metals. The electrochemical performance of the above
the sulfur sites of Ni3S2 makes the SH* bonds weaker, thus mentioned Mo-based materials can be further enhanced by
promoting the Heyrovsky step efficiently. Liu group synthe- nanostructure and defect engineering or doping onto/into con-
sized Fe-doped NiS2 NSs which displayed η10 = 121 mV with ductive carbon frameworks/CNT.[92] The Mo-phosphide (MoP)
ζ = 37 mV dec−1 and stable HER performance after 1000 CV which has high thermal and electrical conductivity exhibits high
stability test in 0.5 m H2SO4 solution.[88b] Similarly, Yang and HER activity compared to Mo having a zero-valence state.[91a,93]
co-workers synthesized Fe-NiS ultrathin NSs as an acidic HER In this instance, Xiao et al. compared the HER activity of
electrocatalyst which showed η10 = 105 mV, ζ = 40 mV dec−1, Mo and MoP, among which MoP showed high HER activity
and high stability.[88c] Qu et al. developed vanadium doped (η10 = ≈135 mV with ζ = 54 mV dec−1) than Mo (η10 = ≈ 500 mV
Ni3S2 NW on NF, which showed η10 = 68 mV and stability for with ζ = 92 mV dec−1).[93] Wang and coworkers reported the
8000 CV cycles in basic solution.[89] Recently, Wang et al. syn- hybrid of MoP/CNT as HER electrocatalyst.[91a] The optimized
thesized platinum–nickel/nickel sulfide NWs (Pt3Ni/NiS NWs) MoP/CNT (MoP/CNT-700) displayed η10 = 83/86 mV with
as a HER electrocatalyst for basic media.[90] The catalyst dis- ζ = 60/73 mV dec−1 in 0.5 m H2SO4/1 m KOH solutions. The
played j = 37.2 mA cm−2 at η = 70 mV in 1 m KOH, which was HER activity of MoP/CNT-700 is contributed to the CNT incor-
≈9.7 times better than state-of-the-art commercial 20% Pt/C. To poration which not only increases the electrical conductivity
get more insight into the role of individual components (PtNi but also reduces the agglomeration of MoP NPs that provided
and NiS in Pt3Ni/NiS NWs) for superb HER activity, the energy more active sites during HER catalyzing reactions. In another
barrier for OHH bond dissociation to Hads on Pt (111) and work, ultrafine NPs of MoP (≈3.15 nm diameter) were uni-
NiS (100) surfaces was calculated (Figure 9a). This energy bar- formly distributed on N/P co-doped carbon NSs (MoP/NPG),
rier on NiS surface (0.32 eV) was much lower than that of Pt, which showed η10 = 90/115 mV in acidic/basic solutions.[94]
indicating that NiS has a more suitable surface for water dis- The HER activity of the as-synthesized MoP/NPG is attributed
sociation than Pt. Second, the ΔGH* for combining Hads to H2 to uniformly distributed MoP NPs on N/P co-doped carbon NSs
was calculated on NiS (100), Pt3Ni (111), and Pt (111) surfaces which provided more active sites during HER catalyzing reac-
(Figure 9b). The ΔGH* of NiS (−0.56 eV) demonstrated that tions. Similarly, Feng and coworkers encapsulated MoP in a P,
the HER kinetics (Hads to H2) on the NiS surface was more Mo codoped carbon layer (denoted MoP@C), which showed
sluggish than that of Pt surface (−0.09 eV) and Pt3Ni surface higher HER activity (η10 = ≈49 mV with ζ = 54 mV dec−1 and 12
(≈−0.088 eV). Thus the DFT calculations reflect that the out- h stability in 1 m KOH) compared to the above-mentioned Mo–P
standing alkaline HER activity of Pt3Ni/NiS NWs originated catalysts.[95] The high HER activity of MoP/NPG has resulted
from the synergistic cooperation of Pt and NiS. from the MoC and PC bonds at the MoP and carbon layer
interfaces which modulated the MoP@C band structure and
facilitated the transfer, accumulation and delocalization of elec-
2.4. Molybdenum-Cluster-Based Electrocatalysts for HER tron for better HER catalyzing reactions.
Recently, molybdenum diselenide (MoSe2), whose struc-
2.4.1. Molybdenum and Molybdenum-Alloying ture is composed of 2D-graphene-like Se–Mo–Se layers held
with Other Transition Metals together by weak van der Waals forces have received con-
siderable attention in energy conversion HER reactions and
Molybdenum (Mo)-based materials, due to their low cost and energy storage sodium and lithium-ion batteries.[96] Theoretical
rich redox chemistry, have attracted tremendous interest as analysis has predicted that the active MoSe2 edges have lower
an anode material for lithium-ion batteries and as promising free energy for H+ adsorption, representing that the MoSe2
Figure 9. a) Energy barrier for water dissociation: NiS (100) surface (red) and Pt (111) surface (black). H2O is the initial state of reaction, TS is transi-
tion state, and (H + OH) is the final state from water dissociation. b) ΔGH* barrier for HER on NiS (100) surface (green), Pt (111) surface (black),
and Pt3Ni (111) surface (red and blue) at 0 V. The white, red, yellow, light blue, and dark blue balls represent H, O, S, Ni and Pt atoms, respectively.
Reproduced with permission.[90] Copyright 2017, Springer Nature.
edges will have favorable sites for H+ adsorptions, however, have large electron donating ability in HER reaction compared
the bulk MoSe2 can hardly catalyze the HER reactions due to to the parent metal.[102b] Similar to other metal nitrides, the
its low number of active catalytic sites and insufficient elec- molybdenum nitride has also a strong ability for HER reac-
trical conductivity.[92a,96b,97] The structure of MoSe2 for effi- tion. For example, in the work of Song and Yuan, mesoporous
cient HER catalyzing reaction can be modified through the Mo2N/NC composite was synthesized as a HER electrocatalyst
following valid strategies: increasing the active sites by engi- which showed η10 = 217 mV with ζ = 115.9 mV dec−1 in 0.5 m
neering the MoSe2 in unique nanostructures, activating its H2SO4 solution.[102a] The HER activity of molybdenum nitride
inert basal plane, exfoliating the stacked layers of MoSe2 into can be further improved by alloying it with other transition
a few layers or hybridizing with a conductive matrix.[92,97] For metal.[102b] In the work of Zhang et al., nickel molybdenum
example, Bonaccorso and co-workers reported the hydride of nitride (NiMoN) supported on carbon cloth was synthesized
single-wall CNTs and few-layer MoSe2 flakes (SWCNTs/MoSe2) which showed η10 = 109 mV with ζ = 95 mV dec−1 and 36 h
as HER electrocatalyst.[97] The optimized SWCNTs/MoSe2 stability in 1 m KOH solution.[102b] The HER activity and sta-
exhibited η10/100 = 100/200 mV with ζ = 63 mV dec−1 and bility of the as-synthesized NiMoN electrode is attributed to the
je = 0.203 μA cm−2. In another study, the N dopant and IT phase following factors: i) porous hierarchical structure of electrode
of MoSe2 were introduced into 2H-phase MoSe2–vertical gra- which facilitated the electrode/electrolyte contact and transport
phene (VG) nanoflake arrays (denoted MoSe2/VG) through the of reactant and product; ii) the intimate contact between sup-
annealing process in NH3 atmosphere.[98] In a typical synthesis port and NiMoN granted large stability; and iii) bimetal nitride
process, the VG arrays were first deposited on the carbon cloth alloys generally have superior HER electrocatalytic activity due
through a chemical vapor deposition method. In the second to synergistic effect among bimetal atoms.
step the nanoflakes of MoSe2 were grown along the whole VG
(MoSe2/VG) through the hydrothermal process. Finally, the
MoSe2/VG were converted into N-doped MoSe2/VG (denoted 2.4.2. Molybdenum Sulfides
N-MoSe2/VG) through annealing in NH3 environment at
300 °C. The HR-TEM, XRD, and Raman analyses showed that Molybdenum disulfide (MoS2), which is abundant, inexpensive,
the MoSe2 existed in both IT and 2H phases, representing that highly catalytic-active, and long-term durable in strong basic
during annealing process some of the 2H-MoSe2 converted and acidic solutions, has been recognized as a most promising
into IT-MoSe2. The as-synthesized N-MoSe2/VG displayed catalyst to replace Pt for electrochemical H2 production.[103,104]
η10 = 98 mV with ζ = 49 mV dec−1 and long-term durability The structural unit of MoS2 is composed of S–Mo–S layers
in 0.5 m H2SO4 solution. The HER activity of N-MoSe2/VG is which interact with each other by weak van der Waals forces,
attributed to mixed IT and 2H phases of MoSe2 and dopant N and exist in several possible crystal structures such as 1T (octa-
that enhances the charge transfer and electronic conductivity hedral structure), 1T2 (distorted octahedral structure), and 2H
during HER process. (hexagonal structure).[103–105] Among these structures 2H phase
Molybdenum oxide (MoO3) is environmentally benign low- of MoS2 is more stable at room temperature and is most com-
cost transition metal with high stability. It has been widely monly used as an electrocatalyst for HER.[105] DFT calculations
employed in capacitors, lithium-ion battery and electroca- and experimental evidences have proven that the sulfur edge
talysis reaction.[91b,99] For example, in the work of Luo et al., sites of MoS2 are active for HER, because they possess favorable
mesoporous molybdenum oxide (MoO3) was synthesized, hydrogen adsorption free energy (ΔGH* = 0.08 eV),[106] while its
which showed η10 = 140 mV with ζ = 56 mV dec−1 and 12 h basal plane is catalytically inert (ΔGH* = 2 eV).[107] To exploit the
stability in 0.1 m KOH solution.[100] The HER activity of the HER performance of MoS2, great efforts have been devoted to
as-synthesized MoO3 is contributed to its mesoporous struc- making the MoS2 catalyst with more exposed active edge sites,
ture which facilitated the charge transfer during HER pro- modifying them or generating defective sites in the basal plane
cess. The HER performance of MoO3 can be further improved of MoS2 for high HER activity. For example, Ye et al. deter-
by alloying it with other transition metal because the binary mined the correlation between the number of defects in MoS2
alloys exhibit high HER activity and durability compared to and their HER performance.[103] First, they synthesized pristine
single-metal based catalyst.[99,101] In the work of Chen et al., MoS2 by CVD process. To create triangular holes and cracks in
a hybrid of MoNi4/MoO3-x nanorod with 3D open structure the MoS2 two different strategies of H2 treatment and plasma
was designed from Ni foam and (NH4)6Mo7O24·4H2O salt exposure were used. A huge number of cracks with irregular
using hydrothermal and calcination approaches.[99] The as- shapes were generated in monolayer MoS2 by plasma treat-
synthesized MoNi4/MoO3-x exhibited η10/500 = 17/114 mV with ment, while nanometer and micrometer scale triangular shaped
ζ = 36 mV dec−1 and 20 h stability in 1 m KOH solution. The holes were formed by H2 annealing method. These defect sites
high HER activity of MoNi4/MoO3-x has resulted from the syn- in MoS2 led to high improvement in the HER performance
ergistic effect of MoO3-x and MoNi4 which reduced the water compared to pristine MoS2. Furthermore, the MoS2 activated
dissociation energy and facilitated the charge transferred reac- through H2 annealing was better in HER performance with
tion during alkaline HER reactions. more defects compared to the O2 plasma method. Kim et al.
Transition-metal nitrides have attracted great attention in developed an effective strategy for catalytic activation of the
HER catalysis reaction due to their low electrical resistance, basal plane of pristine MoS2.[104] First, TiO2 islands were depos-
large melting point, superior mechanical strength and excel- ited on the basal plane of pristine MoS2 by ALD technique, and
lent corrosion stability in both acidic and basic solutions.[102] then the deposited TiO2 was dissolved on the surface of MoS2
Moreover, the metal nitrides have modified d-band; therefore by in-situ electrochemical activation method, which resulted in
distortions on the basal planes of MoS2. The catalyst was supe- MoS2. The high HER activity of MoS2 foam compared to pris-
rior in HER activity with ζ = 80–90 mV dec−1 compared to pristine MoS2 was due to the following factors: i) the macroscale
tine MoS2 (ζ = 180 mV dec−1). Qi et al. showed from a combined mesoporous MoS2 foam can effectively facilitate the transport
experimental and DFT study that the adsorbed Pd on the basal of H3O+/H2 and the surface accessibility of MoS2, and ii) the
plane of defect-rich MoS2 (DR-MoS2) modulates the electronic vertical nanoscale growth around mesopores increases the
state and active catalytic sites of MoS2 for enhanced HER abundance of active edge sites for catalytic reactions. Second,
activity.[108] Three different decoration strategies including Co was doped into MoS2 foam for further enhancement of cata-
assembling spherical NPs, direct epitaxial growth, and assem- lytic activities. The optimized Co-doped-MoS2 foam (Co con-
bling Pd nanodisks were used to adsorb Pd on the basal plane tent: 16.7%) showed impressive HER performance with η10 =
of DR-MoS2. It was found that the Pd nanodisks were only dec- 156 mV, ζ = 74 mV dec−1 and high stability compared to pris-
orated specifically on the basal plane of DR-MoS2. Then, the tine MoS2. The high HER activity of Co-doped-MoS2 foam was
basal plane of modified Pd-DR-MoS2 has a low hydrogen further confirmed from the ΔGH* values of pristine MoS2 and
adsorption free energy (ΔGH* = 0.01 eV) much smaller than Co-doped-MoS2 foam. The ΔGH* value of pristine MoS2 at basal
pristine MoS2 (ΔGH* = 1.8 eV), indicating that the energy bar- plane was about 2 eV, far away from the optimal 0 eV, while in
rier required to drive the HER process is very small. Finally, the case of Co-doped MoS2 foam, the ΔGH* value was almost
they checked experimentally the HER activity of Pd-DR-MoS2 close to 0 eV. To modify the electronic properties of MoS2 for
in 0.5 m H2SO4, which exhibited ηo = 40 mV with high dura- enhanced HER process, Zeng and co-workers constructed
bility, large je = 426.58 μA cm−2 and ζ = 41 mV dec−1. To accel- MoS2-black phosphorus (BP) NSs (MoS2−BP) through the dep-
erate the sluggish kinetics of HER through MoS2 osition of catalytically active MoS2 on the NSs of black phos-
electrocatalysts, Ni atoms were doped into MoS2 edge by a phorus.[111] In the case of MoS2−BP NSs, efficient transfer of
simple hydrothermal approach.[109] The catalyst exhibited high electron from BP to MoS2 was obtained due to smaller Fermi
HER activity with η10 = 98 mV, ζ = 60 mV dec−1, high level of MoS2 than BP. The catalyst exhibited remarkable HER
je = 0.98 mA cm−2, large TOF of 0.32 s−1 and robust durability with small η10 = 85 mV and ζ = 68 mV dec−1. Due to electron
for 100 h in 1 m basic solution. This high HER activity was fur- transfer from BP and their accumulation on MoS2, the MoS2−
ther investigated from the kinetic energy barrier of Volmer step BP displayed je = 0.66 mA cm−2 which was 22 fold higher than
(ΔGH2O for water dissociation step), the adsorbed free energy of that of pristine MoS2. More recently, Liu et al. explored the
OH−(GOH−) and the combination of intermediates H*s into H2 effect of P doping on the catalytic activity of inert basal plane of
(ΔGH*, Heyrovsky or Tafel step). The pristine MoS2 exhibited MoS2.[107] Both experimental and theoretical observation dem-
high ΔGH2O (≈1.17 eV) and very low GOH− (≈−5.24 eV). Substi- onstrated that the HER activity and conductivity of P-MoS2 was
tuting a Mo atom with a Ni along the MoS2 edge decreased the impressively improved over pristine MoS2. It delivered low η10 (
ΔGH2O dramatically to 0.66 eV and increased the GOH−1 to = 43 mV) with small ζ (= 34 mV dec−1) and high TOF (=1.4 s−1)
−3.46 eV. These dramatic changes in ΔGH2O and ΔGH* values in 0.5 m H2SO4. The calculated ΔGH* value for pristine MoS2
for Ni–MoS2 suggest that the sluggish kinetics of the water dis- was 2.2 eV, much far away from the optimized 0 eV, while in
sociation and desorption of OH− from catalyst surface can be the case P-MoS2, the calculated ΔGH* at S-basal plane was only
promoted effectively after the Ni doping into the edge of MoS2. 0.43 eV, showing that the basal plane of MoS2 after P doping
Also, the ΔGH* of Ni-MoS2 (–0.07 eV) was much lower than was impressively activated for catalytic reactions. Moreover, the
pristine MoS2 (0.60 eV), which shows that the combination of doped P acted as newly created activated sites with ΔGH*
intermediates H* into H2 can occur spontaneously in thermo- (0.004 eV) very close to 0 eV. More interestingly, the P-MoS2
dynamics. Similarly, Xue et al. activated the S-edge and basal possessed expanded interlayer spacing (0.91 nm) compared to
plane of 2H-MoS2 by P doping.[105] Due to the difficulty of P pristine MoS2 (0.65 nm), and the calculated ΔGH* for this
doping into the crystal structure of MoS2, oxygen codoping was region was −0.09 eV. This expanded interlayer spacing with
utilized to dope P successfully into the basal plane of 2H-MoS2. smaller ΔGH* can effectively promote the H+ adsorption and H2
The HER activities of the P-2H-MoS2 at basal plane were evalu- desorption for better HER process. Similarly, Xiao et al. investi-
ated from the ΔGH* values of S atoms surrounded by doped P gated the effect of nitrogen doping on the S-edge and basal
atoms. The calculated ΔGH* value of S atom at basal planes plane of MoS2 for better HER process.[112] A simple one-step
after P doping was much smaller (0.3 V) than that of pristine sintering method was used to synthesize N-MoS2 electrocatalyst
2H-MoS2 (2.08 eV), indicating that the HER activity at basal for best HER performance. The catalyst displayed small η100 =
planes of 2H-MoS2 was significantly improved with P doping. 121 mV with ζ = 41 mV dec−1 (Figure 10a,b) and impressive
Furthermore, the ΔGH* values of P-doped S-edge and Mo-edge stability for 500 CV. To explore the functions of dopants N
were also evaluated, which was much closer to 0 eV (−0.12 eV) toward enhanced HER performance, the relationships of
compared to pristine S-edge (−0.79 eV), indicating that the dopants N with i) the number of catalytic active HER sites and
HER was also enhanced at S edge of 2H-MoS2 after P doping. ii) N-doped MoS2 conductivity were investigated from the Cdl
To confirm the calculation results, the P-doped 2H-MoS2 was and TOF. Figure 10c,d shows that Cdl increases from 5 to 21
tested for HER activity, which exhibited high HER activity with mF cm−2 for N-MoS2-1 (5% N) to N-MoS2-3 (8% N). Similar
ηo (130 mV) and small ζ (49 mV dec−1) compared to pristine trend was also observed for TOF (N-MoS2-1 = 0.9 s−1,
2H-MoS2. Deng et al. introduced a multiscale structural and N-MoS2-3 = 4 s−1) shown in Figure 10e, suggesting that the
electronic control of pristine MoS2 to promote the HER process number of active HER sites increases with increasing the
synergistically.[110] First, mesoporous MoS2 foam was fabricated amount of N doping. To get deep insights into the function of
with high HER activity (η10 = 210 mV) compared to pristine dopants N in MoS2, the energy formation of a single substituted
Figure 10. a) LSV polarization curves. b) Tafel plots of pristine MoS2, platinum, and N-MoS2. c) double-layer capacitance (Cdl) for N-doped MoS2 at
different N concentrations. d) CV curves of GCE and N-MoS2 in pH 7 from −0.2 to −0.4 V versus RHE at scan rate of 50 mV s−1. e) Calculated TOF
of N-MoS2. f) HER energy profile for different S sites in S-edge of MoS2 with different N concentrations [S1: N-MoS2-1 (5% N), S2: N-MoS2-2 (6%N),
NS1: N-MoS2-3 (8%N). Reproduced with permission.[112] Copyright 2016, John Wiley and Sons.
S by N (NS) was calculated in different MoS2 structures activity originated from the following reasons: 1) The Mo2C NPs
including basal plane and edges of MoS2 (Mo-edge and S-edge). with small size are uniformly embedded in the carbon shells,
The formation energy of basal plane, dopants N in S-edge, and helping in high exposure of active catalytic sites during HER
Mo-edge were −2.3, −3.2, and −2.8 eV, respectively. These nega- application. 2) The P and N in the carbon structure improve the
tive formation energies suggest that N can be easily doped into charge distribution on the hybrid structure of Mo2C, also the
MoS2 matrix and the dopant NS will be more stable in the robust interaction between NPC/NP-rGO and Mo2C provides
system. The calculated ΔGH* on pristine S edge at hydrogen resistance free path for the fast transfers of electron and proton,
coverage of 1.00 and 0.25 were −0.71 and −0.78 eV (Figure 10f). promoting impressively the Heyrovsky or Tafel step. 3) The
These negative values suggest a difficult desorption of hydrogen unique structure of this hybrid is favorable for the fast trans-
on the pristine S-edge, making the S-edge inactive in the HER port of reactants for better HER process. Yan group synthesized
process. After substituting one N atom at the S tom in the edge a highly active and stable 3D-hierarchical microporous Mo2C
of MoS2, the calculated ΔGH* changed dramatically to 0.06 eV (3D-HP-Mo2C) HER catalyst by template-assisted process.[114] In
at hydrogen coverage of 0.25 (Figure 10f), which revealed that a typical synthesis process, N-doped-C framework with a high
the dopant NS successfully activated the S-site in MoS2 edge for specific surface area (2330 m2 g−1) was first synthesized from
the HER performance. solvothermal treatment of pyridine and sodium precursors. It
was then converted into 3D-HP-Mo2C through simple calcina-
tion approach. The catalyst exhibited remarkable HER activity
2.4.3. Molybdenum Carbides with η10 = 97 mV, ζ = 60 mV dec−1, and je = 0.28 mA cm−2 in
0.5 m H2SO4 solution. This high catalytic activity can be attrib-
Molybdenum carbides (MoxC) have attracted enormous atten- uted to its high surface area and microporous structure, which
tion from HER research because of its similar d-band electronic provided resistance free path for past proton transport toward
structure to that of Pt, low-cost, and high efficiency toward the interior pore surface of the catalyst during the HER process.
hydrogen production.[113,114] The HER activity of MoxC can Cheng et al. synthesized MoC nanoribbons encapsulated in
be enhanced significantly by improving its electron conduc- N-doped carbon nanolayers (denoted as MoC@NC nanoribbon)
tion through nanostructure and heterostructure engineering, by simple calcination approach.[115] The catalyst had not only
phase control, intercalation, and doping.[113,114] For example, abundant catalytic active sites and a multielectron pathway
Li et al. fabricated a 2D hybrid of Mo2C encapsulated by for the efficient charge/mass transportation, but significantly
P, N codoped carbon shells and P, N codoped rGO (Mo2C@ accelerated the hydrogen desorption from the electrode surface
NPC/NP-rGO).[113] This hybrid exhibited outstanding HER with high HER performance in both acidic and basic solutions.
activity with 0 mV onset potential, small ζ = 33.6 mV dec−1 and This catalyst exhibited ηo = 24 mV with ζ = 54 mV dec−1 in
long-term durability in 0.5 m H2SO4 solution. This high HER acidic solution and ηo = 36 mV with ζ = 51 mV dec−1 in basic
solution. Recently, Lu et al. synthesized Mo2C encapsulated in sites; 3) the high surface area and nanoporous structure of the
N-doped porous carbon (Mo2C@2D-NPC) as an efficient elec- synthesized catalyst provide an effective and active path.
trocatalyst for HER in both acidic and basic solutions by simple The MoxC doped with nonmetal or integration of Mo with
and highly efficient interfacial and calcination approach.[116] In conducting carbon matrix shows high HER activity. However,
a typical synthesis protocol, the Mo4O13−2 anchored polyani- the more negative ΔGH* of MoxC (due to high-density unoccu-
line (PANI) NSs (denoted by Mo@2D-PANI) was fabricated by pied d-orbitals of Mo) increases strong H adsorption on the cat-
in-situ polymerization using aniline as a monomer, GO as a alyst surface (Volmer step), but hampers the H* desorption (the
template, and Mo4O13−2 as a Mo source. The obtained Mo@2D- Heyrovsky or Tafel step).[119] The MoxC with electron-rich den-
PANI was then converted into Mo2C@2D-NPC through calci- sity to optimize the hydrogen adsorption/desorption step can
nation under argon/ hydrogen (5%) atmosphere. The catalyst further boost the HER process.[119] For example, Lin et al. devel-
exhibited very high HER activity with small η10 = 45 mV, small oped MoC-Mo2C hetero-NWs (H-NWS) as an effective HER
ζ = 46 mV dec−1 and high durability in 1 m KOH solution. In electrocatalyst, which was fabricated from MoOx–amine-NWS
acidic electrolyte it delivered η10 = 86 mV with ζ = 62 mV dec−1. through controlled carbonization approach.[119] The MoC–
The superior HER performance of Mo2C@2D-NPC was due to Mo2C-H-NWS was 1D heterostructures, composed of well-
the following aspects: 1) Mo2C with small size particles (5 nm) defined NPs with a large surface area and rich nanoporosity.
is uniformly embedded in carbon NSs, which insures a large This hybrid with optimized conditions delivered η10 = 126 mV
number of exposed catalytic active sites; 2) the derived carbon with a small ζ = 43 mV dec−1 in 0.5 m H2SO4 solution. The
matrix from PANI provides high electrical conductivity; 3) the HER activity of this catalyst was also tested in 1 m KOH solu-
robust interaction between NPC and Mo2C reduces the energy tion, which displayed η10 = 120 mV with small ζ = 42 mV dec−1.
barrier for HER. To get more insight into the outstanding HER The high HER performance was attributed to the moderated
performance of Mo2C@2D-NPC, the ΔGH* at different condi- electron distribution on the carbide surface, optimizing the
tions were calculated. The obtained ΔGH* for pristine graphene hydrogen binding to electrode surface for better HER. Similarly,
was 1.73 eV, indicating that it is an energetically poor candidate Shi et al. developed P-doped Mo2C at hierarchical carbon NWs
for HER. The calculated ΔGH* for graphene doped with pyri- (P-Mo2C at C-NWs) with optimized ΔGH*, from the carboniza-
dinic-N having one vacancy (named as Pyr.N3) or two vacancies tion of MoOx-phytic acid-polyaniline nanohybrids (MoOx–PA–
(Pyr.2VN3) was −2.04 and −1.37 eV, respectively, demonstrating PANI).[120] The P doping into Mo2C nanostructure efficiently
low catalytic HER activities. Due to these more negative ΔGH* increased the electron density at the Mo2C Fermi level, leading
for Pyr.N3 and Pyr.2VN3, the H* will be adsorbed very strongly to weakened MoH bonding strength toward promoted HER
to the surface, and so too large energy will be required for kinetics. This observation was further evaluated from DFT cal-
desorption of H* from the surface to form molecular H2. The culations that the negative ΔGH* on pure Mo2C (−0.26 eV) grad-
ΔGH* for Mo2C-graphene and Mo2C-N-graphene was 0.44 and ually increased with P doping due to transfer of electron and
0.65 eV, respectively, which were much lower than those of steric hindrance of P on the surface of Mo2C, representing the
pristine graphene and N-doped graphene. Moreover, the ΔGH* decrease in bonding strength of Mo and H. At optimized condi-
for Pyr.N3-Mo2C and Pyr.2VN3-Mo2C were −0.33 and −0.04 eV, tions, P-Mo2C (P: 2.9 wt%) exhibited benchmark HER activity
respectively, showing a favorable route for the H* adsorption with η10 = 89 mV, ζ = 42 mV dec−1, and high je = 0.18 mA cm−2.
and H2 desorption, which are in well accord with the experi- Similarly, Gao et al. studied the effect of cobalt doping on the
mental observations. Wang et al. synthesized Ni- encapsulated- electron density around the Mo2C Fermi level.[54c] The Co–
N-doped carbon vesicle modified by MoxC (MoxC-Ni@NCV) Mo2C was synthesized from simple annealing of Co modified
through a simple solid-state thermolysis method.[117] The XRD Mo3O10(C6H5NH3)2·2H2O. From XPS analysis it was found
and TEM analysis showed that the MoxC-Ni@NCV was com- that the peaks of Mo after Co doping shifted toward lower
posed of graphitic carbon, γ-MoC, β-Mo2C, and metallic Ni NPs. binding energy, indicating high electron density around the Mo
The as-synthesized MoxC-Ni@NCV exhibited η10 = 75 mV with atoms transferred from Co due to its lower electronegativity
small ζ = 45 mV dec−1, high je = 0.95 × 10−3 A cm−2, and long- than Mo. This observation was further confirmed from valance
term stability in 0.5 m H2SO4 solution. The high HER activity band (VB) approach using ultraviolet photoelectron spectros-
of MoxC-Ni@NCV is resulted from doped N that tuned the copy. Compared to pure Mo2C, the Co–MoC2 has one new peak
electron density of graphite surface and the synergistic effect at 3.45 eV due to the high electron density at the Fermi level
of γ-MoC with encapsulated Ni NPs. Chen et al. synthesized of Mo. As expected, this Co–MoC2 displayed very small η100 =
pomegranate like N-P-doped-Mo2C@C by simple polymeriza- 195/200 mV with small ζ = 44/39 mV dec−1 in 1.0 m KOH/0.5 m
tion and carbothermal reduction of pyrrole (Py) and phospho- H2SO4 solution.
molybdic acid (PMo12).[118] The catalyst exhibited outstanding MoxC derived from MOF has high crystallinity, large
HER activity with small η10 = 47 mV, and ζ = 71 mV dec−1, surface area, and rich porosity so that it can be applied to
high je = 2.042 mA cm−2, and large TOF (3.71 × 10−3 s−1 at HER catalysis.[121,122] For example, Wu et al. synthesized
η = 10 mV) in basic electrolyte. The excellent HER activity of porous MoCx nanooctahedrons through facile MOF assisted
N-P-doped-Mo2C@C can be explained in the following charac- strategy, based on carburization reaction of Cu-based MOFs
teristic features of the synthesized hybrid catalyst; 1) the con- (HKUST-1) as a host and Mo-based polyoxometalates (POMs)
ductive carbon matrix and shell prevent aggregation of Mo2C as a guest.[121] The MoCx catalyst was composed of small-
nanocrystals and facilitate electron transfer efficiently; 2) the sized, uniform and mesoporous nanocrystallites encapsu-
uniform doping of N and P in the carbon matrix/shell and lated in a carbon matrix. This MOFs derived MoCx catalyst
plenty of Mo2C provide a large number of highly active catalytic exhibited remarkable HER activity in acidic/basic electrolytes
with η10 = 142/151 mV, ζ = 53/59 mV dec−1. Table 1. HER electrocatalysts in 0.5 m H2SO4 @ glassy carbon electrode (GCE).
The activity of MoCx nanooctahedrons for
HER might be due to the following aspects: Catalyst Overpotential η10 Tafel slope ζ ΔGH* [eV] Refs.
1) MoCx possesses high intrinsic HER per- [mV] [mV dec−1]
formance, which is probably due to their 20% Pt/C ≈30 ≈28 ≈−0.09 [41]
similar electronic and chemical properties Pt-GT-1 18 24 0.04 [129]
like Pt; 2) MoCx nanocrystallites with small
CoMoP@C 41 49.73 0.103 [66]
size and high porosity can expose more elec-
P-doped MoS2 43 34 S/P sites = 0.43/0.004 [107]
trochemical active surface and active sites
MoS2 sheet = −0.09
during HER process; 3) the mesoporous
structure and uniform morphology of MoCx N-doped MoS2 45 41 0.06 [112]
are expected to promote effectively the mass CoP@NC 78 49 C1/2 = 0.212/0.158 [62]
and charge transfer within the large octa- Zn0.30Co2.70S4 80 47.5 0.32 [70]
hedral particles. Similarly, Wang et al. syn- MoS −BP 85 68 – [111]
2
thesized Ni-decorated MoC hollow structure
Mo2C@2D-NPCs 86 62 0.04 [116]
from Mo-based POM guest and Ni-based
MOF host precursors. [122] Initially, Mo-POM CuFeS 2 88.7 47 0.19 [46]
incorporated Ni-MOF hollow structure was Co@BCN 96 63.7 0.188 [51]
prepared via dissolution-regrowth approach. Fe3C/Mo2C@NPGC 98 45.2 – [31]
Then carbon nitride polymer was coated
α-INS 105 40 – [88c]
on the surface of the synthesized hollow
structure and finally converted into carbon FeP-CS 112 58 – [35b]
coated-Ni decorated MoC hollow structure Co–C–N 138 55 −0.15 [49]

through calcination in the N2 atmosphere FeP 144 58 – [34]
at 500 °C. Due to the unique configura-
tion and composition, this hollow structure
displayed remarkable HER activity and stability with η10 = 2.5. Single Atom Electrocatalysts for HER
123 mV with ζ = 83 mV dec−1 in 1 m KOH solution. On the
basis of performance the role of coated carbon and Ni deco- The main aspects for large scale hydrogen fuel generation are
rated MoC hollow structure is summarized as: 1) the layer developing high current density with small η using economical
of carbon polymer avoids the aggregation of particles during electrocatalysts. The electrocatalytic activity and stability of
the calcination process and thus maintains the structural cluster-sized catalysts for scientific and industrial scale appli-
integrity; 2) the carbon layers after calcination provide the cations have been widely investigated in the past decades. The
mechanical reinforcement to inner particles, and efficiently exposure of active sites to electrochemical reactions is directly
reduces the morphological collapse, corrosion, and oxida- proportional to the catalysts performance,[124] while the avail-
tion of the catalyst in extremely high alkaline environment; able traditional catalysts exhibit particle morphologies which
3) the unique structure, conductive carbon layer and enriched suffer from a large loss of active electrochemical sites during
porosity of the catalyst ensure the easy contact among the applications.[125] Also the electrochemical performance of tran-
electrolyte and electrode surface, facilitating the mass and sition metal-based catalysts is strongly influenced by their
charge transfer effectively; 4) the synergistic effect of Ni and composition and grain size.[126] It has been well established
MoC enhances the catalytic activity for HER performance. that the metal atoms with unsaturated coordination in a cata-
Tang et al. fabricated highly porous nanostructured MoC lyst are more active and stable catalytic centers than those with
embedded in graphitized carbon shells (MoC@GS) through saturated coordination.[127] Therefore, during optimization of
in situ carburization of Mo-based MOF in the N2 atmos- catalysts for better electrochemical performance, it is desirable
phere.[123] The ultrafine small size (3 nm) MoC NPs confined to reduce the particle size and increase the fraction of metal
by 1–3 GS significantly favored the high HER in basic (1 m atoms with unsaturated coordination. In this regard, the single-
KOH)/acidic (0.5 m H2SO4) media with η10 (77/124 mV), atom catalysts (SACs), which contain only a single metal atom
small ζ (50/43 mV dec−1) and large je (0.212/0.015 mA cm−2). in the main active site are emerging as a new exciting research
The remarkable HER performance of this catalyst is credited area.[124]
to the synergistic effect of small-sized MoC NPs, ultrathin Given that some of the chemical properties of single atom
and conductive GS, and large porosity. in SACs are significantly different from the sub-nanometer
Tables 1 and 2 summarize the best reported electrocatalysts clusters or NPs, the SACs have extraordinary catalytic activity,
for catalyzing HER, showing that N-doped MoS2, P-doped selectivity, and durability. The SACs show i) unsaturated coor-
MoS2, Co-CoP/NF, and RuCo@NC exhibit excellent HER dination environments of catalytic metal centers with the max-
activities in acidic and basic solutions. Moreover, this section imum number of active atoms for electrochemical reactions;[124]
also concludes that the electrocatalyst with large surface active ii) quantum size effects where the electrons confinement pro-
sites for the accommodations of reactant intermediate and vides a discrete level of energy distribution;[124] iii) strong chem-
+
optimum free energy for H adsorption and H2 desorption ical bonding between metal atom sites and the support due to
shows high HER activity. which SACs exhibit high stability.[128] The conductivity at SACs
Table 2. HER electrocatalyst in 1 m KOH solution at different electrode.
Catalyst Substrate Overpotential η10 [mV] Tafel slope ζ [mV dec−1] ΔGH* [eV] Refs.
Ni3N/Ni/NF NF 12 29.3 0.01 [77b]
RuCo@NC GCE 28 31 0.31 [56]
Co–CoP/NF NF 35 71 – [63]
Ni–N0.19 CFP 42 125 Ni (111)-1N = −0.06 [77a]
Ni (111)-2N = 0.05
Mo2C@2D-NPC GCE 45 46 0.04 [116]
Mo2C@C GCE 47 71 – [118]
Ni5P4 Ti foil 47.1 56 0.152 [83]
Co(OH)2 NRs/MECN NF 69.2 61.9 – [53]
Pt3Ni/NiS GCE 70 @ 37.2 – −0.088 [90]
Fe0.54Co0.46S0.92/CNTs CC 70 64 – [47]
Nano-MoC@GS GCE 77 50 – [123]
Ni3S2|POM+P123 NF 77 67 – [87c]
Zn0.30Co2.70S4 GCE 85 – 0.32 [70]
Ni–MoS2 CC 98 60 −0.07 [109]
CoP@NC GCE 129 58 C1/2 = 0.212/0.158 [62]
HNDCM-Co/CoP GCE 138 64 – [58]
Ni0.7Fe0.3S2 NF 155 109 – [43]
Co–Mo2C GCE 118 44 – [54c]
can be increased by the presence of their NPs.[129] Furthermore, Even though the above-mentioned metal oxide has been
the catalytic performance can be predicted from DFT calcula- extensively applied as supports for different SACs fabrication,
tions, which can save the screening time for catalyst optimiza- they usually suffer from low electrical conductivity and poor
tion toward a specific catalytic reaction. stability in harsh acidic or basic electrolytes, due to which it
The concept of SACs has recently been receiving a great cannot be applied readily to electrochemical HER and OER
attention in heterogeneous catalysis. It maximizes the effi- applications.[134] In this regard, single metal atoms supported
ciency of atomic properties and exhibits excellent and stable in carbon or nitrogen doped carbon (the carbon may be derived
catalytic performance in water–gas shift reaction,[127a] CO from graphene oxide, melamine or metal organic framework)
oxidation,[130] and electrochemical (HER, OER, and ORR) offer several advantages, including high electrical conductivity
reactions.[131] However, the controlled synthesis of electrocata- for charge transfer acceleration,[135] large theoretical specific
lytically active SACs is still in its infancy and remains as a huge surface area (≈2600 m2 g−1 for graphene)[136] that can host a
challenge due to the large surface free energy of single metal large number metal-based active sites and high flexibility with
atoms in a catalyst which allows SACs to aggregate to form NPs dopants (for example; single atom can anchor at graphene edge
or nanoclusters.[132] An effective way to overcome it is to reduce due to the dangling C bonds, or can substitute the carbon in
the free surface energy of metal atoms by anchoring it in an graphene lattice, or can coordinate with ligands on graphene
individual form on a supporting substrate via a strong metal lattice). In general, pyridinic or pyrrolic N with large defect sites
atom–support interaction. In recent years, various support provided rich coordination sites for single metal atom binding.
materials (such as MgO, SiO2, Al2O3, TiO2, ZnO, FeOx, MoC, Recently, our group designed a stable and efficient HER elec-
CeO2, etc.)[124a,125b,130,133] have been used to prevent metal trocatalyst in which graphitic tubes (GT) encapsulated an
aggregation during synthesis of multiple SACs. For example, alloy of Fe3Co7 NPs with a thin layer of Cu on the inner tube-
Zhang and co-workers synthesized Pt-SACs supported on FeOx walls and ultralow Pt (only 1.4 µg cm−2) in atom and cluster
nanocrystallites (Pt/FeOx) with metal dispersion, which showed forms embedded on the outer layer of GT surface (denoted by
high activity and stability for CO oxidation.[130] The high activity Pt-GT-1).[129] This Pt-GT-1 required very small η10 = 18 mV with
of Pt/FeOx toward Co oxidation is attributed to partially unoc- small Tafel slope of 24 mV, high TOF of 7.22 s−1, large exchange
cupied 5d orbitals of high-valent positively charged Pt atoms. current density (je = 1.14 mA cm−2) and impressive stability for
Besides noble metals, nonprecious metal-based SACs can also 10 K CV cycles. To obtain a deep insight into the role of this tiny
be prepared as outstanding heterogeneous catalysts. As a typical amount of Pt on the HER performance of Pt-GT-1, the ΔGH* for
example, Lin and co-workers synthesized SiO2 confining Fe–N different active sites and formation energies for defective sites
(Fe–N–C) as SACs, which showed high ORR activity compared generation in GT and ingraining of single Pt atoms and Pt clus-
to commercial Pt/C.[133] The DFT calculations revealed that the ters in the defect sites of Pt-GT-1 were calculated. The forma-
high ORR activity of the Fe–N–C SACs is attributed to lower tion energies calculation predicted that during the synthesis of
energy barrier for ORR reaction compared to commercial Pt/C. GT, the defect sites with N3C1, N2C2, N4, in conjunction with
Figure 11. a) The HAADF–STEM image of Pt atoms and Pt clusters on the GT surface. b) The EDX images of Pt atoms and Pt clusters; scale bars:
1 nm. c) Hydrogen-adsorption free energies (ΔGH*) for different active sites. Reproduced with permission.[129] Copyright 2018, Springer Nature.
N2C1 and N3 structures are formed easily in harsh acidic solu- representing that the Co atoms in N-doped graphene is not
tion due to its small formation energy (ΔE < 2 eV), and single highly active for HER reaction in acidic solutions, may be due
Pt atoms and some small Pt clusters can be readily captured in to the poor ΔGH* value that can bind the H* more favorably to
such defect sites, which was clearly elucidated from aberration- electrode surface and so hinder the ready detachment of H* in
corrected TEM analysis (Figure 11a,b). The DFT calculation order to combine with adjacent H+ and electron (the following
demonstrated that the atomic Pt–N2C2 sites have very low ΔGH* assumption has been made on the basis of their Tafel slope
(0.04 eV) compared to Pt (111) surface (−0.20 eV, Figure 11c), valve ≈82 mV dec−1). However, Wei and coworkers reported
which strongly supported the experimental results that the HER that the atomically dispersed Co1–N4 moiety in phosphorized
reaction at Pt–GT-1 should be far better than Pt (111) surface. carbon nitride (PCN) (denoted by Co1PCN) showed reason-
Graphene confining nonprecious SACs can also show high ably good HER performance (ζ = 52 mV dec−1), though slightly
HER performance compared to their nanocluster counter- poorer performance than commercial Pt/C (ζ = 38 mV dec−1),
parts.[135,137] Li and coworkers synthesized single Mo atoms sup- in 1 m KOH solution.[137a] In this study, the Co atoms supported
ported on N-graphene, which exhibited higher catalytic activity on PCN NS were synthesized by incipient wetness impregna-
toward HER than MoN and Mo2C bulk electrocatalysts and tion and pyrolysis reaction. The HAADF-STEM images showed
longer durability than commercial Pt/C.[138] The extended X-ray that Co atoms were uniformly distributed on PCN NS. The
absorption fine structure (EXAFS) analysis showed that the Co1PCN displayed η10 = 89 mV. To identify the geometric and
single Mo atoms anchored with one N-atom and two C-atoms structural changes on the Co site during HER reaction, oper-
in the form of Mo1N1C2. The DFT calculation revealed that ando EXAFS in conjunction with Fourier transform infrared
the ΔGH* value of Mo1N1C2 sites is near zero (0.08 eV) com- spectroscopy measurements was used, which revealed that the
pared to other bulk counterparts (Mo2C, MoN, and N-doped unsaturated single atom Co coordination is highly susceptible
graphene 0.26, 0.40, and 0.67 eV). Furthermore, the density to the alkaline environment, and upon hydroxyl adsorption the
of states (DOS) of Mo1N1C2 was much higher near the Fermi valence-state changes to highly oxidized HO–Co1–N2 moiety.
level than those of MoN and Mo2C, which disclosed that the The DFT calculation demonstrated that the highly oxidized Co
uniform distribution of Mo atoms on N-graphene can impres- sites reduce the water dissociation energy and increase their
sively improve the d-electron for higher charge transfer and catalytic performance for HER reaction. Generally, the HER
catalytic reaction. The above-mentioned studies disclosed that reaction in acidic solution is more simple and facile than that
the introduction of nitrogen dopants into graphene as coordina- in basic solutions, because the reaction source in acidic solu-
tion sites leads to capture and anchor the uniformly distributed tion is proton (H+) which can receive an electron easily from
single metal atoms and suppress their aggregation and migra- the electrode surface. While in basic solution, the source of a
tion. Toward this end, Tour group reported uniformly dispersed proton is water molecule and the high kinetic energy barrier of
atomic Co on N-doped graphene (Co-NG) by simply heating a initial water dissociation (ΔGH2O) makes HER kinetics slow and
small amount of cobalt salt with graphene oxide in the pres- sluggish. Therefore, the catalyst which can reduce the energy
ence of gaseous NH3 atmosphere.[135] High-angle annular dark- barrier for the initial water dissociation reactions will work very
field scanning TEM (HAADF–STEM) and EXAFS analysis well in alkaline solutions. In this regard, the Ni atom sites can
showed that Co atoms were atomically distributed on graphene effectively reduce the energy barrier for water dissociation in
support which resulted from the strong binding interaction of alkaline HER reaction. For example, in the study of Feng and
Co with N atoms in N-doped graphene. The Co-NG showed co-workers, the atomic Ni sites were introduced into MoS2
η10 = 147 mV with high stability in 0.5 m H2SO4. The high sta- NSs (Ni–MoS2) which effectively reduced the ΔGH2O (0.66 eV)
bility of Co-NG is attributed to a strong interaction between and facilitated the OH- desorption better than pure MoS2
Co and N atoms in N-doped graphene. The Co-NG results NSs (ΔGH2O 1.17 eV).[109] As a result, the Ni–MoS2 exhibited
small η10 = 98 mV compared to pure MoS2 NSs η10 = 220 mV. synthesis protocol, first hollow structure of Fe–Co metal
Recently, Zhang et al. reported that single atom Ni sites can organic complex (Fe–Co–MOC) was synthesized from hydro-
also show high HER activity in acidic solution.[137b] In this thermal reaction of metal sources (Co(NO3)2·6H2O and FeCl3)
study, the single atom Ni sites trapped in graphene defects and ligand (trimesic acid). In hydrothermal reaction, the
(Ni@DG) were fabricated by incipient wetness impregnation hollow Fe–Co–MOC structure was obtained from coordination
followed by acid leaching. The Ni@G exhibited almost similar of Fe or Co ions with molecules of trimesic acid. The obtained
HER performance (η10 = 70 mV) to that of commercial Pt/C Fe–Co–MOC was converted to Fe–Co/C hollow spheres and
(η10 = 67 mV) in 0.5 m H2SO4 solutions. They attributed the then finally to Fe–Co–P by simple carbonization and phosphi-
high HER activity of Ni@DG to large defects in graphene and dation approaches. For comparison, FeP and CoP were also
atomically dispersed Ni sites. synthesized. The Fe–Co–P hybrid exhibited j10 at 252 mV with
Overall, the SACs with well-defined atomically metal sites ζ = 33 mV dec−1 which was 45 and 100 times better than CoP
and their strong interaction with N-doped graphene can effec- and FeP, respectively. To get insight into the high OER activity
tively modulate the electronic structure and maximize the metal of Fe–Co–P hybrid, the electronic structure of CoP, FeP, and
utilization efficiency for HER. Furthermore, SACs can provide Fe–Co–P were inspected from DOS. Compared with CoP and
simplified ideal model systems for a direct assessment of exper- FeP the Fe−Co−P hybrid had a high DOS, suggesting that the
imental results through DFT calculations. However, from an Co in the low valence state was stabilized by electrochemically
industrial point of view, there are still large gaps in HER activity induced high valent Fe, leading to high OER activity and
of SACs (excluding the single Pt atoms capture in N-doped gra- stability of the hybrid. Similarly, Zhang et al. presented the
phene) and benchmark Pt catalyst. Thus tremendous efforts on role of Fe in atomic gold supported on NiFe layer double
the synthesis and design of SACs are needed to improve their hydroxide (LDH) (Au/NiFe LDH) OER electrocatalyst.[140] This
HER activities. At this point, advanced in situ characterization Au/NiFe LDH delivered η10 = 237 mV with high stability, while
technologies, such as operando-atomic resolution imaging that in the absence of Au the NiFe LDH delivered η10 = 263 mV.
can directly see the reaction process at the active sites, and To explore the high OER activity of Au/NiFe LDH, the DFT
highly sensitive surface spectroscopic techniques that can well calculations were conducted. As discussed in the introduction
address the molecular structure and catalytic behavior of the section that the OER activity is determined by the energetics
SACs during HER are required. of the adsorbed intermediates (*OH, *O, and *OOH) on the
A quick summary of the best reported single atom and active sites of the catalyst and adsorption energy difference
cluster-based-electrocatalysts for HER in acidic and basic solu- (ΔGO* − ΔGOH*) is the main descriptor for the activity trends
tions are tabulated in Tables 1 and 2. in different materials. The ΔEOH* and ΔEOOH* binding energies
for Au/NiFe LDH was 0.93 and 3.46 eV with favorable Gibbs
energy (ΔG1 = 1.33 eV, ΔG2 = 1.15 eV, ΔG3 = 1.41 eV and ΔG4 =
3. Electrocatalysts for OER 1.03 eV), which is close to ideal OER process (ΔEOH* = 0.86 eV
and ΔEOOH* = 3.3 eV). These experimental and theoretical
3.1. Iron-Cluster-Based Electrocatalysts for OER observations demonstrate that the Fe in Au/NiFe LDH should
be OER active sites, while Au can help in charge distribution
Iron is the most attractive metal in the designing of electro- of the hybrid by transferring electron to LDH which further
catalysts for ORR, OER and HER due to its low toxicity, neg- enhances the overall OER performance. Zhang et al. synthe-
ligible environmental impact, and inexhaustible supply.[139] sized gelled FeCoW oxyhydroxides, which delivered very small
Many groups reported that single Fe based materials have poor η10 = 191 mV with high stability.[141] The high OER activity
OER activity, however, it works as an OER promotor for many of this hybrid can be attributed to the synergistic interplay
multimetallic electrocatalysts.[139] For example, Bian et al. syn- between iron, cobalt and tungsten in producing an auspicious
thesized nickel hydroxylphosphate single-wall nanotubes modi- electronic structure and coordination environment for effec-
fied with iron hydroxide (NiPO/Fe(OH)x SWNTs) as an OER tive water oxidation reactions. Sun et al. fabricated ß-Co(OH)2
electrocatalyst.[139a] This NiPO/Fe(OH)x SWNT hybrid displayed NSs decorated with Fe3O4 (Fe3O4/Co(OH)2 NSs) as an OER
η10 = 248 mV which was better than pristine NiPO/SWNT electrocatalyst.[142] The Fe3O4/Co(OH)2 NSs exhibited low η10 =
(η10 = 360 mV). The high OER activity of NiPO/Fe(OH)x SWNTs 390 mV compared to single Co(OH)2 and Fe3O4 (η10 = 480 and
compared to NiPO/SWNT is attributed to partial charge transfer 540 mV). The high OER activity of Fe3O4/Co(OH)2 NSs com-
from Fe(OH)x to NiPO, high surface area and synergistic effect pared to single Co(OH)2 or Fe3O4 is attributed to the following
of incorporated iron and nickel phosphate. Dutta et al. pre- aspects: i) the NSs of Co(OH)2 as a substrate which displayed
sented OER electrocatalyst having an amorphous NixP shell intrinsically high catalytic OER activity; ii) the water molecule
and crystalline Fe3O4 core (denoted by Fe3O4/NixP).[139b] For which adsorbed more favorably on the Fe3O4/Co(OH)2 NSs
comparison, Ni12P5 and Fe3O4 were also synthesized, and the surface compared to pure Co(OH)2; iii) the dopant Fe which
OER activity of Ni12P5 was η10 = 320 mV with ζ = 128 mV dec−1, changed the electronic structure and surface properties of the
while Fe3O4 showed almost no activity for OER. Fe3O4/NixP catalyst and synergistically boosted the OER activity. Morales
showed η10 = 260 mV with ζ = 43 mV dec−1. These results dem- et al. studied the consequence of Mn, Cr and Fe doping on the
onstrated that the Fe3O4 core activates the Ni electrochemical OER activity of Ni-based double hydroxides (NiMOOH).[143]
processes and dramatically enhances the OER activity. Liu et al. Compared to pure NiOOH, the doping with Mn/Cr/Fe reduced
synthesized alloy nanostructures of iron–cobalt phosphide the η for delivery of η0.5 of about = 60/100/130 mV. The
(Fe–Co–P) as an active OER electrocatalyst.[139c] In a typical metal doping in NiOOH changed the OER limiting step from
Figure 12. a) TEM images of FeOOH/Co/FeOOH HNTs. b) linear sweep voltammetry curves of FeOOH/Co/FeOOH HNTAs-NF, FeOOH NTAs-NF
and NF for OER with scan rate of 5 mV s−1. c) Nyquist plots of FeOOH NTAs and FeOOH/Co/FeOOH HNTAs-NF. d) Chronopotentiometric stability
of FeOOH/Co/FeOOH HNTAs-NF, FeOOH NTAs-NF and NF. e) NBO charge distributions on O and Fe atoms before and after hybridization. f) Free
energy profiles of FeOOH and Co-FeOOH. Reproduced with permission.[144] Copyright 2016, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim.
high to low potential (from *OH → *O to *O →*OOH) and to FeOOH NTAs/NF the FeOOH/Co/FeOOH HNTAs/NF
resultant into high OER activity. Li and coworkers designed reduces the energy barriers for OER intermediates and products,
nanotube arrays (NTAs) and hybrid NTAs (HNTAs) of FeOOH/ improving the overall electrocatalytic OER.
Co/FeOOH supported on NF (FeOOH/Co/FeOOH HNTAs/ Recently, Chen group exploited the geometric sites of Fe and
NF) (Figure 12a).[144] The hybrid delivered η20 = 250 mV with Co ions in a different weight ratio of Fe doped cobalt oxide elec-
high stability compared to FeOOH NTAs/NF and Co NTAs/NF trocatalysts (denoted CoFey) and their effect on OER activity.[145]
(Figure 12b,d). The high OER activity of FeOOH/Co/FeOOH The positive trend in OER activity was observed with increasing
HNTAs/NF is attributed to i) the synergistic effect of FeOOH the Fe content in CoFey (CoFe0 < CoFe0.16 < CoFe0.28 < CoFe0.38 <
and Co layers; ii) the larger conductivity of central layer of Co CoFe0.44). Utilizing X-ray absorption spectroscopy (XAS) it was
metal which provides superhighways for transferring of elec- found that the Fe ions occupied the octahedral sites (Fe+3(oh))
tron during OER (Figure 12c, Nyquist plots of FeOOH NTAs in CoFe0.44 and confined the Co ions to only tetrahedral sites
and FeOOH/Co/FeOOH HNTAs/NF), iii) the high surface area, (Co2+(Td)), which strikingly improves their OER activity (η10 =
anisotropic morphology, and hollow nanostructures of the syn- 229 mV and η100 = 281 mV). While with further enrichment of
thesized hybrid which improve drastically the utilization rate of Fe in CoFey the decline in OER activity was observed (CoFe0.49:
FeOOH in water oxidation reaction. To support the high OER η10 = 237 mV), because in such condition the Fe ion would prob-
activity of FeOOH/Co/FeOOH HNTAs/NF, the electronic inter- ably occupy the tetrahedral sites and reduce the active Co2+(Td)
actions among Co and FeOOH were investigated, because the sites for efficient OER catalyzing reactions. The obtained OER
charge distribution on the catalyst surface is an important feature results with CoFe0.44 and CoFe0.49 suggested that the electrocat-
for OER. The natural bond orbital (NBO) charge redistribution alytic activity was related with tetrahedral active sites of Co2+,
represents that the Fe and O atoms after hybridization have less while the Fe+3(oh) promoted the OER activity. Xu et al. synthe-
positive and negative charges, respectively, representing that Co sized nickel iron diselenide derived oxide (NixFe1−xSe2-DO) as
and FeOOH have strong electronic interactions in FeOOH/Co/ an OER electrocatalyst and compared their OER activity with
FeOOH HNTAs/NF hybrid (Figure 12e). Furthermore, the high NiSe-DO.[146] The NixFe1-xSe2-DO delivered small η10 = 195 mV
OER activity of FeOOH/Co/FeOOH HNTAs/NF hybrid com- compared to NiSe-DO (η10 = 253 mV), showing that the Fe
pared to FeOOH HNTAs/NF was also investigated from binding sites dramatically boosted the OER activity of the NixFe1-xSe2-
energies of intermediates and products involved on catalyst sur- DO electrocatalyst. Sun and co-workers synthesized core–shell
face during OER (Figure 12f). Figure 10f shows that compared NiFeCu on NF by simple electrodeposition from mixed solution
of Ni(Cl)2·6H2O (80 × 10−3 m), Cu(SO4)·5H2O (40 × 10−3 m), structure composition. For every heterogeneous catalyst, the
and Fe(NO3)3·9H2O (25 × 10−3 m) at a constant potential of OER activity of the Co3O4 depends on its surface structure,
−1.10 V versus Ag/AgCl.[147] The as synthesized catalyst exhib- and it is essential to get more insight into its phase changes
ited very small η10 = 180 mV with ζ = 33 mV dec−1 and high during water oxidation reactions. The first constructive report
stability. The OER activity of this designed electrocatalyst on the OER performance of spinel Co3O4 has been made by
can be attributed to the synergistic effect of Fe, Ni, and Cu. Rasiya and Tseung, and since then, various studies were con-
Zhuang et al. designed NSs of iron–cobalt oxide (FexCoy–O) ducted to elucidate its active structure and mechanism for
with abundant oxygen vacancies, high specific surface area catalyzing water oxidation.[151] The literature disclosed that
(261.1 m2 g−1) and ultrathin thickness (1.2 nm).[148] The catalyst Co atoms in Co3O4 exist in two different oxidation and coor-
exhibited η10 = 308 mV with ζ = 36.8 mV dec−1 in 0.1 m KOH dination environments: such as tetrahedral-coordinated Co(II)
solution. The high OER activity of this catalyst can be attrib- (Co2+Td) with intermetallic distance of 3.36 Å, and octahedral-
uted to the synergistic effect of Fe and Co, high surface area, coordinated Co(III) (Co3+Oh) with intermetallic distances of
atomically thin sheets and abundant oxygen vacancies. Shen 2.85 and 3.36 Å.[151] Between Co2+Td and Co3+Oh, the former
group studied the effect of Fe and Mo on the OER activity of has been reported as a better OER active center, because in
Ni(OH)2/NiOOH NSs (denoted by MoFe:Ni(OH)2/NiOOH).[149] the anodic potential region (before onset potential) the Co2+Td
The synthesized MoFe:Ni(OH)2/NiOOH displayed high OER at the catalyst surface is converted into cobalt oxyhydroxide
activity and impressive stability (η100 = 280 mV) compared to (β-CoOOH) intermediate, which possesses more feasible water
Ni(OH)2/NiOOH NSs (η100 = 400 mV). The XPS studies of oxidation capability than pure Co3O4.[151,152] Therefore, the cata-
MoFe:Ni(OH)2/NiOOH showed that the Ni peak after addition lytic activity of Co3O4 can be tuned by increasing the ratio of
of Fe and Mo shifted toward high binding energy, indicating Co2+Td to Co3+Oh. For example, Wang et al. demonstrated the
that the dual modification with Fe and Mo synergistically independent OER activities of Co2+Td and Co3+Oh centers by
increased the interaction strength of Ni with OER intermediate synthesizing spinel ZnCo2O4 (containing only Co3+Oh center)
species and boosted the OER activity of the designed catalyst. and spinel CoAl2O4 (only Co2+Td center) as water oxidation
The aforementioned literature showed that the Fe itself is catalysts.[152a] Here, Zn2+ and Al3+ ions were OER inert, which
not an active metal for OER but mostly working as an OER pro- allowed determining the intrinsic water oxidation capability of
moter in the catalyst. However, the pure Fe in nitride or phos- Co centers. The EXAFS data showed that during water oxida-
phide form intercalated in 3D porous architectures or grown on tion process the Co2+Td ions at the surface of CoAl2O4 formed
conductive substrate, is found to work as an active center for an active β-CoOOH intermediate phase which dramatically
OER. This type of porous and conductive architectures increase reduced the energy barrier for water oxidation reaction, while
the active catalytic sites, charge transport between metal and the Co3+Oh ions at the surface of ZnCo2O4 were simply oxi-
supporting substrate, and their contact area with electrolyte dized into Co4+ without having much effect on OER. Similarly,
solution during OER.[150] For example, Ren and coworkers grew Menezes et al. fabricated a partially Mn3+-substituted spinel
nanoporous film of iron nitride (Fe3N/Fe4N) on highly conduc- Co3O4 NPs (denoted by MCO) and introduced metal defec-
tive 3D-graphene/Ni foam by simple thermal nitridation (NH3 tive sites to the surface of MCO by removing Mn3+ ions in a
was used as a nitridation source during heating) approach at postsynthetic treatment.[152b] The removal of Mn3+ from octa-
400 °C.[150a] The as-designed catalyst delivered η10 = 238 mV hedral sites provided the Co3O4 surface with highly exposed
with ζ = 44.5 mV dec−1, Faradaic yield of 96.7%, and high Co2+Td centers, which led to the enhanced formation of OER
stability. The high OER activity of this catalyst is attributed to active β-CoOOH intermediate. The MCO-derived defect-rich
its high surface area, abundant active sites, nonporous struc- OER catalyst showed low η10 = 320 mV compared to pristine
ture and conductive support which facilitated the charge mass Co3O4 (360 mV) and Mn2O3 (560 mV). Although the removal
transport between electrolyte and electrode during OER. Liu of Co3+Oh sites allows more feasible water oxidation, it may
and co-workers synthesized hollow-type iron phosphide–phos- negatively affect the electronic structure of the catalyst and
phate nanotubes (FeP-FePxOy-NTs) by two-step hydrothermal may dramatically reduce its electrical conductivity. Therefore, it
and phosphidation approaches.[150b] The as designed catalyst is more practical to convert less active octahedral Co3+ centers
displayed j10 at η = 280 mV with ζ = 48 mV dec−1, large TOF into more active tetrahedral Co2+, while maintaining the total
of 0.10 s−1 and high stability. Similarly, Song and coworkers amount of metal ions in the lattice.[153] For example, Xu et al.
fabricated FeP4 cubes as an OER catalyst, which delivered demonstrated that oxygen plasma etching of Co3O4 can remove
η10 = 283 mV with ζ = 41.4 mV dec−1 and high stability.[150c] oxygen atoms from the surface of the catalyst, which converted
the Co3+ ions to Co2+.[153] As a result, higher abundance of OER
active Co2+Td centers in plasma-treated Co3O4 promoted effi-
3.2. Cobalt-Cluster-Based Electrocatalyst for OER cient and facile water oxidation with η10 = 300 mV which is sig-
nificantly lower than η10 = 570 mV of pristine Co3O4. To further
3.2.1. Cobalt Oxides increase the electrical conductivity and OER activity of Co3O4,
the oxygen deficient Co3O4 can be hybridized with highly con-
The OER volcano plot (Figure 3b) illustrates that among non- ductive carbon matrix, which can provide a solid platform for
precious metal oxides the cobalt oxide (specifically spinel facile electron transfer. Tong et al. synthesized ultrathin NSs
Co3O4) has the lowest theoretical η for water oxidation reac- of boron and nitrogen-rich graphene coupled with oxygen defi-
tions, and therefore can be an attractive target for designing cient CoOx NPs (CoOx NPs/BNG), which showed a low η10 =
efficient OER catalyst by modifying its morphology and 295 mV with ζ = 57 mV dec−1. The enhanced OER activity was
closely related to oxygen defect rich structure of CoOx, which polarization, the surface of CoP catalyst was oxidized into a
tuned the electronic structure of the material and increased the nanolayer of CoOx, which was responsible for facile OER. The
oxygen affinity of the catalyst.[154] Also, the formation of strong CoP-NR/C required η10 = 320 mV with ζ = 71 mV dec−1. Simi-
CoNC and CoBN bonds increased the electrical conduc- larly, Xuqiang et al. fabricated hierarchical microstructure wires
tivity of the catalyst and facilitated the electron transfer toward of cobalt phosphide NSs supported on NF (CoP NS@MW/NF)
OER active Co metal centers. through facile hydrothermal growth from Co(H2PO4)2·2H3PO4
Even though tuning the composition of Co3+ and Co2+ in microarrays.[159] The CoP NS@MW/NF showed η100 = 296 mV
Co3O4 provides a facile and easy way for obtaining highly OER with high durability.
active catalysts, its conductivity is still a major issue. Therefore, The catalytic performance of CoPx can be further improved
to increase the water oxidation activity and electrical conduc- by doping with first-row transition metal.[160] Incorporation of
tivity, the Co3O4 can be doped with first row transition metals, transition metals into lattice can modify the electronic struc-
such as Fe, Ni, Cu, Cr, V, etc.[155] The metal doping can modify ture of the CoPx, and therefore tune the binding energies of
the electronic band structure of the spinel cobalt oxide, and Co centers for OER intermediates.[160] If the cobalt phosphide
increase its affinity toward OER active species (O*, HO*, and is doped with transition metal, the free energy formation for
HOO*). For example, Lin and McCrory demonstrated the OER HOO* and O* (rate determining step) may be decreased sig-
activity of chromium doped spinel cobalt oxide (Cr0.75Co2.25O4), nificantly. The work of Xiao et al. demonstrated that the metal
and correlated its enhanced performance with the increased doping together with smart catalyst architecture design can
oxygen affinity of Co2+ centers through embedment of highly yield outstanding OER characteristics.[160] Homobimetallic
electrophilic Cr3+ ions.[155c] The Cr3+ ions substituted for cobalt phosphide NSs codoped with 1/20 atomic ratio of tran-
the OER inert Co3+ in the octahedral centers, and enhanced sition metals (CoM-P-NS, M = Cu, Zn, Mn, Ni) derived from
the electron transport throughout the whole catalyst surface. mixed metal zeolitic-imidazolate frameworks through hydro-
The fabricated Cr0.75Co2.25O4 had a low η10 = 350 mV compared thermal treatment could outperform state-of-the-art OER cata-
to pure Co3O4 (η10 = 420 mV). An amorphous Co0.75V0.25Ox lysts such as Ir/C and RuO2. The fabricated CoNi-P-NS, CoMn-
prepared by Liardet and Hu showed very high OER activity, P-NS, CoCu-P-NS, and CoZn-P-NS catalysts showed reduced
due to integration of electropositive V3+ ions into the lattice of η10 = 273, 298, 281, and 276 mV, respectively. The DFT calcu-
CoOx.[155d] XPS analysis confirmed the formation of oxyhydrox- lation revealed that doping of Ni into CoP lattice reduces the
ides at the surface of the catalyst, and the obtained Co0.75V0.25Ox ΔGO* (rate-determining step for OER) from 1.62 to 1.57 eV,
required anodic η10 = 347 mV on a GC-electrode. The η10 of which promotes facile oxygen release. Similarly, Garcia et al.
Co0.75V0.25Ox was further decreased to 254 mV by depositing fabricated Fe codoped CoP NPs ((Co0.54Fe0.46)2P) as OER elec-
it on 3D conductive NF. Tahir et al. synthesized NiO and trocatalyst which showed η10 = 280 mV.[161] Overall, the metallic
Co3O4 hybrid NPs on N-doped carbon (NC) nanotubes as OER nature of cobalt phosphides makes them excellent candidates
electrocatalyst.[155e] The XPS analyses revealed the presence of for OER electrocatalysis, and their activity can be easily tuned
high oxidation states of Ni and Co atoms in the hybrid com- by transition metal codoping.
pared to pristine NiO and Co3O4, and strong coupling between
metal centers and N atoms of the carbon matrix, which was
responsible for oxygen affinity, enhanced electrical conductivity, 3.2.3. Cobalt Sulfides
resulting in excellent OER performance. The NiO/Co3O4@NC
delivered η10 = 240 mV on GC-electrode, which was further Among other emerging cobalt-based OER catalysts, cobalt
reduced to η10 = 200 mV by loading on NF. sulfides play a significant role, even though water oxidation
performance of sulfides is not as good as their oxide or phos-
phide counterparts. Several OER active sulfides have been
3.2.2. Cobalt Phosphides investigated, such as Co3S4, Co1-xS, CoS2, CoS, and Co9S8, how-
ever, their performance is hampered by low conductivity and
Among OER active cobalt compounds, Co3O4 has the highest less exposed active sites.[162] Recent efforts are being directed
stability and tolerance to corrosion under water oxidation condi- toward Co-based sulfide to increase their surface area and to
tions. However, the intrinsic catalytic performance of the Co3O4 make its composite with highly conductive heteroatom-doped
is significantly lower compared to cobalt phosphide alloys carbon matrices. For example, Ganesan et al. synthesized
(CoPx). Cobalt phosphides (Co2P, CoP, CoP2) have metallic both CoS2 and Co9S8 phases of cobalt oxide through in situ
nature due to a small difference in electronegativity between Co growth on N, S-doped GO sheets by controlling the synthesis
and P atoms,[156] and therefore possess high intrinsic electrical temperature.[162a] The CoS2 and Co9S8 delivered η10 = 380 and
conductivity. This feature can significantly enhance the cata- 400 mV, respectively. Similarly, Qiao group demonstrated the
lytic activity of CoPx compounds, which arises from the surface OER activity of Co1-xS hollow nanospheres hybridized with
oxidation of CoPx under anodic polarization condition to give N, S-doped graphene NSs (Co1-xS/N,S-G).[162b] The fabricated
OER active CoOx layer. These CoOx layers mainly consist of material required η10 = 371 mV with ζ = 63 mV dec−1. The
cobalt (oxy)hydroxyl species, similar to β-CoOOH in Co3O4, that catalyst is benefited from the hollow structure of the cobalt
is responsible for facile water oxidation.[157] For example, the sulfide NPs having largely exposed OER active sites. The
work of Chang et al. demonstrated the activity of carbon-sup- catalytic activity of cobalt sulfides can also be enhanced by O
ported CoP nanorods (CoP-NR/C), derived from hydrothermal doping directly into the CoSx lattice. The incorporation of
synthesis, as a water oxidation catalyst.[158] Upon anodic O atoms can lead to reduction in ΔGO* of Co centers, which
clearly facilitates the further oxygen evolution. Cai et al. per- as-synthesized FexNiy-BDC (BDC = benzenedicarboxylate) elec-
formed a synthesis of O-doped cobalt sulfide porous nanocubes trocatalyst displayed η10 = 260 mV with ζ = 35 mV dec−1. The
(CoS4.6O0.6) as an OER electrocatalyst.[163] The fabricated mate- porous nature of MOF-derived matrix provided an enhanced
rial showed low η10 = 290 mV, which was comparable to state- surface area while the electronic synergy between Fe and Ni
of-the-art RuO2 OER electrocatalyst (η10 = 300 mV). Other than allowed stabilization of OER active species. Similarly, Zhang
nonmetal doping of cobalt sulfides, their OER performance and co-workers fabricated NiFe-based Prussian Blue analog
can be improved by transition metal codoping. Copper doping (NF-PBA), which, upon an electrochemical in situ activation
can provide more O binding sites to a Co3S4 OER electrocata- was capable to generate η10 = 258 mV with ζ = 46 mV dec−1.[168]
lyst, as well as modify the electronic structure of the Co3S4 for The electrochemical activation of the catalyst allowed a com-
enhanced water oxidation catalysis. Chauchan et al. fabricated plete conversion of Ni into Ni(OH)2, which was the active spe-
nanoaggregates of hierarchical NSs of CuCo2S4 as an OER elec- cies for OER. The coalloying of Fe enhanced the stabilization of
trocatalyst.[164] The nanoaggregates had high surface area, as active species during OER. Wang et al. fabricated NiCo/Fe3O4
well as interconnected NSs architectures, which ensured high heteroparticles entrapped within MOF-74-derived matrix.[169]
conductivity and active site availability. The obtained CuCo2S4 The electrocatalyst was derived by temperature controlled
showed η10 = 310 mV and extraordinary stability up to 10 000 annealing of CoNiFe-MOF-74, which showed η10 = 238 mV
LSV cycles without any current decay. with ζ = 29 mV dec−1. The DFT calculations revealed that the
Cobalt oxides, phosphides, and sulfides have their own NiCo species promoted the stabilization of OER active spe-
advantages for water oxidation. Cobalt oxides show extraordi- cies during electrocatalysis. The synergetic effect of Fe3O4 and
nary stability under anodic polarization, which is the result of NiCO was also contributed to high OER activity of the NiCo/
attaining (oxy)hydroxide phase that acts as a robust platform Fe3O4 hybrid.
for oxygen adsorption and oxidation. Though cobalt phosphides Compared to metallic nickel, nickel selenides (NiSe2) are
generate the same OER active intermediate (β-CoOOH) at the more versatile and can be easily synthesized or grown into
surface of the catalyst due to oxidation of phosphorus atoms, various porous nanostructures with high conductivity and sur-
their intrinsic charge conductivity is significantly higher com- face area. NiSe2 is proven to act as a precatalyst for OER cata-
pared to oxide counterparts. Therefore, it might be a future lyzing reaction since during oxidation potential it is converting
target to design OER catalysts that can utilize suitable proper- into electrocatalytically active nickel oxides and hydroxides.
ties of both oxides and phosphides and show the synergetic Moreover, the OER performance and stability of NiSe2 can
effect on water oxidation be improved drastically once it is deposited on some conduc-
tive carbon matrix or alloying with other transition metal. In
this regard, Ni0.85Se on nitrogen-doped hollow carbon spheres
3.3. Nickel-Cluster-Based Electrocatalysts for OER (Ni0.85Se-NHCS) were fabricated by Pan and co-workers.[170]
The ratio of Ni(III)/Ni(II) was tuned in order to achieve higher
3.3.1. Nickel and Ni-Alloying with Other Transition Metals oxygen affinity provided by Ni(III) ions in the lattice. The as-
synthesized Ni0.85Se-NHCS catalyst showed η10 = 353 mV
Nickel (Ni) as an earth-abundant 3d transition metal has a with ζ = 91.95 mV dec−1 in 1 m KOH solution. Similarly, Swesi
long history in modern catalysis of many industrial processes, et al. fabricated a metal-rich form of nickel selenides (Ni3Se2)
especially in the field of hydrogenation, secondary alkaline bat- through electrodeposition on Au-coated Si substrate.[171] The
teries, and water electrolysis.[165] As a catalyst, Ni possesses electrodeposited thin film of Ni3Se2, which contained NiNi
many advantages such as low-cost, good catalytic activity, high bond has similar phase structure as sulfur mineral heazle-
alloying efficiency with other metals, and extraordinary sta- woodite, showed η10 = 290 mV with ζ = 97.1 mV dec−1 in 0.3 m
bility in alkaline solutions.[165b–d] Metallic Ni shows moderate KOH solution. Such OER activity was attained due to annealing
to good catalytic activities toward OER. However, continuous at 300 °C which introduced more Se defective sites for more
operation under OER conditions leads to corrosion of the cata- efficient catalysis and enhanced overall crystallinity of the
lyst and eventual degradation. Therefore, the catalytic activity electrocatalyst.
and stability of metallic Ni electrocatalysts for OER can be Doping and alloying of transition metals into transition
enhanced by covering the catalyst with a conductive carbon metal OER electrocatalysts has been shown to modify and tune
layer or providing a supporting matrix against aggregation. the electronic structure of the electrocatalyst, which leads to
For example, Ramakrishnan et al. synthesized Ni NPs encap- enhanced OER performance. Thus, the performance of NiSe2
sulated in nitrogen-doped mesoporous carbon nanostructures OER electrocatalysts can be significantly enhanced by doping
(NCNP) derived from nickel-organic complex, which showed or alloying with iron or cobalt metals. For example, Li et al.
water oxidation capability in alkaline solution.[166] The as-syn- fabricated a hierarchical hollow (Co,Ni)Se2@NiFe LDH elec-
thesized NCNP electrocatalyst demonstrated η10 = 370 mV with trocatalyst derived from Ni-doped ZIF-67 structure.[172] Firstly,
ζ = 55 mV dec−1 in 0.1 m KOH solution. In this approach, the the ZIF-67 was doped with Ni ions followed by annealing in
surface of metallic Ni NPs is activated during initial cycling and the selenium atmosphere at 400 °C. The resulting (Co,Ni)Se2
converted into nickel (II) oxyhydroxides, which perform the nanocages were then subjected to solvothermal treatment in
actual oxygen evolution process. To further enhance the OER iron and nickel nitrates solution to deposit with NiFe LHD.
activity of metallic Ni electrocatalysts, it can be alloyed with the The obtained (Co, Ni)Se2@NiFe LDH showed η10 = 277 mV
first-row transition metals. Li et al. synthesized FeNi bimetallic with ζ = 75 mV dec−1 in 0.1 m KOH solution. The catalyst
NPs entrapped inside MOF-derived carbon matrix.[167] The was not only superior to commercial RuO2, but surpassed
the performance of many transition metal catalysts for OER.

Similarly, Wang and coworkers synthesized single-crystalline
porous cubic (NiFe)Se2 pyrite mesocrystals as an OER electro-
catalyst.[173] The as-synthesized crystals were self-optimized into
OER active amorphous S-doped metal oxyhydroxides, which
attained oxygen production at η10 = 260 mV. Gu and co-workers
fabricated iron-doped nickel selenide ultrathin sub-2 nm NWs
(Fe-NiSe2 UNWs) and investigated their OER performance.[174]
An iron doping of 8.4% into the nickel selenide structure had
the best impact on the electrocatalytic performance of the
NiSe2, which allowed to oxidize water into molecular oxygen at
η10 = 268 mV with ζ = 41 mV dec−1 in 0.1 m KOH solution.
The DFT calculations were performed with Fe–NiSe2 and pure
NiSe2, which showed that the OER activity of the catalyst was
resulted from the Fe-doping which tuned the electronic struc-
ture of the NiSe2 that efficiently reduces the energy barriers
for oxygen intermediates involving in OER process. Xu et al. Figure 13. Bode scheme for the redox transformation of Ni(OH)2/
reported that the NixFe1-xSe2 worked as a precursor for in situ NiOOH. Reproduced with permission.[178] Copyright 2015, American
generations of OER active NiFeOx electrocatalyst during oxida- Chemical Society.
tion potential.[146] In this study, the NixFe1-xSe2 was synthesized
through hydrothermal and solvothermal selenization process
and used as OER catalyst. The HR-TEM, TEM-EDX, and XRD phase to β-Ni(OH)2 and then to the higher oxidation state of
analyses showed that during OER process the NixFe1-xSe2 was β-NiOOH phase. However, several studies reported that during
completely converted into highly active NiFeOx and this elec- OER the α-Ni(OH)2 and β-Ni(OH)2 phases change their phases
trochemically derived oxide showed very high OER activity with first to more crystalline β-NiOOH and then to γ-NiOOH due to
η10 = 195 mV, small ζ = 25 mV dec−1 and high durability for the overcharging effect (α-Ni(OH)2 →β-NiOOH →γ-NiOOH).
24 h in 1 m KOH solution. The α-Ni(OH)2 and γ-NiOOH have larger interlayer spacings
(α-Ni(OH)2 = ≈8Å, γ-NiOOH = ≈7Å) than β-phases of Ni(OH)2/
NiOOH (β-Ni(OH)2 = ≈4.6Å, β-NiOOH = ≈4.8Å). On the basis
3.3.2. Nickel Oxide, Hydroxide and Oxyhydroxide of interlayer spacing, the β-phases of Ni(OH)2/NiOOH have a
more compact layer structure which does not allow any guest
Among different Ni-based materials for OER catalysis, one species or ions for intercalation, while α-Ni(OH)2 and γ-NiOOH
with great promise and long history is the nickel hydroxide phases with larger interlayer spacings permit the intercalation
and oxyhydroxide redox pair (collectively termed NiOx),[165b–d] of anion and water molecules (Figure 13). Therefore, compared
which was studied for the first time by Edison in the United to β-phases of Ni(OH)2/NiOOH the α-Ni(OH)2 and γ-NiOOH
States and Junger in Sweden as a cathode material for alka- phases are more OER active due to their larger interlayer
line batteries.[175,176]After this innovative discovery of Edison spacing for the diffusion of OH− ions and H2O/O2 molecules
and Junger the NiOx as a cathode material has become the in the interlayer gallery. In α-Ni(OH)2 and γ-NiOOH phases,
backbone of various secondary alkaline batteries, namely the γ-NiOOH phase has higher oxidation state (≈3.6) and
Ni–Zn, Ni–Fe, Ni–MH (metal hydride), and Cd−Ni recharge- higher OER activity than the α-Ni(OH)2 phase. For example,
able batteries.[176,177] As a commercial importance of NiOx in Yan and coworkers synthesized controllable α- and β-phases
secondary alkaline batteries, it is still highly challenging to of Ni(OH)2 by solvothermal system and compared their OER
boost its activity as a cathode catalyst. As the sluggish kinetics activities.[165b]α-Ni(OH)2 achieved smaller η10 = 331 mV with
of OER is the main hindrance in the metal-air battery perfor- high stability compared to β-Ni(OH)2 (η10 = 440 mV). The
mance,[176,177] much motivation of the early studies was paid to higher OER performance of α-Ni(OH)2 could be attributed to
increase the OER performance of NiOx. To evaluate the NiOx the in situ formation of γ-NiOOH which facilitated the diffu-
for better OER performance it is vital to understand its struc- sion of OER intermediate and their conversion to oxygen mole-
ture, phase transformations and their effect on water oxidation cules. To gain insight into the structural stability of α-Ni(OH)2
reactions. Work of Bode et al. on phases of NiOx using X-ray and β-Ni(OH)2 during OER applications the TEM analysis of
diffraction revealed that the NiOx under an aqueous environ- both phases were performed after 500 CV cycles. The mor-
ment has four different phases with different interlayer dis- phology of α-Ni(OH)2 was well maintained after the CV cycling,
tance such as: two charged phases (β-NiOOH and γ-NiOOH) indicating that the α-Ni(OH)2 changes their phase to γ-NiOOH
and two discharged phases (α and β-Ni(OH)2 (Figure 13, Bode without material swelling and mechanical deformation. In
diagram).[178,179] It is well known that during OER the Ni-based β-Ni(OH)2, considerable particle aggregation and surface corro-
materials change their oxidation state from lower to higher oxi- sion after CV cycling were noted, showing its poor structural
dation state (e.g., Ni+2 →Ni+3) in the anodic potential region stability during OER which is attributed to Jahn−Teller distor-
(the region before onset potential of OER), showing the oxi- tion (spontaneous symmetry breaking in solid state systems)
dation peak in the LSV curve. According to Bode scheme, in of the low-spin d7 Ni3+ centers. More recently Zhang and co-
OER the freshly synthesized α-Ni(OH)2 will first change the workers synthesized 2D α-Ni(OH)2 as an OER electrocatalyst
through the lamellar reverse micelles process which delivered bond length, but the Fe−O bond length exhibited conspicuous
η10 = 260 mV with ζ = 78.6 mV dec−1 and high stability.[180] contraction in oxidized Ni1−xFexOOH. The DFT calculations
The high activity of this catalyst originated from active phase of and EXAFS results revealed that the bond contraction of FeO
γ-NiOOH which was derived from α-Ni(OH)2 during the anodic in Ni1−xFexOOH optimized the binding adsorption energies of
potential region. Similarly, Dou group compared the OER OER intermediates and thus reduced the η for water oxidation
activity of γ-NiOOH phase with NiOOH containing both β- and reaction. Similarly, the DFT+U calculations of Fidelsky and
γ-phases. The OER activity of γ-NiOOH phase was much higher Toroker showed that the Fe-doped NiOOH catalyzes the OER
than those of the mixed β- and γ-NiOOH.[165d] Compared to at low η (= 0.36 V) compared to pure NiOOH (η = 0.61 V).[184b]
β/γ-NiOOH the high OER activity of NiOOH phase is credited Also they showed that the Fe in Fe-doped NiOOH can easily
to its larger interlayer spacing which facilitated the easy diffu- change their oxidation state (from lower to higher) during the
sion of electrolyte and desorption of molecular oxygen from the water oxidation reactions, which is critical for reducing the
catalyst surface. energy barriers of OER intermediates. Wu et al. experimen-
Along with the aforementioned discussion on the struc- tally compared the OER activity of NiO and Fe-doped NiO on
tural and interlayer spacing of β-NiOOH and γ-NiOOH, Yan mesoporous NF (denoted by NiO/NF and Fe11%-NiO/NF).[184c]
et al. demonstrated that the γ-NiOOH is more OER active than The Fe11%-NiO/NF delivered small η10 = 206 mV with high sta-
β-NiOOH.[165b] However, there are still debates as to whether bility compared to pure NiO/NF (η10 = 258 mV). The excellent
γ-NiOOH or β-NiOOH is highly active for water oxidation OER performance of Fe11%-NiO/NF is attributed to mesoporous
reactions. For example, several studies state that the γ-NiOOH architecture of Ni foam and dopant Fe. The mesoporous NSs of
phase is OER active, whereas others claim that β-NiOOH is NF provided abundant open spaces for electrolyte diffusion and
OER active.[165b,c,181] Thus all these contradictory studies on the tight contact of the electrolyte with the catalyst. More signif-
the active sites of NiOx show that along with active phase the icantly, the dopant Fe reduced the energy barrier of OER inter-
OER activities of NiOx catalysts also depend on their designing mediates for the generation of molecular oxygen. Similarly, Sun
and synthesis method, starting precursors (mostly containing et al. compared the OER activities of NiFe-LDH with Ni(OH)2
the trace amount of transition metals impurity such as Fe, Ce, NSs.[185] The NiFe-LDH delivered a smaller η20 = 249 mV com-
Cd, Pb, Zn), cycling of the electrode, morphology, active surface pared to Ni(OH)2 NSs (η20 = 330 mV). In the same study, they
area, and electrolyte.[182,183] For example, Corrigan explored the also showed the effect of vanadium doping on the OER activity
role of Fe and other transition impurities on the OER perfor- of NiFe-LDH (denoted by NiFeV-LDHs). The NiFeV-LDHs
mance of Ni(OH)2.[182] Interestingly he found that the Ce and delivered η20 = 195 mV with ζ = 42 mV dec−1 and showed high
Fe impurities in Ni(OH)2 drastically improved the OER activity stability. The high OER activity of NiFeV-LDHs is attributed to
(with η reduced by more than 100 mV) and other impurities the modified electronic structure of the whole catalyst via vana-
such as Cd, Pb, Zn decreased the OER performance (with η dium doping which improved the electronic conductivity and
increased by ≈20 mV). From these experimental observation, increased catalytic active sites for OER.
Corrigan proposed that such impressive effect of Fe on the
OER activity of Ni(OH)2 could be associated to changes in cata-
lyst conductivity or to the generation of more favorable active 3.3.3. Nickel Phosphides
sites for catalyzing OER intermediates. Similarly, Trotochaud
et al. detected the Fe impurities in NiOOH from analytical TMPs are attractive candidates in many catalysis field due to
grade KOH solution (used as an electrolyte for OER).[183] They its fascinating and unique features such as good conductivity,
found that the small amount of Fe impurity from KOH electro- high stability in basic and acid solutions, facile routes for
lyte dramatically promoted the OER activity of NiOOH, while preparation and their high capacity for the conversion into
in Fe free KOH electrolyte (where stock KOH was completely different phases.[186] The most frequently applied methods
purified from Fe impurity) the NiOOH showed very poor OER for the synthesis of TMP are gas–solid reaction and solution-
activity. The experimental finding of Corrigan and Trotochaud phase reaction. In gas–solid reaction PH3 is an efficient and
certified that the earth abundant Fe metal as a dopant in active source for metal phosphidation, but it is highly noxious
Ni(OH)2 and NiOOH can be utilized for reducing η for OER as and lethal at very low ppm concentration.[32] Hypophosphites
a water electrolyzer.[182,183] Many theoretical and experimental (NaH2PO2 and NH4H2PO2) which are in-situ decomposing
groups studied the role of Fe in OER activity of Ni(OH)2 and and generating PH3 at temperature above 250 °C by reaction
NiOOH, i.e., whether the Fe site itself works as the active center (2NaH2PO2 = PH3↑+ Na2HPO4) are commonly utilized.[186]
or just activates the Ni(OH)2 and NiOOH for better OER per- The generated PH3 reacts directly with metal and forms TMPs.
formance.[184] For example, Friebel et al. reported the DFT with In solution-phase reaction the organic phosphine such as tri-
Hubbard U (DFT+U) calculations for ηOER of pure γ-NiOOH n-octylphosphine (TOP), tri-n-octylphosphine oxide (TOPO),
and Fe-doped γ-NiOOH.[184a] Their calculations showed that triphenylphosphine (PPh3) are used as phosphorus precur-
the Fe-doped γ-NiOOH has much lower η (= 0.43 V) than pure sors. In the solution-phase reaction the target catalyst can be
γ-NiOOH (η = 0.56 V) and the Fe in Ni1−xFexOOH was the phosphatidated at high temperature (≈300 °C at which mostly
active site for water oxidation reaction. To interpret the DFT organic phosphines decompose).[32,186]
results, they experimentally studied the effect of Fe on the struc- It is well known that most of the pure transition metals
ture of Ni(OH)2/NiOOH catalyst (Fe-doped Ni(OH)2/NiOOH are unstable even in weak acidic solutions, but their phos-
was synthesized according to their theoretical design models) phides even at less content of phosphorous (e.g., M3P such
using EXAFS. The Fe addition showed no change in the Ni−O as Fe3P, Ti3P, Ni3P, Cr3P) are highly stable and can be only
dissolved in very strong oxidizing HNO3 solution.[186c] This NiS and Ni3S2 (which have continuous Ni−Ni bonds network in
observation shows that the stability of TMP even in strong oxi- its structure and possess high conductivity) can be applied for
dizing acid can be improved via increasing its phosphorous OER catalysis.[189] For example, Luo et al. synthesized porous
contents.[187] For example, the solubility of MP (such as VP, hollow microspheres of NiS as an OER electrocatalyst by hydro-
CrP, TaP, TiP) are only reported in hot aqua regia (mixture of thermal and calcination process.[189b] Initially, hollow NiS2
hydrochloric acid and nitric acid in a molar ratio of 3:1).[186b] microspheres were synthesized from the hydrothermal reaction
Due to high stability in both acidic and basic solutions the of Ni(NO3)2 and Na2S2O3 and then converted to porous hollow
TMPs are gaining high attention in batteries and water elec- NiS microspheres by heating at 310 °C in H2/Ar atmosphere.
trolysis. As Ni-based materials have high OER activity, most The catalyst exhibited η10 = 320 mV with ζ = 59 mV dec−1 and
of them suffer from poor stability.[187,188] The poor stability high stability. The OER activity of this catalyst might originate
of Ni-based materials can be overcome by using it in phos- from its porous structure having high specific surface area
phide form.[187,188] For example, Paik group synthesized Ni–P and large active sites for water oxidation reactions. Similarly,
via MOF-assisted strategy using Prussian blue analog as a Chen et al. reported NiS NSs grown directly on stainless steel
starting precursors.[187] The catalyst delivered η10 = 300 mV as an OER catalyst which delivered η10 = 297 mV with
with high stability. The OER activity of this catalyst is attrib- ζ = 47 mV dec−1.[189c] Luo and Chen showed that NiSx had OER
uted to uniform distributions of Ni–P in porous carbon. More- activity but required very high η for generation of j10.[189b,c]
over, during OER process the Ni–P was oxidized to Ni-oxides However, Zou et al. showed that the OER performance of NiS
and hydroxides on the catalyst surface. These in situ generated or Ni3S2 was improved by growing it directly on or in some
oxide and hydroxide species provided additional active sites for conductive substrate such as NF.[87b] As in the case of GCE
OER kinetics. Similarly, Lei et al. reported Ni2P hollow micro- the binding polymer (e.g., nafion, which is mostly used for
spheres as an OER catalyst which delivered η10 = 280 mV.[188a] catalyst attachment to surface of GCE) blocked some active

The Ni2P hollow microspheres have a large surface to volume sites of the catalyst from catalytic reaction and thus reduced the
ratio which facilitates the charge/mass diffusion between elec- overall OER activity and conductivity.[190] The in situ growing
trolytes and catalysts for better OER. Although the NiP and of catalyst in conductive NF does not require any binding
Ni2P showed high stability in long run OER application, their polymer and therefore all the active sites will be available for
electrocatalytic activity is not sufficient for efficient OER catal- OER catalysis.[190] Zou et al. fabricated Ni3S2 on NF (Ni3S2/
ysis in water splitting. However, some recent literature shows NF) from direct sulfurization of NF using thiourea (sulfur
that the OER activity of NixP in water electrolysis can be source) in hydrothermal process at 150 °C.[87b] The Ni3S2/NF
improved by designing it in different structure, morphology, or catalyst delivered η10 = 260 mV with impressive stability for
doping with other metals. For example, Xu et al. synthesized 200 h, showing that the direct growth of catalyst on NF increased
aluminum modified Ni5P4−Ni2P foam (denoted by AlNiP) as the OER activity and boosted its stability for long run OER.
an OER electrocatalyst by the sputtering and phosphidation Similarly, Jin et al. synthesized NS of N-decorated nickel-iron
process.[188b] In a typical synthesis process first the pre-treated sulfide (N-(Ni,Fe)3S2) on the alloy of Ni–Fe foam (NIF).[191] The
Ni foam was sputtered with Al (≈500 nm thick layer), followed synthesized catalyst (denoted by (N-(Ni,Fe)3S2/NIF) delivered
by deposition of 50 nm thick Ni layer. To achieve good mixing η10 = 167 mV with small ζ = 33 mV dec−1 and constant activity
and anchoring between Ni/Al and Ni foam the resultant com- for 50 h. The outstanding OER activity of this hybrid is attrib-
posite of Ni/Al/Ni was heated at 600 °C for 2 h in inert atmos- uted to the following: i) the decorated N-anion on the catalyst
phere and then converted to phosphide form by phosphida- surface facilitates the charge transfer during OER; ii) the incor-
tion process. The as synthesized hybrid exhibited very small porated Fe promotes the OER performance of the whole hybrid;
η10/100 = 180/312 mV. This hybrid also showed outstanding iii) the hybrid catalyst has NS-like morphology which is more
stability with no obvious degradation in activity during 8 days conductive than other types; iv) the synergistic effect of Fe and
stability test. The high stability and activity of this hybrid can Ni significantly improves the OER kinetics.
be contributed to its unique structure and morphology. The
XPS and scanning TEM (STEM) results showed that the syn-
thesized AlNiP hybrid was the mixture of Ni5P4 surface/Ni2P 3.4. Molybdenum-Cluster-Based Electrocatalysts for OER
core with Al which was covered with P-rich Ni phosphate
layer. During OER the Ni5P4 /Ni2P was converted to OER- Generally, molybdenum (Mo)-based compounds are well
active Ni(OH)2/NiO nanocrystals and was stabilized by outer known for HER due to their high chemisorption capa-
layer of Ni phosphate for long run OER. bility for hydrogen. Specifically, both molybdenum carbide
and disulfide (Mo2C and MoS2) are inexpensive and earth-
abundant catalysts that exhibit excellent electrocatalytic
3.3.4. Nickel Sulfides activities and stability for HER.[103–108] However, their OER
activities are rarely documented in the literature due high
Among different metal sulfides (MSx) the NiSx has admirable energy barriers for water oxidation reactions on its surface
electrocatalytic and electrochemical activity and therefore has (Figure 3b). For example, Wu et al. demonstrated that the
aroused immense attention in energy storage and conver- chemically exfoliated 1T-MoS2 loaded on the carbon paper
sion devices such as batteries, supercapacitors, solar and fuel (1T-MoS2/CP) delivered η10 = 920 mV with moderate stability
cells.[189] Recently published data show that among various in 0.1 m KOH solution.[192] It revealed that the poor electric con-
phases of NiSx (such as NiS, NiS2, Ni3S2, Ni7S6, and Ni9S8) the ductivity and mass transport properties of MoS2 are the main
hindrance in OER applications, which can be overcome by The designing of MoP hybridized with intrinsically active OER
growing it directly on some conductive nickel or cobalt foam.[193] NiP in 2D or 3D NSs that have rich oxygen vacancies can greatly
In this instance, Yan et al. reported that the MoS2 microspheres improve the electrical conductivity and reduces energy for OH−
on NF (MoS2/NF) required η20 = 310 mV with ζ = 105 mV adsorption on the electrode surface. In this instance, the 3D
dec−1 in 1 m NaOH solution. The higher OER performance of hollow nanoflower of MoNiP (denoted as Mo1Ni1P HNFs) that
MoS2/NF than MoS2 is attributed to good electrical contact of have the structural properties of both 2D and 3D nanostruc-
MoS2 with NF and porous microsphere structure which facili- ture were synthesized through a hydrothermal process using
tated fast electron transfer and mass diffusion during water oxi- NiCl2·6H2O, Na2MoO4·2H2O and NaH2PO2 as Ni, Mo, and
dation reactions.[193a] Similarly, Lieu and co-workers presented P precursors, respectively.[194b] The Mo1Ni1P HNFs exhibited
that the OER activity of MoS2 nanocrystals can be improved by η10 = 275 mV with ζ = 56.3 mV dec−1 and durability for 36 h
growing it directly on Co-foam (denoted by Co @ MoS2).[193b] in 1 m KOH solution. The OER activity of the synthesized cata-
The Co @ MoS2 delivered η10 = 270 mV with ζ = 74 mV dec−1 lyst resulted from the integration of 2D and 3D nanostructure
and high stability in 1 m KOH solution. Although the direct in Mo1Ni1P HNFs with high surface area (262.7 m2 g−1) and
growth of Mo-based catalyst on conductive foam is an impres- heteroatom doping that increased the electronic transport chan-
sive strategy for improving its OER activity, Zhang et al. showed nels for ions diffusion during OER catalyzing reactions. Simi-
that the OER activity of MoS2 can be further improved by inte- larly, Xu et al. reported the hybrid of Ni1Mo1P NSs anchored
grating it with highly conductive and OER active materials on on CNTs surface (denoted Ni1Mo1P NSs @ CNTs) as OER
NF.[193c] The hybrid of Ni3S2 and MoS2 were also directly grown electrocatalyst which displayed η10 = 255 mV with
on NF (Ni3S2/MoS2/NF), which delivered η10 = 218 mV with ζ = 45.1 mV dec−1 and durability for 36 h in 1 m KOH solu-
ζ = 88 mV dec−1 and good stability in 1 m KOH solution. The tion.[196] The OER activity and stability of the Ni1Mo1P
lower η10 of Ni3S2/MoS2/NF than bare MoS2 and Ni3S2 can be NSs @ CNTs is credited to the synergistic effect of bimetallic
attributed to the synergetic effect between Mo and Ni and their phosphide and the strong interaction between Ni1Mo1P NSs
close contact on NF, which facilitated the charge/mass trans- and CNTs.
port for water oxidation reactions. The aforementioned studies Amorphous metallic/bimetallic oxide or oxyhydroxide have
explored high OER activity of MoS2-based materials supported been considered as OER active catalyst, owing to its unique
on NF or integrated with OER active metals. However, still their nanostructure and abundant active catalytic sites.[197] Recently,
OER activities are not sufficient for utilization in whole water it has been reported that the Mo element similar to high-
splitting. valence tungsten metal can further modulate the adsorption
Recently, molybdenum phosphide (MoP) hybridized with energies of bimetallic oxide or oxyhydroxide for water oxida-
other transition metal phosphide (MP) which have high tion intermediates and increases the OER activity.[149,197b]
thermal stability and electronic conductivity has been reported In this regard, Yang and co-workers reported high-valence
as an active OER catalyst.[194] The lone pair electron of P atoms Mo6+ hosted FeCo (oxy)hydroxides (denoted FeCoMo) as
in metal phosphides is modulating the surface charge which OER electrocatalyst.[197b] The FeCoMo hybrid exhibited η10 =
facilitates the reactant adsorption on the catalyst for efficient 277 mV with ζ = 27.74 mV dec−1 and 40 h durability in 1 m
OER catalyzing reactions.[194b] Moreover, the bimetallic phos- KOH solution. The in situ X-ray adsorption data showed that
phide also synergistically enhanced electrochemical proper- the Mo6+ played a significant role in tuning the Fe and Co
ties that can significantly modify the reactants adsorption electronic structures during OER process. During water oxida-
energy.[194] For example, Lee and coworkers reported the hybrid tion, the external potential stimulated the transfer of electrons
of MnPx and MoPy on N/P codoped graphene NSs (MnPx@ to highly oxidized Mo6+ and therefore increased the valence
MoPy/N, P-Gr) as an OER electrocatalyst.[194a] The as-synthe- of the Fe and Co for efficient OER catalyzing reactions. In
sized MnPx@MoPy/N, P-Gr hybrid displayed η20 = 301 mV another study, Mo and Fe modified NiOOH/Ni(OH)2 (denoted
with ζ = 105 mV dec−1 and durability for 30 h in 1 m KOH MoFe:NiOOH/Ni(OH)2) NSs were synthesized through hydro-
solution. The OER performance of MnPx @ MoPy/N,P-Gr thermal and electrochemical oxidation process.[149] The elec-
hybrid is credited to its mesoporous structure, multiple electrochemical analysis showed that the MoFe:NiOOH/Ni(OH)2
troactive sites and synergistic effect of MnPx and MoPy. In displayed high OER activity (η10/100 = 240/280 mV with ζ =
another study, a hybrid of CoP(MoP) and CoMoO3 coated with 47 mV dec−1 and 50 h durability) compared to NiOOH/Ni(OH)2
N-doped carbon shell (CoP(MoP)-CoMoO3@CN) was synthe- (η100 = 400 mV with ζ = 104 mV dec−1). The improved perfor-
sized as OER electrocatalyst through thermal decomposition mance of the catalyst is ascribed to a high Cdl of 0.97 F cm−2
and phosphidation approach.[195] The electronegative P atoms which signifies greater activity. The calculated dopant forma-
on the CoP(MoP)-CoMoO3@ CN and the synergistic effect tion energies of MoFe:NiOOH is significantly lower (−4.51 eV)
of hybrid promoted the deprotonation process a nd p eroxide which shows that the Mo and Fe addition not only decreases
formation during the water oxidation reaction and the refore the formation energy but also assists in improving the struc-
reduced the overpotential for oxygen generation. A s a re sult, ture stability.
the CoP(M o P)-Co Mo O3 @ CN hybrid showed η10 = 296 mV
with ζ = 105 mV dec−1 and stability for 2000 CV cycles in 1 m
KOH solution. 3.5. Single-Atom Electrocatalysts for OER
The electrocatalytic activity of the catalyst strongly depends
on its structural features and electrochemical surface active Graphene confining SACs can also be used as a precious
areas as well as the intrinsic catalytic nature of the metal.[194b,196] metal-free electrode for anodic OER because graphene can
not only modulate the catalytic performance of the single OOH* intermediate (such reaction path is referred to dual-
metal atoms but also provide the active C sites for the OER sites mechanism, Figure 14b), and therefore largely reduce the
catalyzing reactions.[137b,198] Although DFT calculations pre- energy barrier for water oxidation better than single-site mech-
dicted many potential SACs, compared to HER and ORR, anism (Figure 14c). In another study, uniform dispersion of
a few studies devoted to the development of nonprecious single Fe−Nx sites on nitrogen-doped carbon was synthesized,
metal-based SACs for electrocatalytic OER reactions. Recently, which exhibited both the OER and ORR activities.[198b] The cat-
Fei et al. reported a series of metal atoms (Ni, Co, and Fe) alyst displayed η10 = 390 mV for OER and half-wave potential
dispersed in N doped holy graphene matrix (M–NHGFs, at potential 0.86 V for ORR. In Zhang et al. work the single
M = Ni, Co, and Fe).[198a] In a typical synthesis, the aqueous Ni atoms are confined without N ligands in graphene defects
suspension of GO, H2O2, and metal precursor in the desired which showed high OER activity (η10 = 270 mV)[137b] compared
weight ratio were hydrothermally treated to form 3D graphene to MN4C4 ((η10 = 331 mV, as discussed above in the Fei et al.
hydrogel. After freeze-drying, the hydrogel was thermally work[198a]). The DFT calculations demonstrated that the cata-
heated at 900 °C in a gaseous NH3 atmosphere, during which lyst high performance is attributed to unique configurations of
the abundant N from NH3 was incorporated into the graphene Ni atom in the graphene defects, which significantly modified
lattice and provided efficient binding sites for isolated metal the Ni electronic structure for reducing the energy barrier for
atoms. The EXAFS analyses with direct STEM images showed OER reactions.
that the resulting M–N–Cs exhibited the same configuration For OER, the most reported SACs exhibited very poor OER
(MN4C4) with single atom trapped in the di-vacancies of gra- performance compared to commercial Ir/C catalysts and alloy
phene lattice. The as-synthesized catalysts were tested for OER NPs, because the SACs do not constantly show their advan-
activity which followed the trend of Ni (η10 = 331 mV) > Co tages; particularly in the multielectron reaction process. Thus
(η10 = 402 mV) > Fe (η10 = 488 mV). As suggested by DFT great efforts on the design and synthesis of SACs are needed
calculations, the carbon atoms near to nitrogen in N-doped to improve their OER activities. At this point, synthesis of elec-
graphene catalyst are the main binding sites for the OER trocatalyst containing both nanoclusters that will work as active
intermediates. Therefore, in this study, two different reac- center for catalyzing water oxidation reactions and SACS that
tion mechanisms (such as single metal site mechanism and will increase the conductivity of the whole catalyst during OER
metal-carbon dual sites mechanism) were considered for the process are required.
reaction intermediates adsorption on the catalyst sites. The Table 3 summarizes the best OER electrocatalysts reported
DFT calculations concluded that the participation of C atoms in this section, which shows that the hybrid of NiFe with Se,
in the OER process strongly depends on the d-electrons (Nd) Cu, and V exhibits excellent abilities for catalyzing OER in
of the metal atoms in MN4C4 configuration. Specifically, for basic solutions. However, currently there is no good earth-
Co (Nd = 7), and Fe (Nd = 6), all the intermediates strongly abundant metal based electrocatalyst which can catalyze OER
bind at the metal site than the carbon site, and therefore, in acidic solutions. Most of the membranes in fuel cells or
the OER reaction mechanism proceeds on only single atom water electrolyzer are only compatible with acidic environment.
sites (Figure 14a). In the case of Ni (Nd = 8), the OH* and Therefore, the identification of efficacious and stable electro-
O* prefer the C site, while the Ni sites favorably adsorb the catalyst for OER in acidic solutions or fabrication/selection of
Figure 14. Proposed reaction schemes for a) single-site mechanism and b) dual-site mechanism. c) OER free energy diagram on graphene confining
MN4C4 catalysts. Reproduced with permission.[198a] Copyright 2018, Springer Nature.
Table 3. OER electrocatalyst in 1 m KOH solution. however, bifunctional Fe-based active materials for water split-
ting have only recently been extensively studied. For example,
Catalyst Substrate Overpotential η10 Tafel slope ζ Refs. Li et al.[202] synthesized borides of iron in the form of FeB2
[mV] [mV dec−1] NPs for overall water splitting via a facile reduction of Fe2+ by
AlNiP NF 180 27 [188b] LiBH4. The size of FeB2 NPs was around ≈20–50 nm. The cata-
NiFeCu NF 180 33 [147] lyst for HER exhibited cathodic/anodic η10 = 61/296 mV with
ζ = 87.5/52.4 mV dec−1, je = 0.245 mA cm−2, and TOF = 0.165 s−1
G-FeCoW NF 191 – [141]
at η = 100 mV. When this catalyst was assembled as cathode
NiFeV LDHs NF 195@20 42 [185]
and anode for whole water splitting, it required Φ10 = 1.57 V
NixFe1–xSe2-DO NF 195 28 [146] with good stability. The overall performance of this catalyst is
NiO/Co3O4@NC NF 200 73 [155e] attributed to the increased boride in FeB2 as compared to Fe2B
Fe11%-NiO/NF NF 206 49.4 [184c] (considered for comparison sake). The boride rich FeB2 NPs
exhibited better overall water splitting capability in contrast to
MoS2Ni3S2 NF 218 88 [193c]
its counterpart. The rich boride in FeB2 influences the charge
CoFe-0.44 NF 229 64.2 [145]
distribution and facilitates the reaction intermediates by setting
Fe3N/Fe4N NF 238 44.5 [150a] up the balance between chemisorption and desorption. In addi-
NiPO/Fe(OH)x GCE 248 45.4 [139a] tion, the larger surface area is also vindicated by a large value
Fe–Co–P GCE 252 33 [139c] of its Cdl (7.25 mF cm−2) which facilitates the electrocatalytic
reactions. Martindale and Reisner studied the HER and OER
CoNi(20:1)-P-NS GCE 273 45 [160]
activities of metallic Fe and FeOx. The metallic Fe displayed
Ni–P GCE 300 64 [187]
cathodic/anodic η10 = ≈430/420 mV. FeOx showed the cathodic
η10 = ≈460 mV and anodic η10 = ≈400 mV. As a water electro-
suitable anionic membrane for water electrolyzer would be a lyzer, it required Φ10 = 2.2 V with good stability. Chen et al.[203]
major challenge in water splitting. reported 3D iron nickel nitride NPs grown on CC (Ni3FeN/CC)
as an electrocatalyst for overall water splitting. This Ni3FeN/
CC electrocatalyst showed cathodic/anodic η10 = 238/241 mV
4. Electrocatalysts for Whole Water Splitting with ζ = 46/59 mV dec−1. As a water electrolyzer, it required
Φ10 = 1.81 V with high stability of 130 h. The overall efficiency
Water splitting is a foresighted technique to produce green, of this catalyst is attributed to its larger active catalytic surface
clean, and cheap energy to drive our energy requirements for area, and the direct growth of Ni3FeN on CC reduced the resist-
the future. This technique can be better described by a method ance for charge/mass transferred between electrolyte and elec-
of producing hydrogen and oxygen as fuels either by electro- trode. Ma et al.[204] fabricated NSs of Ni–Fe LDH assembled
chemical or by photo-electrochemical conversion from elec- with rGO (denoted by Ni2/3Fe1/3-rGO) as a bifunctional HER
trical energy to chemical energy for energy storage or transport and OER electrocatalyst by precipitation and exfoliation proto-
applications. The overall water splitting is an uphill process cols. This hybrid showed cathodic/anodic η10 = 210/230 mV
due to its two simultaneous reactions, namely, HER and OER, with ζ = 40/42 mV dec−1. When this hybrid was assembled as
demanding more η for activations. Noble metal Pt and its alloys cathode and anode for overall water splitting, Ф10 = 1.5 V was
along with Ir/Ru oxides have setup a benchmark electrocata- required with good stability. The overall water splitting capa-
lysts for HER and OER, respectively, but its scarcity and high bility of the catalyst is ascribed to various factors; first, the LDH
costs are stumbling blocks toward industrial deployment.[199,200] NSs aggregation is prevented by the incorporation of GO/rGO,
Therefore, it is very demanding to develop efficient and stable secondly, the synergistic effect between the direct contact of
electrocatalyst for water splitting. The recent few decades have LDH NSs and GO/rGO favored the OER activity of the electro-
seen unprecedented developments in earth abundant transi- catalyst, and more importantly the intimacy of LDH NSs with
tion metals and its alloys (including Ni, Co, Fe, Mo, and Cu) as rGO due to its removal of oxygen functional groups provided
a bifunctional electrocatalyst for overall water splitting. Here- better contact and easy flow of electrons during the electrolysis.
after, we will discuss the bifunctional electrocatalysts for overall In the work of Panda et al. a highly active FeSe2 electrocatalyst
water splitting. mimicking bioinspired molecular 2Fe–2Se cluster core sup-
ported by a β-diketiminate ligand was synthesized.[205] The cata-
lyst was electrophoretically deposited on NF for HER, OER and
4.1. Iron-Based Electrocatalysts overall water splitting testing in alkaline media. For OER this
catalyst displayed η10/100 = 245/308 mV. Toward HER it achieved
Iron based bifunctional electrocatalysts have gained signifi- η100 = 262 mV. The enhanced activity of this catalyst toward
cant importance in the recent past due to its abundance, less OER stems from the selection of precursor (β-diketiminate
toxic effects to human and environment, and has often easier ligand supporting the all-ferric molecular 2Fe–2Se cluster).
fabrication pathways. Fe enjoys the privilege of the most abun- This precursor allows the synthesis of small yet defined par-
dant transition metals than Co and Ni; thus, Fe is an obvious ticle size, formation of Fe-rich Fe(OH)2/FeOOH species at the
choice and highly attractive element in the design of low-cost surface, and the main important factor is the creation of defec-
electrocatalysts for overall water splitting. Fe-based electrocat- tive sites due to the loss of Se from the surface. The creation
alysts have been broadly studied for either HER or OER,[201] of anionic defective sites offers an increased catalytic surface
area and facilitates the adsorption of OH− and stimulates the reaction capability; 2) the open structures of spherical nano-
transport of electrons, thus promoting OER. The enhanced structures offers larger interaction of its active sites with electro-
activity in HER is corroborated with the bond strength of lytes. Wang et al. synthesized iron doped nickel phosphide NS
Se–H (276 kJ mol−1) and S–H (363 kJ mol−1). The lower bond arrays (NSAs) for overall water splitting.[209] The nickel phos-
strength dictated the promotion of easy release of H2. When phide catalyst supported on NF denoted as (Ni1.85Fe0.15P NSAs/
assembled as an alkaline water electrolyzer FeSe2/NF∥ FeSe2/ NF) exhibited better HER/OER achieving η10/20 = 106/270 mV,
NF, it displayed Φ100 = 1.73 V. Cui group reported a lithium with ζ = 89.7/96 mV dec−1. When assembled as a water electro-
induced bifunctional electrocatalyst based on transition metal lyzer Ni1.85Fe0.15P NSAs/NF//Ni1.85Fe0.15P NSAs/NF exhibited
oxides for overall water splitting.[206] Lithium-extracted ultras- Φ10 = 1.61 V. The overall performance of the catalyst is ascribed
mall NiFeOx NPs were drop casted on carbon fiber paper (CFP) to many factors; for instance, 1) the Cdl of 8.48 mF cm−2 is
denoted as NiFeOx/CFP and tested for OER and HER perfor- an indication of larger electrochemical surface area, which is
mance. Toward OER, the increased valency of transition metal often the choice of design consideration for better catalytic per-
centers and the increased Fe-3d and O-2p hybridization states formance; 2) the charge transfer resistance (Rct) is less than
facilitated the water oxidation reactions, which is well displayed 10 Ω indicating fast charge transfer capability of this catalyst;
by an anodic Φ10/20 = ≈1.53/1.58 V. For HER, it displayed a 3) better OER activity is attributed to the reaction intermediate
cathodic η10 = 88 mV. As a water electrolyzer, it required Φ10 = species like NiOOH and Ni(OH)2. These intermediates pro-
1.51 V. The overall performance of the catalyst arises from dif- viding an easy pathway for OER are attributed to the oxidation
ferent factors; for instance, the polycrystalline NP nature of of Ni2+ to Ni3+. The higher metallic content provides better elec-
the catalyst increases the active surface area and the number trical conductivity required for easy charge transfer during the
of active sites, and the use of conducting carbon as a substrate electrocatalytic reactions of water splitting. In another study, a
helps in binder free fabrication of catalyst empowering larger hybrid of FeP/Ni2P supported on NF was synthesized which
current and circumventing the bubble-release problems. showed a tremendous potential toward HER/OER and whole
water splitting in alkaline media.[210] Toward OER, this catalyst
displayed high catalytic activity with η10 = 154 mV, minimal
4.1.1. Iron-Phosphides ζ = 22.7 mV dec−1 and high Cdl = 19.3 mF cm−2. The smaller
ζ and high Cdl values indicated that the OER reaction kinetics
Iron in its elemental state has not shown a significant impact favors a faster mass and electron transfer on the FeP/Ni2P sur-
in water splitting and hence its alloying with other transition face. This material executed the HER activity at η10 = 14 mV
metals is required. Its efficiency and activity can be further with ζ = 24.2 mV dec−1. When assembled as a water electro-
increased by doping with electronegative atoms such as phos- lyzer, the FeP/Ni2P hybrid exhibited Φ10 = 1.42 V with excellent
phorous. Doping with pentavalent phosphorous favors the stability even at a high current density of 30 and 100 mA cm−2
electron rich sites and promotes faster catalytic reactions. In for 36 h. The simulation results performed on the FeP(001)/
addition to this, strong PO bonds are a strategy often used Ni2P and FeP(010)/Ni2P surfaces demonstrated that there is
in the electrochemistry to avoid the blockage of electron trap- a substantial electron transfer from Ni2P to FeP surface. This
ping sites. Yan et al. designed a flexible electrode based on electron transfer from the Ni2P to FeP surface created a vacancy
iron phosphide nanotubes toward full water splitting.[207] The at the Ni2P surface and increased holes which shifted down-
synthesized material consisted of FeP covered with iron oxide/ ward the Fermi level of Ni2P surface, thus facilitating the OER
phosphate film generated H2 from acidic/alkaline electrolyte process. The excellent HER activity arises from a high Cdl value
with η10 = 88/120 mV and ζ = 35.5/59.5 mV dec−1. OER was of 907.8 mF cm−2 giving high active surface area in the reac-
achieved with η10 = 288 mV and ζ = 43.0 mV dec−1. When tion. This resulted in an excellent overall water splitting capa-
assembled as overall water splitting it consumed Φ10 = 1.69 V. bility of the catalyst.
The overall performance of this catalyst is attributed to the
surface iron oxide and phosphate, which facilitates easy water
splitting steps and provides catalytic behavior. Huang et al. syn- 4.1.2. Iron-Sulfides
thesized iron tuned Ni2P catalyst for overall water splitting by
tuning the atomic ratio of Ni/Fe.[208] The bifunctional catalyst The catalytic behavior of iron toward water splitting can be
assembled on 2D carbon fiber (CF) denoted as (Ni1.5Fe0.5P/ improved by doping it with another electronegative atom,
CF) demonstrated larger active sites and open structures which i.e., sulfur. Doping with tetravalent sulfur favors the elec-
ultimately favored better HER and OER properties. Toward tron rich sites and promotes faster catalytic reactions, though
OER, the Ni1.5Fe0.5P/CF displayed η10/20 = 264/280 mV with at a slight lower rate than phosphorous which provides five
ζ = 55 mV dec−1. The smaller ζ is an indication that the reac- electrons. In addition, this strategy is co-used in conjunction
tion kinetics is faster for mass and electron transfer. Toward with phosphorous doping to avoid the blockage of electron
HER, it displayed η10 = 282 mV with ζ = 125 mV dec−1. As a trapping sites. Yu et al. synthesized economical, efficient,
water electrolyzer, it generated j = 10/20 mA cm−2 at a poten- and stable bifunctional (Ni0.7Fe0.3S2) electrocatalysts toward
tial 1.589/1.635 V. The overall performance of the synthesized overall water splitting.[43] A hierarchically porous 3D ternary
catalyst emanated from the following factors: 1) incorporating nickel iron sulfide microflowers are grown directly on Ni
Fe in the Ni2P structure not only modifies the electronic struc- foam. The synthesized Ni0.7Fe0.3S2 demonstrated HER activity
ture but also helps in modifying the surface properties, which with η10 = 155 mV and ζ = 109 mV dec−1, Cdl = 3.0 mF cm−2
ultimately offer larger catalytic surface area leading to better and good stability in 1 m KOH solution. For OER it delivered
η10 = 198 mV with ζ = 56 mV dec−1. When assembled as an When assembled as a water electrolyzer it displayed Φ10 = 1.7 V
overall water splitting electrolyzer, it consumed Φ10 = 1.625 V with good durability.
with good stability. This efficient water splitting was attributed Although cobalt based materials have substantial poten-
to effective Fe doping along with its 3D hierarchical flowery tial for the catalysis of overall water splitting, it required large
structure. The addition of Fe altered the morphology of cata- η and their stability is also a major issue on many occasions.
lyst from vertical alignment to 3D hierarchical flowery struc- Hence, alloying Co with other elements is highly demanded
ture. The obtained structure not only provided larger catalytic to overcome these aforesaid problems. Doping with other
active area but also facilitated the mass transfer during water transition metals helps in modifying the electronic structure
splitting reaction. of Co. Doping with transition metals in the presence of ele-
ment like nitrogen improves HER activity due to the electron
donating characteristics of N. Addition of elements from transi-
4.2. Cobalt-Based Electrocatalysts tion metal such as Cu (Cu2+) which generally lies at octahedral
sites improves the catalytic activity as compared to the divalent
Cobalt has come up with substantial potentials for overall water radicals at tetrahedral sites[217] and also offers better corro-
splitting due to its nonprecious, economical, and potential cata- sion resistance. Wang et al. fabricated porous and hierarchical
lytic activity nature. It is reported that Co has low energy barrier N-doped carbon coated CuCo2Nx NS on carbon fiber (NC@
for hydrogen absorption[211,212] favoring HER catalysis, but as an CuCo2Nx/CF) as an electrocatalyst which catalyzed both HER
overall water splitting electrocatalyst, its OER activity must be and OER.[218] This hybrid delivered a cathodic/anodic η10 =
improved. Published literature supports compounds of cobalt 105/230 mV with ζ = 76/84 mV dec−1. As a water electrolyzer,
for instance Co3O4 as an efficient OER catalyst, but pure Co3O4 this catalyst displayed Φ10 = 1.62 V. Interestingly, in the pres-
is prone to easy accumulation and its poor conductance causes ences of 15 × 10−3 m benzyl alcohol in 1.0 m KOH solution, this
blockage of active sites resulting in severely deteriorating trans- catalyst required only 1.5 V to deliver j10 with stability for 60 h.
port of protons or electrons during oxidation.[213,214] In this situ- The performance of this hybrid electrocatalyst for whole water
ation it becomes imperative to look for an alternative catalyst splitting is attributed to its hierarchical architecture which
that can catalyze both HER and OER. However, cobalt oxides offered a large surface area for electrolyte diffusion and the
on carbon supports offer better conductivity, huge surface area synergistic effect between Cu3N and Co5.47N NPs and conduc-
to enhance catalytic activity, structural stability and robust toler- tive N-coated carbon which facilitated the effective charge/mass
ance to various chemical environments. For example, Jin et al. transportation during HER and OER. Liu et al. synthesized two
synthesized N-doped carbon hybrids consisting of cobalt–cobalt different catalysts for HER and OER such as Co NSs on NF
oxide denoted as CoOx@NC as an efficient electrocatalyst for (Co-NSs/NF) for HER which delivered a cathodic η10/100/400 =
overall water splitting.[212] This hybrid catalyst exhibited onset 20/60/83 mV with ζ = 42.6 mV dec−1, and cobalt-iron-boron
potential of 85 mV, cathodic/anodic η10 = 232/260 mV with oxide NS on NF (CoFeBO-NSs/NF) for OER which generated
ζ = 115 mV dec−1. As a water electrolyzer, this catalyst displayed anodic η10/100 = 240/280 mV.[219] When both catalysts were
Φ20 = 1.55 V with good stability. The performance and stability assembled for whole water splitting (Co-NSs/NF for HER and
of this hybrid bifunctional electrocatalyst is credited to the CoFeBO-NSs/NF for OER), Φ10/400 = 1.5/1.8 V was required.
synergistic effect of cobalt and cobalt-oxide and their uniform Moreover, these catalysts when assembled as an overall water
distribution on high surface area of carbon which offers full electrolyzer also showed high stability even at j = 400 mA cm−2
exposure of its active sites and good conductivity for charge/ for 20 h. The better catalytic performance is attributed to the fol-
mass transport during catalytic reactions. Stability of this lowing factors: 1) the better adherence of Co-NSs and CoFeBO-
hybrid was assured from the encapsulation effects of graphitic NSs to NF avoids the possibility of aggregation during long
carbon, which protected Co from leaching during long-run sta- term electrolysis; 2) the NSs structures of Co-NSs and CoFeBO-
bility applications; and adding nitrogen enhanced the electron NSs offer better and larger contact with electrolyte; and 3) the
donating effect ultimately leading to improved catalytic effect. effective electrical connectivity, NSs structure, and higher mass
Guo et al. synthesized amorphous cobalt boride on cobalt dis- loading provide efficient catalytic activity and improve overall
elenide NSs (Co2B/CoSe2) for overall water splitting in alka- water splitting. Babar et al. synthesized cobalt iron hydroxide
line medium.[215] This bifunctional catalyst exhibited anodic/ on NF (CoFe/NF) as a bifunctional electrocatalyst by electro-
cathodic η10 = 320/300 mV with ζ = 56/76 mV dec−1. This cata- deposition method, which showed a cathodic η10 = 110 mV
lyst has je = 33.5 µA cm−2, demonstrating its high OER activity with ζ = 54 mV dec−1 and anodic η10 = 220 mV with ζ = 40 mV
due to its better Cdl = 36.2 mF cm−2. Its shows better HER dec−1.[220] The water electrolyzer showed Φ10 = 1.64 V with sta-
activity due to its high Cdl (30.9 mF cm−2) with je = 23.8 µA cm−2. bility of 50 h. The overall performance of the catalyst is attrib-
As a water electrolyzer, this catalyst displayed Φ10 = 1.73 V with uted to the synergistic effect between Co and Fe. Xiao et al. filled
stability of 30 h. The performance of this bifunctional electro- the oxygen vacancies in Co3O4 with phosphorous to enhance
catalyst is attributed to its better electrochemical double layer, the capability of this catalyst toward overall water splitting.[221]
indicating relatively larger surface area which in turn offers The catalyst denoted as P-Co3O4 was based on the idea that
larger catalytic surface area for catalytic activity. Wang et al. the stabilization of vacancies can be easily achieved by filling
synthesized cobalt based catalyst encapsulated in nitrogen the coordination numbers with heteroatoms. The phosphorus
doped carbon material denoted as (Co@NC).[216] This electro- contains 3p orbitals and vacant 3d orbitals, which instigates
catalyst displayed bifunctional activity toward overall water the local charge density to accumulate on the surface, thereby
splitting, which exhibited a cathodic/anodic η10 = 210/400 mV. increasing the electrocatalytic performances. The synthesized
P-Co3O4 showed cathodic η10 = 120 mV with ζ = 52 mV dec−1 electrocatalysts toward overall water splitting techniques.[226]
and anodic η10 = 280 mV with ζ = 51.6 mV dec−1. The charge The synthesized nanocomposites (CoP/rGO-400) were pre-
transfer resistance Rct of this catalyst is 3.45 Ω indicating annealed at 400 °C, which worked efficiently in water splitting.
toward better participating capability in the reaction during The as-obtained bifunctional electrocatalyst showed good
water splitting. The P-Co3O4//P-Co3O4 couple, as water elec- activity and stability toward both HER and OER. The larger sur-
trolyzer, required Φ50 = 2.23 V. The overall performance of the face area (1500 m2 g−1) of this catalyst offered an efficient expo-
catalyst can be derived from the electrons entering in octahedral sure of catalytic active sites for free diffusion of gas (H2 and O2)
Co-3d orbitals rather than tetrahedral sites. When phosphorous and electrolyte. Therefore, the resulting electrocatalyst
atoms enter these vacant spaces, electrons are transferred out of offered cathodic η10 = 150 mV with ζ = 38 mV dec−1. OER was
the 3d orbitals and more Co2+ and Co3+ states are left in P-Co3O4. achieved at η10 = 340 mV with ζ = 66 mV dec−1. It also demon-
The high metallic content favors the electronic conductivity, thus strated stability over 22 h with j10 (for HER or OER). When
favoring the overall catalytic reactions. assembled as water electrolyzer it required Φ10 = 1.7 V. The syn-
ergistic effect between CoP and rGO added into porous nano-
structures is the major responsible factor for the superior,
4.2.1. Cobalt-Phosphides durable and high conductivity of this catalyst during overall
water splitting. Jin et al. fabricated Co2P NWs (Co2P-NWs) as a
TMPs demonstrate high stability allied with better electrical bifunctional electrocatalyst using microwave-assisted tech-
conductivity. Combing Co with phosphates, phosphides, and nique.[227] This Co2P-NWs showed HER/OER activity with
phosphonate raises the electrical conductivity and can be uti- cathodic/anodic η10 = 95/260 mV. In whole water splitting this
lized as an electrocatalyst for overall water splitting.14-16 Among Co2P-NWs delivered Φ10 = 1.44 V. The bifunctional property of
them, cobalt phosphides have gained due attention and remain this catalyst toward overall water splitting is attributed to the
to be one of the most investigated bifunctional electrocatalysts electron donating property of phosphorous in Co2P-NWs. The
for water splitting.[222] In this pursuit, numerous research partial negative charge over phosphorous (δ−) and partial posi-
groups have come up with different methodologies to under- tive charge over metallic cobalt (δ+) site act as a proton and a
stand the hidden science behind it and have engineered the hydride acceptor, respectively. DFT calculations provided that
cobalt phosphides-based compounds for overall water splitting. the electron density near the Fermi level is more in Co2P-NWs,
Sun and coworkers synthesized hybrid NPs of CoP and Co2P which promoted lesser resistance and superior electrical con-
encapsulated in N-doped carbon matrices (denoted by Co-P/ ductivity. Yang et al. synthesized NW arrays of cobalt phosphide
NC) by MOF assisted carbonization and phosphidation grown on Ti mesh (TiM) (CoP-NWs/TiM) for overall water split-
methods.[223] The catalyst possessed mesoporous structure with ting.[228] This catalyst displayed a cathodic η10 = 72 mV with
large BET surface area of 183 m2 g−1. This electrocatalyst ζ = 65 mV dec−1 and anodic η10 = 310 mV with ζ = 87 mV dec−1.
achieved cathodic η10/20/100 = 191/212/277 mV and anodic When this CoP-NWs/TiM was assembled as a cathode and
η10 = 354 mV. As a water electrolyzer it delivered Φ165 = 2.0 V anode for whole water splitting, Φ10 = 1.64 V was required. The
for 24 h. The high activity of this catalyst can be ascribed it to efficient performance of this catalyst for HER/OER can be
large surface area and porous structure which facilitated the ascribed to the following aspects; i) 1D growth direction of the
charge/mass transport and exposure of active catalytic sites catalyst facilitated the faster electron transfer and the open
during the reactions as well as to the high intrinsic HER and spaces between nanostructured wires allowed exposure of more
OER activities of CoP/Co2P. Meanwhile, the stability for whole active sites and favored easy diffusion of electrolytes, ii) close
water splitting of this catalyst originates from encapsulation contact between CoP and TiM due to direct growth of CoP onto
effect of N-C, which protected the NPs from leaching in solu- TiM offered better mechanical strength and superior electrical
tion during long-term durability test. Similarly, Jiang et al. fab- conduction, iii) high mass loading capacity of CoP on TiM
ricated Co–P film on copper foil as a bifunctional electrocatalyst without polymeric binder improved the conductivity and
by electrodeposition method.[224] This Co–P exhibited superior increased active catalytic sites for whole water splitting. Wu et al.
HER activity with ζ = 42 mV dec−1 and η10/20/100 = fabricated a 3D porous nanosphere of cobalt phosphide on CC
94/115/158 mV and reasonable OER activity with ζ = 72.2 mV via topotactic phosphidation of Co3O4 (denoted by CoP3/CC).[229]
dec−1 and η10/100/500 = 345/413/463 mV. As a two-electrode The synthesized catalyst denoted as CoP3/CC showed cathodic/
system this catalyst required Ф10 = ≈1.56 V with stability for anodic η10 = 121/291 V with ζ = 66/72 mV dec−1. When this
24 h. Chang et al. fabricated CoP NS (CoP-NS) as a bifunctional catalyst was assembled as cathode/anode for whole water split-
electrocatalyst from simple phosphodization of Co3O4.[225] This ting, Φ10 was achieved at 1.54 V with stability of 10 h. The
CoP-NS generated cathodic η10/20/50 = 111/139/191 mV and overall performance of this catalyst is attributed to various fac-
anodic η10 = 277 mV with ζ = 85.6 mV dec−1. As a cell electro- tors; for instance, its high phosphorous content increases the
lyzer this CoP-NS required Φ10 = 1.54 V with good stability. The accumulation of protons ultimately leading to acceleration of
overall performance of this bifunctional electrocatalyst is the electrolytic process, yet another factor is its intrinsic 3D
ascribed to surface passivation effect of CoP-NS which pro- porous structure which facilitated the transfer of electrons and
tected the electrodes from degradation and thus maintained the the exposure of larger surface area toward electrocatalytic
electrolysis uninterruptible, and the nanoporous structure of reactions. The important factor which boosted the overall water
CoP provided numerous catalytic sites and thus facilitated mass capability is the directly grown of CoP3 on CC, which offered a
transport during electrolysis. Jiao et al. synthesized a sandwich- better electrical contact and facilitated the better electrical con-
type MOF/GO as a template and CoP/rGO composites as ductivity and mechanical stability. Cheng et al. synthesized a
bifunctional electrocatalyst consisting of CC supporting cobalt water splitting is attributed to the high electron density around
phosphide (CoP/CC).[230] The catalyst demonstrated catalytic the d-orbital of Co from the electron transfer of NCNHP to CoP
activity for HER in alkaline and acidic media and OER in alka- (Figure 14e). The calculated ΔGH* for 0/50/100% surface-oxi-
line environment. This bifunctional catalyst exhibited cathodic/ dized CoP is 0.22/0.29/0.49 eV (Figure 14f). These ΔGH* values
anodic η10 = 131/300 mV with ζ = 64/124 mV dec−1. The OER are a reasonable explanation of hydrogen activity in HER and a
activity of the catalyst was attributed to the synergistic effect showcase that a higher surface oxidized CoP decreases HER
between the metallic oxides formed on the surface of the cata- activity.
lyst and CoP. As a water electrolyzer, this catalyst displayed
Φ10/20 = 1.68/1.78 V, with stability for ≈28 h. The performance
of this catalyst toward overall water splitting was attributed to 4.2.2. Cobalt Sulfides
the fact that CoP nanostructures were grown vertically or per-
pendicularly to CC, thereby offering larger electrocatalytic sur- Cobalt sulfides based bifunctional electrocatalysts for overall
face area. In addition, these perpendicular structures could water splitting have recently attracted attention due to its nat-
encounter the electrolyte, effectively offering better electrolytic ural abundance, inexpensive, and most importantly its electrical
performance. Pan et al. synthesized NPs of CoP embedded conductivity at small η[232] allied with mechanical and thermal
inside a nitrogen doped CNTs bearing a polyhedron structure stability displaying 100% Faradaic efficiency.[233] Doping with
denoted as (NCNHP) obtained via a three step process of pyrol- electronegative sulfur atom induces a partial negative charge
ysis–oxidation–phosphidation strategy derived from core–shell (δ−) in the catalyst. These partial negative sites act as a base and
of zeolitic imidazolate frameworks ZIF-8 at ZIF-67.[231] The cat- a center for trapping protons and helps in faster discharge pro-
alyst denoted as (CoP/NCNHP) demonstrated HER activity in cess, thus promoting HER sites in the electrocatalyst reactions.
acidic(0.5 m H2SO4)/ basic(1 m KOH) solutions with η10 = The electrocatalyst involved in OER is prone to get corroded
140/115 mV (Figure 15a) and ζ = 53/66 mV dec−1. The HER as the reactions are mainly carried out in either highly alka-
activity of this hybrid is attributed to the larger electrocatalytic line or acidic medium. Sulfide based catalysts offer resistance
active sites as reflected from the higher Cdl (16.8 mF cm−2). to corrosion are often used as corrosion inhibitors.[234] Zhu
Toward OER this hybrid showed η10 = 310 mV (Figure 15b) and et al. synthesized cubical cobalt sulfide (Co9S8) decorated with
ζ = 70 mV dec−1 with stability 1000 CV cycles in 1 m KOH solu- layers of MoS2 on carbon nanofibers (CNFS) as a bifunctional
tion. When fabricated as a water electrolyzer it displayed Φ10 = electrocatalyst (denoted by Co9S8@MoS2/CNFs).[235] This
1.64 V (Figure 15c) with stability of over 36 h (Figure 15d). DFT hybrid showed cathodic/anodic η10 = 190/430 mV, respec-
calculations proved that the high activity of this material toward tively. When this hybrid was assembled as cathode and anode
Figure 15. a) LSV polarization curves of CoP/NCNHP in 1 m KOH solution for HER. b) LSV polarization curves of CoP/NCNHP in 1 m KOH solution
for OER. c) LSV polarization curve of the overall water splitting for CoP/NCNHP∥CoP/NCNHP electrode in 1 m KOH at 5 mVs−1 scan rate with iR
compensation in a two-electrode system. d) Chronopotentiometric curve of water electrolysis at varying current densities in 1 m KOH. e) DOS curves
for pure CoP and CoP/NCNHP. f) Calculated free energy diagram of the HER on 0/50/100% surface-oxidized CoP. Reproduced with permission.[231]
Copyright 2018, American Chemical Society.
for whole water splitting, Φ10 was achieved at 1.60 V with sta- electrocatalyst exhibited HER activity over substantially longer
bility of 10 h. The overall performance of this hybrid is attrib- cycles well over 1000 CV at a scan rate of 300 mV s−1 due to its
uted to the synergistic effect emanating from contact surface phase and structural integrity retention. The other contributing
of core Co9S8 with MoS2 shell as well as the surface defective factor arises from the morphological arrangements of octahe-
sites generated on the surface of this hybrid from the stacking dral CoS6 in which Co2+ and Co3+ ions exist in partial oxidized
effects of MoS2 layers around the Co9S8 core. Dai et al. syn- states in the pyrite type CoS2. The presence of electron rich S
thesized a nonstoichiometric compound consisting of cobalt sites in CoS2 offers more proton–acceptor centers in the cata-
mono-phosphosulfide with a hexagonal close-packed phase lyst for better desorption and adsorption, thereby facilitating
for overall water splitting.[236] In the synthesized Co0.9S0.58P0.42 HER activity. The OER activity of the catalyst is offered by a
hybrid, the Co3+/Co2+ couples were preferentially activated by larger Cdl = 20.05 mF cm−2 and a lower charge transfer resist-
tuning the P/S ratio by controlling the degree of sulfuriza- ance of 1.35 Ω. The larger capacitance value offers larger elec-
tion. This hybrid showed anodic/cathodic η10 = 266/139 mV trocatalytic surface area, and the lower value of charge transfer
with ζ = 48/72 mV dec−1. As a water electrolyzer it required resistance facilitates easy charge flow with less dissipation of
Φ10 = 1.59 V. The synthesized catalyst has a unique yolk–shell applied potential. When assembled as a water electrolyzer in
sphere structure offering greater catalytic surface area. The alkaline environment it showed j10 at 1.54 V at 60 °C with a
better OER can easily be understood from the fact that the OER Faradaic efficiency of 100%.
activity mainly relies on surface chemisorption and interfacial
free energies. This catalyst had higher Co3+ oxidation states
added to Co2+ states in Co0.9S0.58P0.42, which further increased 4.3. Nickel-Based Electrocatalysts
the catalytic activity of this bifunctional catalyst. Wang et al.
fabricated a 3D array architecture consisting of conducting 4.3.1. Nickel with Ni-Alloying Elements
substrate of facile carbon paper (CP) and carbon tubes (CT)
on which Co–S sheets are grown successfully.[237] The thick- Nickel is identified as a potential candidate material in water
ness of deposited cobalt sulfide was around ≈130 nm. The syn- splitting due to its nonprecious and nature-abundant ele-
thesized catalyst denoted as CP/CTs/Co–S showed cathodic/ ment placed in the same group of Pt in the periodic table. In
anodic η10 = 190/300 mV with ζ = 131/72 mV dec−1. The j10 commercial practice, Ni, particularly Ni foam, is often a decent
for HER/ OER was 0.039/0.83 µA cm−2. This catalyst exhibited choice for cathode material in most electrolysis units in alka-
TOF of 1.2 × 10−1 s−1 at η = 250 mV in HER and 1.6 × 10−2 s−1 line media. However, as a catalyst, Ni shows poor stability for
at η = 300 mV for OER. When this catalyst was assembled as water splitting. Thus, doping Ni metal or its selenides, sulfides,
cathode and anode for whole water splitting, Φ10 was achieved phosphides, and oxides with other transition-metal might offer
at 1.743 V with stability of 7000 s. The overall performance some new solutions to this problem.[240] Doping nickel with
of this catalyst was attributed to the increased stability and selenides in different stoichiometry has improved the catalytic
the internal gaps between the structured nanoarrays of Co–S, activity and has been used as active bifunctional electrocatalysts.
which exposed more catalytically active sites. The larger surface For instance, Tao et al. synthesized NSs and NWs morphology
area is also vindicated by large value of its Cdl = 103.7 mF cm−2. of nickel cobaltite (NiCo2O4) for HER and OER in alkaline
The other factor is the provision of continuous electron transfer medium for overall water splitting.[241] In this technique two
pathway due to the presence of strong contacts between CTs different morphologically active catalysts for HER and OER
and CP. Zhu et al. developed a hydrophilic bifunctional elec- are assembled together for overall water splitting. The syn-
trocatalyst for overall water splitting consisting of Co3S4.[238] thesized NiCo2O4 showed cathodic/anodic η10 = 170/230 mV
This hydrophilic catalyst denoted as Co3S4-L has a NS architec- with ζ = 63/85 mV dec−1. This catalyst exhibited TOF of
ture consisting of hydrophilic surface which facilitated the easy 0.26/0.07 s−1 at η = 0.30 V for HER/OER. When this catalyst
diffusion of reactants into the pores of electrodes toward the was assembled as cathode and anode for whole water splitting,
catalytic active sites. The Co3S4-L catalyst showed a cathodic/ the j = 20 mA cm−2 was achieved at potential 1.70 V with long
anodic η10 = 270/360 mV with ζ = 124.5/84.7 mV dec−1. The term stability. The overall performance of this catalyst is attrib-
performance of this catalyst was far better than the hydro- uted by the following factors. First, the larger catalytic surface
phobic bifunctional catalyst denoted as Co3S4-B. The better area of the synthesized NSs and NWs morphology is vindi-
performance of the Co3S4-L catalyst suggested that the hydro- cated by a large value of its Cdl = 60 mF cm−2 which favored
philic nature is important for the bifunctional catalysis. When toward the increased performance of individual HER and OER.
this catalyst was assembled as cathode and anode for whole Secondly, the theoretical calculations of energy distribution of
water splitting, j10 was achieved at potential of 1.63 V with d-band in NCO-NSs and NCO-NWs along the planes of (311)
stability of 10 h. The overall performance of this catalyst was were −2.156 and −1.787 eV respectively, very close to those
attributed to the increased hydrophilic sites of Co3S4-L which of Pt (111) (−2.37 eV) and RuO2 (110) (−1.393 eV). This low
offered better contact between electrolyte and catalyst. Ma energy value is an indication of ample contact and interaction
et al. synthesized compositional and phase controlled hollow between various species and electrolyte leading to better elec-
nanospheres of cobalt sulfide (CoSx: Co3S4, Co9S8, and CoS2) trochemical performances. It is well known that the suitable
toward overall water splitting. Among these synthesized cata- positioning of d-orbital with respect to the Fermi level is vital
lyst CoS2 demonstrated better electrocatalytic property toward in determining the active sites within the catalyst for enhanced
water splitting.[239] The catalyst showed cathodic/anodic η10 = electrochemical activity.[242] Benefiting from the negative energy
193/290 mV and the corresponding ζ = 100/57 mV dec−1. This level of the d-band of NCO-NSs (−2.156 eV) and NCO-NWs
(1.787 eV), which are close to that of Pt (111) (−2.37 eV) and for HER and OER in alkaline media. The cathodic/anodic
RuO2(110) (−1.393 eV) along the (311) plane additionally η10 = 94/270 mV was achieved with ζ = 90/54 mV dec−1. The
boosted the catalytic performance of the synthesized catalyst. enhanced activity of this catalyst is attributed to high electrical
Wu et al. developed a technique of hetero-structures assembly conductivity of nitride loaded with bimetals (Fe and Ni) and
for overall water splitting.[243] In this technique two separately the 3D-rGO aerogel structure supports an efficient mass trans-
active catalysts for HER (NiMoN) and OER (Ni3N) are assem- port. When assembled as electrolyzer in alkaline media using
bled together for overall water splitting. The synthesized assem- Ni3FeN/r-GO as electrode material, it consumed only 1.60 V to
bled catalyst denoted by Ni3N-NiMoN showed anodic/cathodic achieve j10 and demonstrated a durability well over 100 h.
η10 = 277/31 mV with ζ = 64/118 mV dec−1. The j and TOF The idea of 3D core–shell nanostructure supported on some
for HER of this catalyst was 3.24 mA cm−2 and 0.265 s−1 at conductive substrate due to their efficient charge transfer,
η = 100 mV, respectively. When this catalyst was assembled as large surface area and intimate contact with electrolyte are of
cathode and anode for whole water splitting, j10 is achieved at interest in the field of water splitting.[248] Due to the inherent
1.54 V with long term stability. The overall performance of this stability of core–shell structures, the catalyst designed with this
catalyst is attributed to the increased performance of individual idea possesses inherent stability in corrosive environments
HER and OER catalytic reactions. The larger surface area is also which are often encountered to water splitting catalysts.[248] In
vindicated by a large value of its Cdl (241 mF cm−2). Pu et al. this direction, a Cu core shelled with layered double hydroxide
synthesized alloy of NiSe2 on Ti plate (NiSe2/Ti) by electrodepo- NSs of NiFe on Cu foam (denoted Cu@ NiFe LDH) has been
sition method, which showed cathodic η10 = 96 mV with ζ = synthesized for whole water splitting.[248] The OER activity of
82 mV dec−1 and anodic η20 = 295 mV with ζ = 82 mV dec−1.[244] this catalyst is displayed at η10/100 = 199/281 mV with small
When this catalyst was assembled as cathode and anode for ζ = 27.8 mV dec−1. Toward HER, this catalyst demonstrated
whole water splitting, j10 was achieved at 1.66 V with long term η10/100 = 116/192 mV with ζ = 58.9 mV dec−1. When Cu@
stability. The overall performance of this catalyst is attributed NiFe LDH was coupled as a cathode and anode for whole water
to the following factors. The Cdl (27 mF cm−2) and the rough- splitting catalyst, it demonstrated j10/100 at 1.54/1.69 V with
ness factor of 11.2 which is nearly thrice that of Ni(OH)2/Ti, high stability. The performance of this bifunctional catalyst is
giving much exposure to catalytically actives sites of NiSe2/Ti ascribed to various factors such as core shelled structures offers
for participation in electrochemical reactions. The other factor relatively better stability, small Tafel slope indicating faster reac-
is conductive network of NiSe2 NPs which serves as an elec- tion kinetics, high catalytic surface area and most importantly a
tron pathway and helps in OER. In yet another attempt, Xu smaller charge transfer resistance (Rct ≈ 2.8 Ω) offering a larger
et al. synthesized nanoforest of Ni3Se2 on Ni foam (Ni3Se2/NF) charge transfer capability.
by simple hydrothermal method.[245] This synthesized bifunc-
tional electrocatalyst showed cathodic η10/100 = 203/279 mV
with ζ = 79 mV dec−1 and anodic η10/20/100 = 239/242/353 mV. 4.3.2. Nickel Phosphides
As a water electrolyzer, this catalyst delivered j10 at 1.612 V with
high stability of 140 h. The overall performance of this cata- Nickel has gained much attention in the field of water split-
lyst is attributed to the following factors. The synthesized 3D ting due to its better performance than many other nonpre-
hierarchical nanoforest structures of Ni3Se2 have larger open cious metals used today. Using nickel alone is avoided as it is
and conducting surface of Ni foam. Its activity was further prone to corrosion and hence doping with suitable element
improved due to the presence of rhombohedral Ni3Se2 phase is the key option to offer a better corrosion resistance. It is
displaying metallic character, thus adding overall activity for known that doping with phosphorus content to a <15 atomic
water splitting. Other feature of this catalyst is its low imped- % increases the corrosion resistance far more than the bare
ance value, which offers a larger current during electrochemical nickel in alkaline medium. It has also been reported that using
process. Zhang et al. fabricated alloy of Ni0.9Fe0.1 encapsulated the phosphorus as a doping element increases je to a larger
in N-doped CNTs (Ni0.9Fe0.1/N-CNT) by simple carbonization value. Tang et al. demonstrated that NP of Ni–P grown on NF
of urea with Fe and Ni salt at 700 °C in the inert atmosphere, (Ni–P/NF) can catalyze HER/OER with η10 = 80/309 mV.[249]
which worked for both HER and OER.[246] The cathodic/anodic As a whole water electrolyzer the j10 was achieved at 1.67 V
η10 = 85/270 mV was achieved with ζ = 111/45 mV dec−1. Its with high stability. The activity of Ni–P/NF is attributed to
OER activity is ascribed to the reduction in nickel oxidation close contact of Ni–P and NF, which facilitated the charge/
states because of partially induced charge transfer due to Fe. mass transfer across the electrodes and electrolyte. Wang
The foremost is the structural transformation of nickel catalyst et al. fabricated Ni–P on carbon paper (Ni–P//CP) by elec-
into more catalytically active centers for reactions. As a cell electrodeposition and phosphorization methods.[250] In a typical
trolyzer this catalyst produced j10 at 1.58 V with reasonable sta- synthesis process Ni was first electrochemically deposited
bility. The overall performances of this catalyst are ascribed to on CP (Ni/CP) and then converted to NiP/CP by phospho-
various factors. Firstly, the nitrogen doping into carbon gave not rization at 500 °C in inert atmosphere. The catalyst showed
only chemical stability but also thermal stability by s ynergistic cathodic j = 10/20/100 mA cm−2 at η = 117/150/250 mV
effect between carbon support and catalytic active sites. Second, in alkaline medium with ζ = 85.4 mV dec−1 and anodic
doping with Fe can significantly increase electronic conduc- j = 20/50.4 mA cm−2 at η = 0.18/0.3 V with ζ = 73 mV dec−1.
tivity. Gu et al. synthesized a 3D Ni3FeN NPs/rGO aerogel In addition to alkaline medium, this catalyst also demonstrated
via an ion exchange process for overall water splitting.[247] better performance in acidic medium by consuming only
The catalyst demonstrated good electrocatalytic performance η100 = 162 mV. Using this catalyst for whole water splitting,
the j = 10/20 mA cm−2 was achieved at 1.63/1.73 V and the and 80% with various micro and mesopores. These pores offer
system can run without capacity fading till 100 h. The overall larger surface area and enhance catalytic activity for overall water
performance of this catalyst is attributed to the macroporous splitting. Zhu et al. synthesized microsphere of NiS as a bifunc-
3D structures of NF which exhibited larger active surface area tional electrocatalyst by sulfurization of Ni foam using S powder
for electrocatalytic reaction, facilitating easier mass transport at 350 °C, which showed a cathodic η20 = 158 mV and anodic
and release of H2/O2 gas from the surface. Other contributing η50 = 335 mV.[254] When assembled as a water electrolyzer it
factor is the formation of Ni–P, which is intrinsically favoring offered j10 at 1.64 V with high stability. Sivanantham et al. grew
HER activity due to the presence of electron donating P group NiCo2S4 NWs on NF by hydrothermal method, which showed
and the formation of Ni–P/NiO/Ni(OH)x is another beneficial cathodic/anodic η10 = 310/340 mV with ζ = 96/51 mV dec−1.[255]
factor toward OER. Wu et al. synthesized hybrid of MoOx-Ni3S2 As a water electrolyzer, it offered j10 at 1.63 V. The enhanced
on NF, which displayed η10/100/200/500 = 106/224/312/486 mV activity of this NiCo2S4 catalyst is attributed to the larger S2−
for HER and 136/310/373/496 mV for OER.[251] When assem- anion with Ni and Co occupying various tetrahedral and octahe-
bled as an overall water splitting system it demonstrates j10 dral sites, respectively. This structure is a close match to spinel
at 1.45 V with an excellent stability over 100 h. This excellent structure which offers its larger octahedral sites for OER. Chen
HER/OER activity can be ascribed to the following aspects; i) et al. developed the 3D-Ni/Ni8P3 as a bifunctional electrode
Ni3S2 intrinsically possess bifunctional HER/OER active cata- from oxidation, sulfurization and phosphidation of NF, which
lytic sites, ii) the synergistic effect of MoOx and Ni3S2 improves displayed cathodic η10/30 = 230/270 mV with ζ = 123.3 mV dec−1
both HER and OER, ii) MoOx-Ni3S2 /NF is a self-supported and anodic η30 = 340 mV with ζ = 109.8 mV dec−1.[256]
structure without any binder which reduces any amount of Using this electrode as cathode and anode, Φ10 = 1.61 V
interfacial overpotential between electrolyte and electrode. Li was required. The higher activity is ascribed to 3D cluster-like
et al. reported nickel phosphide (NixPy) bifunctional electrocata- morphology, which offered large catalytic active surface area
lysts for overall water splitting. The synthesis protocol consists for reaction by forming NiO on the Ni9S8 surface that provides
of heating ultrathin Ni(OH)2 plates in the presence of sodium an easy path for gas evolution at electrode. Luo et al. designed
hypophosphite (NaH2PO2·H2O) at 325 °C.[252] The richest phase two different compositions of nickel sulfide such as NiS2 for
of bifunctional nickel phosphide catalyst is denoted by (Ni5P4- HER and NiS for OER.[189b] In a typical synthesis, the hollow
325). The catalyst demonstrates a remarkable HER and OER microspheres of NiS2 were synthesized first by hydrothermal
activity along with overall water splitting. The catalyst achieved process and then converted to porous NiS via calcination. NiS2
a cathodic η20 = 62/160 mV with ζ = 46.1/107.3 mV dec−1 in as a HER electrocatalyst offered cathodic η10 = 148 mV with ζ =
acidic/alkaline medium. The TOF of this catalyst is 0.75 s−1 at 79 mV dec−1. NiS as an OER electrocatalyst delivered anodic
η = 72 mV. The enhanced activity toward HER is attributed to a η10 = 320 mV. When NiS2 as a cathode and NiS as an anode
slightly positive charge on Ni (δ+). The induced slightly positive were applied for whole water splitting, the j10 was generated at
charge on the metallic center promotes hydrogenase-like cata- 1.58 V. The performance of this catalyst can be assigned to the
lyst delivering higher HER activity. In OER, this catalyst dis- formation of tiny channels and defective sites during the for-
plays anodic η10 = 320 mV, corresponding to ζ = 72.2 mV dec−1. mation of porous structure of NiS2 and NiS, which facilitated
The formation of surface NiOOH species contributes to high the charge/mass transport between electrode and electrolyte.
capability of this catalyst toward OER. In whole water splitting Song and co-workers synthesized pyrite type NSs of NiS2 doped
assembly, it consumes a minimal voltage of 1.57 V to deliver with vanadium heteroatoms as a bifunctional electrocatalyst.[257]
j10 and displays stability well over 60 h without capacity fading The as-synthesized electrocatalyst exhibited an anodic/cathodic
with ≈100% Faradaic efficiency in alkaline medium. η10 = 290/110 mV and ζ = 45/90 mV dec−1 with a reasonable
stability in alkaline medium. When assembled as a water elec-
trolyzer it offered j10 at 1.56 V with high stability. DFT calcu-
4.3.3. Nickel sulfides lations and experimental evidence proved that the doping with
vanadium reconfigured the electronic structure of NiS2 from
Nickel sulfides have been the most studied and investigated semiconductor to metallic characteristics. The calculation also
among water splitting catalysts. Doping with varying content of brings out the band gap of NiS2 to be 0.41 eV which is a charac-
sulfur offers nickel to achieve many different crystallographic teristic of semiconductor and vanadium doped NiS2 to be zero
structures, for instance (NiS, Ni3S2). These varying structures as a representative of metallic characteristics.
make nickel a better candidate material in water splitting.
Earth-abundant nickel sulfides with high electrical conductivity,
thermal and mechanical stability, higher electrocatalytic activity 4.4. Molybdenum-Based Electrocatalysts
and long-term durability in acidic/basic environments have
been considered as an interesting class of potential catalysts In HER section of this review, we discussed that the moly
for HER and OER applications. Sun and coworkers fabricated bdenum in sulfides or carbides forms is very efficient and stable
hierarchically porous nickel sulfide (h-NiSx) supported on NF for hydrogen production and can replace commercial Pt in
by electrodeposition and phosphidation methods.[253] The cata- future. However, it cannot be applied as a bifunctional electro-
lyst exhibited cathodic/anodic η10 = 60/180 mV. For whole water catalyst for both HER and OER due to their poor and unstable
splitting this catalyst required potential of 1.47 V. The enhanced OER performance. While designing a bifunctional catalyst, care
activity of this catalyst is attributed to super hierarchical 3D must be taken to design catalysts with better OER functionality,
structure which contains NiS2 and NiS in the molar ratio of ≈20 as water splitting reaction kinetics is greatly dependent upon
the sluggish rate kinetics of OER. Therefore, the molybdenum- structure of MoS2. The coupling interface between Mo(1-x)WxS2
based materials can only be utilized as a bifunctional electro- and Ni3S2 increases the electronic conductivity. Gao et al. intro-
catalyst by improving their OER performance. The OER activity duced the hybrid of MoS2 (active sites for HER) and Ni3S2
of molybdenum-based materials can be enhanced by alloying (active sites for OER) on NF (MoS2-Ni3S2/NF) as a bifunctional
or hybridizing it with some OER active transition metals. Yoon electrocatalyst, which exhibited cathodic/anodic j10 for HER/
et al. pointed out that the hybrid of CoS-doped β-Co(OH)2 and OER at η = 98/249 mV.[259] When this catalyst was assembled
amorphous MoS2+x on NF (CoS-Co(OH)2@aMoS2+x/NF) can as a water electrolyzer, it requires only a potential of 1.50 V
catalyze both HER and OER at very small η.[240d] The binder to display j10. Recently, Ray et al. have come up with another
free CoS-Co(OH)2 at aMoS2+x/NF was synthesized by refluxing bifunctional catalyst consisting of cobalt molybdenum sulfide
Co(NO3)2 ·6H2 O and H8N2MoS4 on NF at 100 °C. The cata- incorporated with phosphorous on CC (P-CoMoS/CC).[260] This
lyst delivered a cathodic/anodic η10 = 143/380 mV with high catalyst demonstrated excellent HER and OER performances.
stability (Figure 16a,b). The ζ for HER of this hybrid catalyst This catalyst displayed cathodic/anodic η10 = 66/260 mV with
lies between 44 and 98 mV dec−1 (Figure 16d) and its ζ for OER ζ = 60.1 mV dec−1 and offers a low resistance of 6.99 Ω. When
lies between 56 and 97 mV dec−1 (Figure 16e). The HER activity assembled as overall water splitting it requires only a potential
of this catalyst is attributed to amorphous MoS2+x sites and of 1.54 V to display j10 with reasonable stability of 24 h main-
OER by CoS-doped β-Co(OH)2. Using this catalyst as a cathode taining 90% of initial j and 100 h at retention of 89.8%. The
and anode, the j10 was generated at 1.58 V with high stability efficiency of this bifunctional catalyst is attributed to unsatu-
(Figure 16c). The CV curves of the two-electrode system reveal rated metal based active sites. The replacement of few sulfur
the redox process of CoII/CoIII at ± 0.15 V (Figure 16f). The atoms by phosphorus atoms resulted in enhancing the cata-
superior activity of this hybrid catalyst emanates from the 3D lytic activity and increasing the durability and stability of this
nanoplates which formed during its coating on Nickel foam. catalyst. In addition to this feature, this catalyst also had the
These plates expose more catalytic surface area between elec- synergistic effect of bimetallic composite structure and anion
trolyte and catalyst interface and thus increase the reaction rate. substitution, which ultimately reduced the value of η.
Zheng et al. reported an alloy of Mo(1-x)WxS2 on Ni3S2 It can be inferred that electrocatalytic performance of the
(Mo-W-S-2@Ni3S2) as a bifunctional catalyst, which showed bifunctional catalyst based on Co, Ni, Mo, and Fe differ widely
a cathodic/anodic η10 = 98/285 mV.[258] In this catalyst the and the selection of a catalyst depends upon the many engi-
Mo(1-x)WxS2 sites worked for HER and WxS2 /Ni3S2 for OER. neering factors, for instance, the number of defective sites,
As a water electrolyzer this catalyst delivered j10 at 1.62 V. The morphological structures suitable for exposing wider cata-
added benefit of W to the catalyst is to optimize the electronic lytic surface area, compositional variations, stability, electrical
Figure 16. a) LSV polarization curves of MoS3, NiS-Ni(OH)2/aMoS2+x, CoS-Co(OH)2at aMoS2+x, and commercial 20% Pt/C in 1 m KOH solution for
HER. b) LSV polarization curves of MoS3, NiS-Ni(OH)2/aMoS2+x, CoS-Co(OH)2at aMoS2+x, and IrO2 in 1 m KOH solution for OER. c) Chronopotentio-
metric curve of CoS-Co(OH)2 at aMoS2+x/NF at 1.6, 1.7 and 1.8 V. d) Tafel plots in 1 m KOH solution for HER. e) Tafel plots in 1 m KOH solution for
OER. f) Cyclic Voltammetry. Reproduced with permission.[240d] Copyright 2016, John Wiley and Sons.
Table 4. A quick summary of advancements in earth-abundant overall water splitting catalysts. and stable electrocatalysts for OER in acidic
solutions or fabrication/selection of suit-
Catalyst HER overpotential OER overpotential Overall water splitting Refs. able anionic membrane for alkaline water
η10 [mV] η10 [mV] [V] electrolyzer; viii) interpretation of the HER/
FeP/Ni2P 14 154 1.42 [210] OER activity of designed catalysts through
Co2P-NWs 95 260 1.44 [227] reasonable theoretical understanding such
as DFT models which are closer to the real
MoS2–Ni3S2/NF 98 249 1.50 [259]
reaction systems and easier and more ben-
P-CoMoS/CC 66 260 1.54 [260]
eficial for the researchers to design suitable
NiFeOx/CFP 40 300 1.51 [206] and efficient electrocatalysts. All these strat-
CoOx@NC 232 260 1.55 [212] egies are of vital importance, but most of
Co–P/Co–P 94 345 1.56 [224] them are already known. In this regard, here
what we particularly stress is the following.
CoSCo(OH)2@aMo S2+x/NF 143 380 1.58 [240d]
Owing to large surface area and precisely
Mo–W–S2@Ni3S2 98 285 1.62 [258]
controlled atomic properties of SACs sup-
CoP/NCNHP 140 310 1.64 [231] ported on conductive templates, strenuous
CoP/rGO-400 150 340 1.7 [226] efforts are being made to utilize SACs which
are able to have near zero adsorption Gibbs
free energies of the catalyst surface for the
conductivity, mass transport, etc. Among these parameters, it is maximum H+ adsorption and desorption of H2 molecules for
hard to find a single bifunctional catalyst satisfying all the req- HER and to optimize binding free energies of the reaction
uisites and demand, so a compromise must be made, while yet intermediates such as O*, OH*, and HOO* for OER. Most
optimizing the parameters to get best out of the catalyst at the works on SACs have focused on metal-Nm or metal-Cn active
disposal. A quick summary of the bifunctional electrocatalyst is sites on template. However, metal-NmCn sites provide much
tabulated in Table 4. diverse and useful choices to obtain optimal free energies for
HER/OER processes. For example, PtN2C2 and RuN2C2 are
excellent HER SACs. Therefore, first, to obtain optimal free
5. Summary and Outlook energies for highly efficient SAC driven HER and OER pro-
cesses, various atoms in different sites of diverse templates
In this review paper we have summarized the recent progress can be considered with different types of coordination environ-
in designing of earth-abundant metals based electrocatalysts for ment. Second, for high durability of SACs various defect sites
HER, OER and whole water splitting. Much support in the fab- in templates need to be carefully studied. For example, a 2nd Pt
rication of effective HER/OER electrocatalysts has come from atom can easily attach on the Pt atom on triangular defect sites
volcano plots and DFT calculations. However, Tables 1 and 2 of N-doped graphene-like sheets, hence eventually forming Pt
reveal that the HER performance of earth-abundant metals clusters. However, it hardly attaches on the Pt site embedded
electrocatalyst is still not compatible to the state-of-the-art Pt in the tetragonal sites because of the unique quantum feature
HER catalysts. The OER and whole water splitting electrocata- of Pt (planar d4+dsp2 electron configuration having 16-electron
lysts are only limited to basic solutions (Tables 3 and 4), but rule versus octahedral d3+d2sp3 electron configuration having
there is no good earth-abundant metal based electrocatalyst 18-electron rule).[129] This kind of coordination gives a high
which can catalyze OER and whole water reactions in acidic or stability of SACs. Thus, strong binding energy between single
neutral solutions. Most of the membranes in fuel cells or water atom and the coordinating ligand atoms attached to the tem-
electrolyzers are only compatible with the acidic environment. plate should be considered. Finally, one should understand
Therefore, future research should be devoted to designing elec- that single atoms alone show some drawbacks because the fast
trocatalysts which can catalyze HER, OER and whole water reaction such as Tafel reaction may not be feasible in the case
splitting reaction at low overpotential with high durability. The when the adjacent single atom sites are not close enough and
efficient and durable HER/OER electrocatalysts can be achieved furthermore the single atom sites embedded on template are
using the following possible strategies: i) the proper selections not highly conductive, which slows down the charge transfer
of metals from HER/OER volcano plots; ii) the encapsulation process. Thus, in this case, it would be highly useful to utilize
of core metals in a single thin layer carbon materials such as the synergistic effect between single atom and metal clusters
graphene, CNT or fullerene; iii) optimization of adsorption because metal clusters help in conductivity of the single atom
Gibbs free energies of the catalyst surface for the maximum H+ sites on the template.[129] Consequently, further improvement
adsorption and desorption of H2 molecules for HER; iv) opti- can be made regarding the synthesis of SACs and cluster-based
mization of binding strength of the reaction intermediates electrocatalysts. In this respect, the SACs with nanoclusters
such as O*, OH*, and HOO* for OER; v) the defective sites will have a bright future for wide-ranging applications, both
generation in the encapsulated graphitic layers and metal cores on academic and industrial scales. In this type of electrocata-
for facile charge-transfer and mass-diffusion during HER/ lyst, the single atoms will work as active catalytic sites and the
OER; vi) increasing the surface area of the electrocatalysts nanoclusters will enhance the conductive channel for charge
which can accommodate a large number of reactant inter- flowing during the electrochemical reaction. We believe that in
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Advanced Energy Materials - 2019 - Sultan - Single Atoms and Clusters Based Nanomaterials For Hydrogen Evolution Oxygen

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16146840, 2019, 22, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.201900624 by Technische Universitat Darmstadt, Wiley Online Library on [24/02/2023].

Single Atoms and Clusters Based Nanomaterials

demand is around 15 terawatts (TW), and

have attracted considerable interest in the past few decades,

the given j (in mA cm−2), the Φ value will be denoted as Φj,

is hydronium cation; while in the case of alkaline electrolytes OOH*  * + O2 + ( H+ + e − )

coated-Ni decorated MoC hollow structure Co–C–N 138 55 −0.15 [49]

Table 2. HER electrocatalyst in 1 m KOH solution at different electrode.

the performance of many transition metal catalysts for OER.

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