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PROGRESS REPORT
Water Electrolysis
Self-Supported Transition-Metal-Based Electrocatalysts
for Hydrogen and Oxygen Evolution
Hongming Sun, Zhenhua Yan, Fangming Liu, Wence Xu, Fangyi Cheng,* and Jun Chen
Electrochemical water splitting is a promising technology for sustainable
conversion, storage, and transport of hydrogen energy. Searching for earth-
abundant hydrogen/oxygen evolution reaction (HER/OER) electrocatalysts
with high activity and durability to replace noble-metal-based catalysts plays
paramount importance in the scalable application of water electrolysis.
A freestanding electrode architecture is highly attractive as compared to
the conventional coated powdery form because of enhanced kinetics and
stability. Herein, recent progress in developing transition-metal-based
HER/OER electrocatalytic materials is reviewed with selected examples of
chalcogenides, phosphides, carbides, nitrides, alloys, phosphates, oxides,
hydroxides, and oxyhydroxides. Focusing on self-supported electrodes, the
latest advances in their structural design, controllable synthesis, mechanistic
understanding, and strategies for performance enhancement are presented.
Remaining challenges and future perspectives for the further development of
self-supported electrocatalysts are also discussed.
1. Introduction
Electrochemical water splitting is an attractive hydrogen
generation technology with advantages including zero
carbon emission, high-purity product, and the ability to
store intermittent renewable energy (i.e., wind and solar
energy).[1,2] As a strongly uphill reaction, water electrolyzers
usually operate at a much larger voltage of 1.8–2.0 V relative
to the theoretical limit of 1.23 V. The use of efficient electro-
catalysts for hydrogen/oxygen evolution reactions (HER/OER)
can effectively improve the sluggish kinetics of HER/OER
and therefore decrease the overpotential.[3] Up to now, the
state-of-the-art HER and OER electrocatalysts are Pt-based
materials and the oxides of Ru or Ir, respectively; but the scar-
city and high cost hinder their widespread deployment.[4,5]
Extensive efforts have been devoted to nonprecious electrocata-
lysts including transition-metal compounds such as sulfides,
Dr. H. Sun, Dr. Z. Yan, F. Liu, Dr. W. Xu, Prof. F. Cheng, Prof. J. Chen
Key Laboratory of Advanced Energy Materials Chemistry
(Ministry of Education)
College of Chemistry
Renewable Energy Conversion and Storage Center
Nankai University
Tianjin 300071, China
E-mail: fycheng@nankai.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201806326.
DOI: 10.1002/adma.201806326
Adv. Mater. 2020, 32, 1806326 1806326  (1 of 18)
www.advmat.de
selenides, phosphides, carbides, nitrides,
alloys, oxides, hydroxides/oxyhydroxides,
phosphates, etc.[6,7] However, the activity
and durability of most noble-metal-free
electrocatalytic materials remain far from
satisfactory.
Nanostructuring is a widely adopted
strategy to enhance the performance of
transition-metal-based electrocatalysts.[2,8,9]
However, practical applications of nano-
structured catalysts suffer from several
issues. On the one hand, nanoparticles
need to be casted on the current collector
using polymeric binder (e.g., polytetra-
fluoroethylene or nafion), which inevitably
increases the resistance, buries the active
sites, and inhibits mass transport,[10] as
shown in Figure 1a. Moreover, the low elec-
trical conductivity of electrocatalysts neces-
sitates the use of conductive additive such
as nanocarbon materials.[11] Under OER
condition, the carbon additive is prone to oxidized and etched
at high potential, which deteriorates electrode performance.[12]
On the other hand, owing to the low adhesive force between the
catalytically active phase and substrate, the loading mass of the
nanocatalysts is usually less than 1 mg cm−2, providing limited
catalytically active sites. Furthermore, coated catalysts could be
easily peeled off from the substrate during long-term or large-
current electrocatalysis.[13] Thus, the powdery electrodes work
well only at small current densities (<100 mA cm−2) for dozens
of hours and cannot meet the requirements of practical indus-
trial electrolyzers that usually operate at high current densities
above 500 mA cm−2 for thousands of hours.[2,14]
Compared with conventional powdery electrocatalysts, the
self-supported electrodes with catalytically active phase in situ
grown on the conductive substrates are more desirable as they
are characterized with the following merits (Figure 1b). First, the
in situ growth of catalysts on conductive substrates avoids the
postcoating process and the addition of binder and conducting
agent, which simplifies the electrode preparation process and
lowers the cost.[15] Second, the substrate materials can rivet and
disperse catalysts, resulting in high loading of active components
and thus providing abundant catalytic sites.[16] Third, the
binding of catalytic materials and substrates is more intimate
without additional binder. The seamless contact ensures rapid
charge transfer while the tight integration prevents catalyst
shedding. Finally, the preparation of self-supported electrode is
easier to realize surface hydrophilic/hydrophobic engineering
by purposefully adjusting the morphology and microstructure.
Hydrophilic electrode could accelerate the bubble detachment,
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Figure 1. Schematic illustration of the structural and electrochemical
features of: a) conventional powdery catalysts coated on current collectors
with polymer binder and carbon additives, and b) self-supported electrode
with in situ grown catalysts on the substrates.
enhance the electrocatalyst/electrolyte contact, and promote
charge and ion transfer.[17,18] All these advantages favor boosting
the catalytic activity and long-term stability of self-supported
electrode for practical large-current-density electrolysis.[19]
Recently, substantial progress has been achieved in the
development of self-supported electrode for electrocatalysis,
which however lacks a comprehensive summary. In this article,
we intend to provide an overview on recent advance in self-
supported transition-metal-based HER/OER electrocatalysts,
with focus on their structure design, electrode preparation, and
catalytic performance. After a brief introduction of the widely
employed synthetic strategies, a review is presented on presenta-
tive self-supported electrocatalysts separately for HER, OER,
and overall water electrolysis. The selected electrocatalytic mate-
rials include sulfides, selenides, phosphides, carbides, nitrides,
alloys, hydroxides/oxyhydroxides, oxides, and phosphates
of transition metals. Finally, the challenges and prospects
are discussed in future developments of the self-supported
transition-metal-based electrocatalysts.
2. Design and Preparation of Self-Supported
Electrode
To prepare self-supported electrode, the catalytically active phase
is in situ grown on the substrate during the synthesis process.
Typical synthetic strategies include hydro/solvothermal, elec-
trodeposition, vapor deposition, vacuum filtration, freeze
drying, and the combination of different methods. The applied
approach depends on the selective substrate material and the
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Hongming Sun received his
B.E. degree from Shandong
University of Technology
in 2012 and M.S. degree
from Tianjin Polytechnic
University in 2015. He then
joined Professor Fangyi
Cheng’s group in the College
of Chemistry at Nankai
University and received his
Ph.D. degree in 2018. Now,
he works in the College
of Chemistry at Tianjin Normal University. His research
focuses on developing transition-metal-based materials for
electrocatalytic hydrogen evolution and oxygen evolution.
Fangyi Cheng is a Professor
of Chemistry at Nankai
University. He received his
B.S. degree in 2003 and
Ph.D. degree in 2009 from
Nankai University. He was
a visiting scholar at UCLA
in 2015–2016. His research
interests cover the design
and synthesis of advanced
materials for energy conver-
sion and storage applica-
tions, particularly focusing on nonstoichiometric electrode
materials for electrocatalysis and batteries.
target catalyst component. At present, transition metal elements
of Fe, Co, Ni, Mn, Zn, Ti, Cu, V, Mo, and W are the most widely
investigated to construct self-supported transition-metal-based
electrocatalysts due to the low cost and unique physicochemical
properties (Figure  2). Common substrates are mainly focused
on metal, carbon, and a few other conductive materials in
different forms, including carbon fiber papers (CFP), carbon
cloth (CC), graphite plate, metal foam (e.g., Ni/Cu foam),
metal mesh (e.g., Ti/Cu mesh), metal plate/foil (e.g., Ti plate
and W/Mo/Cu foil), fluorine-doped tin oxide (FTO), and so on.
Featuring with mechanical strength and flexibility, graphene
and carbon nanotubes can be coupled with nanocatalysts to
form freestanding film electrode via post-treatments. In addi-
tion, some monolithic substrate-free alloy materials can directly
function as self-supported electrocatalysts.
The hydro/solvothermal method is an effective strategy to
prepare inorganic catalytic materials such as metal oxides and
hydroxides/oxyhydroxides at modest temperature in a pressure-
tight reactor.[20–22] In hydro/solvothermal reaction, the surface
defects and oxyl groups on the substrates serve as sites for the
nucleation and conformal growth of active materials, resulting
in a uniform deposition of nanostructure on the substrates.
For example, a hydrothermal method was applied to prepare
a series of coralloid trimetallic WCoFe oxyhydroxides with a
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Figure 2. Substrate materials and transition-metal elements that
are used to build self-supported electrodes for electrocatalytic water
splitting.
sponge-like structure, adjustable composition, and homoge-
neous distribution on nickel foams (NF) (Figure 3a).[22] The syn-
thesized transition metal oxy-compounds can be directly used
as electrocatalysts or act as the precursors to synthesize other
compounds such as sulfides, selenides, phosphides, carbides,
nitrides, and alloys through post-treatment. Specifically, self-
supported electrodes of MoS2 nanosheets/CC,[23] Co3Se4 thin
nanowires/cobalt foam,[24] and Ni2P nanorods/NF[25] have been
prepared by one-pot hydro/solvothermal route.
Electrodeposition is another versatile technique to prepare
self-supported electrodes. The electrodeposition process is
generally carried out in a three-electrode electrochemical cell
with selected conductive substrates as working electrodes, on
which target materials are uniformly and rapidly deposited under
applied electric field.[26] Most transition-metal-based materials
including oxides, hydroxides, oxyhydroxides, sulfides, selenides,
phosphides, and alloys can be electrodeposited on a conducting
substrate. Figure 3b shows an example of electrodeposited 3D
Ni–Mo electrocatalysts supported on Cu foam.[27] The deposi-
tion was realized by implementing a constant current density
between 2 and 200 mA cm−2 in an electrolyte solution containing
nickel sulfate, sodium citrate, ammonium molybdate, sodium
chloride, and ammonium hydroxide. In addition to rapid syn-
thesis, another advantage of electrodeposition is the controllable
catalyst loading on the substrate by adjusting deposition time
and applied potential/current density.[16]
In combination with hydrothermal and electrodeposition
methods, chemical vapor deposition (CVD) has been widely
used to synthesize self-supported transition-metal-based elec-
trocatalysts. Under sintering at high temperature, some metal
substrates or metal oxides/hydroxides/oxyhydroxides grown on
substrates can react with the gas phase of nonmetal precursors
such as phosphorus (PH3 or P), sulfur, selenium, carbon (CH4
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or CO), and nitrogen (NH3 or N2) to form the corresponding
phosphides, sulfides, selenides, carbides, and nitrides. In
a typical example, the component-controllable WS2(1−x)Se2x
nanotubes were in situ synthesized on carbon fibers by chemical
transforming the carbon fibers supported WO3 nanotubes with
sulfur and selenium vapor, respectively (Figure 3c).[28] Apart
from the CVD method, physical vapor deposition (PVD) is also
a feasible method to deposit catalysts on a specific substrate. For
example, nanostructured MoS2 was prepared by the PVD depo-
sition of bulk MoS2 on CC via a magnetron sputtering system.[29]
The above synthetic strategies for self-supported catalysts
depends largely on in situ growth. Self-supported electrodes can
also be prepared without any ready-made substrate but with post-
composing treatment. Typically, carbon nanotubes (CNTs) and
reduced graphene oxide (rGO) owning high conductivity, large
surface area, and low density have received intensive attention
as catalyst supports, on which nanostructured catalysts can be
uniformly and strongly coupled.[30–32] Via a simple vacuum filtra-
tion, the rGO and catalysts hybrid could form a flexible 3D nano-
architectured film that directly serves as a monolithic electrode.[31]
Similarly, 3D CoS2/RGO–CNT nanocomposite architectures
were synthesized by a hydrothermal growth of CoS2 nanosheets
on rGO, followed by vacuum filtration with CNT (Figure 3d).[30]
Moreover, alloying/dealloying is another robust method to fab-
ricate porous self-supported monolithic electrodes without sub-
strates. In a dealloying process, the more reactive component
is selectively dissolved or etched and the remaining component
reorganizes into a 3D porous network. This versatile and scalable
method has been successfully applied to obtain transition metal
phosphide and alloy electrocatalysts, such as amorphous metallic
NiFeP, nanoporous (Co1−xFex)2P, and Cu–Ti bimetallic alloy.[33–35]
3. Self-Supported Electrocatalysts for HER
The electrochemical HER involves multiple steps.[2] In acidic
electrolyte, the first step (Volmer reaction) is reducing protons
on catalytic sites (M) to form adsorbed hydrogen (Hads).
At low coverage of Hads on the catalyst surface, Hads will
preferably combine with a proton and an electron to generate
a H2 molecule (Heyrovsky reaction). In the case of high Hads
coverage, two adjacent Hads atoms bind to form H2 (Tafel reac-
tion). Mechanistic studies suggest that molecular H2 forms
via Volmer–Heyrovsky or Volmer–Tafel pathway. Similarly,
the HER proceeds through similar pathways under alkaline
condition. Differently, the Volmer reaction is facile in acid
due to abundant available protons while it is kinetically more
sluggish in alkaline media as it involves water dissociation
prior to H absorption. The HER process can be described using
the following elementary steps[4,6]
Volmer reaction : H+ + M + e − → MHads ( in acid ) (1)
H2 O + M + e − → MHads + OH− ( in alkali ) (2)
Heyrovsky reaction : MHads + H+ + e − → M + H2 ( in acid ) (3)
MHads + H2 O + e − → M + OH− + H2 ( in alkali ) (4)
Tafel reaction : 2MHads → 2M + H2 (5)
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Figure 3. Typical synthetic strategies for self-supported electrodes. a) Hydrothermal growth of oxyhydroxides on nickel foam. Reproduced with
permission.[22] Copyright 2017, Wiley-VCH. b) Electrodeposition of Ni–Mo electrocatalysts on Cu foam. Reproduced with permission.[27] Copyright 2014,
Wiley-VCH. c) Chemical vapor deposition of WS2, WSe2, and WS2(1−x)Se2x on carbon fiber. Reproduced with permission.[28] Copyright 2014, American
Chemical Society. d) Filtration and peeling off process to obtain freestanding nanocomposite of CoS2 and reduced graphene oxide–carbon nanotubes
(RGO–CNT). Reproduced with permission.[30] Copyright 2014, Wiley-VCH.

Both Volmer–Heyrovsky and Volmer–Tafel pathways 3.1. Transition Metal Sulfides

involve the formation of intermediate Hads. The free energy
change of H adsorption (ΔGH*) is thus an important figure
of merit to predict/estimate the activities of HER catalysts.
An ideal catalytic site for the HER should have a ΔGH* near
zero. The ΔGH* is closely associated with the inherent surface
chemistry and electronic structure of the materials. In recent
years, extensive efforts have been put forward to developing
highly active HER catalysts such as transition metal sulfide,
selenide, nitride, phosphide, carbide, nitride, and alloy. Next,
we focus our discussion on those electrocatalysts with self-
supported structure.
As bioinspired HER electrocatalysts, transition metal sulfides
have gained extensive interest over a decade. Among them,
MoS2 is the most extensively developed because of its unique
structural and electronic properties. Both experimental and
computational studies have shown that the catalytic activity
of bulk MoS2 is poor and highly dependent on the number
of exposed edge sites.[36] Thus, it is desirable to design and
modulate MoS2 catalysts with maximum exposed edge sites.
In this regard, Cui’s group prepared a MoS2 thin film with
vertically aligned layers on a flat substrate.[37] The obtained

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Figure 4.  Self-supported Co chalcogenides for the HER. a) Synthesis of CoS2 in forms of film, microwire array and nanowire array on graphite disk
substrates and b) the corresponding polarization curves. The inset in (b) schematically depicts bubble release behaviors on different electrode surfaces.
a,b) Reproduced with permission.[41] Copyright 2014, American Chemical Society. c) Image of the CoSe2 catalyst on a piece CFP. d,e) SEM images of
CoSe2 nanoparticles on CFP. f) Polarization curves of CoSe2 nanoparticle/CFP, CoSe2 nanoparticle/glassy carbon, CoSe2 film/glassy carbon and the
CFP in 0.5 M H2SO4. c–f) Reproduced with permission.[44] Copyright 2014, American Chemical Society.

MoS2 catalyst with rich edges showed superior catalytic perfor-
mance to the bulk counterpart. Afterward, MoS2 nanosheet
arrays vertically aligned on NF and edge-oriented MoS2 films
loaded on Mo substrate were also developed as self-supported
HER catalyst.[38,39] Besides simply increasing the number of
exposed edge sites, attention was also paid on tailoring the
MoS2 edge surface. Recently, a stepped edge surface-termi-
nated MoS2 sheet array (se-MoS2) was fabricated on CFP by a
microwave hydrothermal method.[40] Compared with a flat edge
surface-terminated sheet array and randomly grown MoS2,
se-MoS2 showed a lower overpotential because of the optimal
hydrogen adsorption energy (ΔGH) value.
Similar with MoS2, WS2 adopts a layered structure with
adjustable electrical properties and exposed edge sites being the
active HER centers. Likewise, studies on WS2 are mainly focused
on synthesizing nanostructured WS2 with more edge sites. An
exemplified 3D self-supported film electrode through coupling
2D 1T-WS2 nanolayers and P-, N-, and O-doped graphene sheets
was recently fabricated via a vacuum-filtration process.[31] The
edge-rich 1T WS2 nanosheets and the synergistic effect between
the WS2 nanolayers and heteroatom-doped graphene sheets
were proposed to boost the HER activity of the integrated film
electrode, which attained a current density of 10 mA cm−2 at an
overpotential of 125 mV.
Besides Mo and W, Co-based sulfides are demonstrated to
be active for the HER. Particularly, extensive interest has been
directed to the pyrite-phase CoS2 with metallic conduction
and long-term stability in both acidic and alkaline conditions.
Notably, Jin’s group synthesized CoS2 with different shapes
of film, microwire, and nanowire on a graphite disk substrate
by adjusting synthesis parameters (Figure  4a).[41] Compared
with planar film electrode, nanostructured CoS2 exhibited not
only superior catalytic activities but also increased stability due
to facilitated release of gas bubbles from electrode surface,
as shown in Figure 4b. The catalytic activity of CoS2 can be
further improved by partly substituting S by P to form a ternary
pyrite-type cobalt phosphosulfide (CoPS) as the introduction of
P atom could optimize the GH* of hydrogen adsorption at the
Co site.[42]
Compared with Co, Ni and Fe are cheaper and more
abundant and logically the related sulfides have been widely
investigated as HER catalysts. Remarkably, 3D hierarchically
porous Ni3S2 film on a nanoporous copper substrate was syn-
thesized via an unusual galvanic replacement approach using
the nanoporous copper substrate as the template and nickel
chloride and thiourea as the starting materials.[43] Such in situ
homogeneous growth of active phase on the restructuring
nanoporous copper skeleton enhanced accessible active sites.

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Additionally, the unique architecture accelerated the mass
transport and favored more efficient utilization of active sites.
In acidic media, the self-supported Ni3S2 electrode displayed
high HER catalytic activities with a high turnover frequency
(TOF) of 0.052 s−1 (@η100 mV) and a large exchange current
density (j0) of 0.492 mA cm−2. In alkaline solution, the self-
supported Ni3S2 electrode also exhibited superior HER catalytic
ability with a large exchange current density of 0.786 mA cm−2,
higher than that in acidic condition. There are rarely any non-
precious catalysts that could exhibit comparable HER activity in
both acidic and alkaline media. For iron sulfides, Hu’s group
reported a novel strategy of in situ loading FeS2 nanoparticle
on RGO by a current-induced high-temperature rapid thermal
shock of iron pyrite.[32] The embedding of ultrafine FeS2 nano-
particles in RGO resulted in a freestanding FeS2–RGO film
electrode, which achieved a current density of 10 mA cm−2 at
an overpotential of 139 mV.
3.2. Transition Metal Selenides
Generally, transition metal selenides have a higher intrinsic
catalytic activity in comparison to the corresponding sulfides.[45,46]
Accordingly, there is an increase interest to develop the transition
metal selenide-based HER electrocatalysts. Owing to the homol-
ogous structure of MoS2 and MoSe2, strategies investigated
for improving the HER activities of MoS2 such as increasing
conductivity by phase transformation, exposing active sites by
fabricating vertical array, and coupling with conductive mate-
rials were also demonstrated beneficial for MoSe2.[37,47] As an
example, N-doped 1T–2H MoSe2/graphene shell/core nano-
flake arrays on CC act as an advanced self-supported HER
electrode.[48] The N doping and introduction of 1T phase into
2H-MoSe2 improved the electrical conductivity and favored the
exposure of more active edge sites of MoSe2. Furthermore, the
porous graphene coupled with the preferential thin nanoflakes
of MoSe2 effectively accelerated electronic and ionic transfer. In
the 0.5 m H2SO4 solution, the composite delivered a small onset
overpotential of 45 mV and a low Tafel slope of 49 mV decade−1.
The Co-based selenide catalysts are more frequently reported
selenide HER catalysts. Nanoparticulate CoSe2 with cubic
pyrite–type phase on CFP is a representative example in case.[44]
The synthesis followed a two-step process: drop-casting and
pyrolysis of the precursor ink to form cobalt oxide nanoparticles
on CFP, and post selenizaiton in Se vapor. As shown in
Figure 4c–e, a layer of CoSe2 nanoparticles was conform-
ably covered on carbon fibers. The CFP-supported CoSe2
nanoparticle film gave a current density of 100 mA cm−2 at an
overpotential of ≅180 mV (Figure 4f). Aside from cubic-pyrite-
type phase, CoSe2 can also crystallizes into an orthorhombic
macarsite-type structure. Xie’s group purposively prepared
the cubic-pyrite-type and orthorhombic macarsite phase of
CoSe2 on a flexible CC.[49] Experimental and computational
results unveiled that the metallic cubic pyrite CoSe2 possessed
higher electrical conductivity, optimal water adsorption energy,
and faster transformation efficiency of Hads into molecular
hydrogen, thus outperforming the orthorhombic phase.
Considering the importance of hydrophilic/aerophobic
electrode surface that facilitates gas release from the
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electrode surface and diminish the bubble shielding effect,
surface modulating and structure engineering have been
attested to enhance and stabilize the electrocatalytic per-
formance. For selenides, a hydrophilic Ni3Se2 nanoforest/
NF electrode and a hydrophobic microsphere-like Ni3Se2/
NF electrode were reported recently.[50] During the HER
process, in situ videos showed that the bubbles adhered on
the surface of Ni3Se2 nanoforest/NF electrode have weaker
adhesive force and smaller size than those attached on the
microsphere-like Ni3Se2/NF electrode. As a result of accel-
erated gas-bubble detachment, the Ni3Se2 nanoforest/NF
electrode exhibited a much better catalytic performance
compared with the microsphere-like counterpart. Besides
binary metal selenides, ternary metal selenides with doping
element were attractive HER electrocatalysts as well. Novel
3D Ni0.89Co0.11Se2 mesoporous nanosheet networks on NF
were synthesized by selenizing the NiCo layered double
hydroxide (LDH) nanosheet arrays.[21] The doping of Co in
NiSe2 facilitated the adsorption of both H+ and H2O, pro-
viding high electrical conductivity and integrated electrode
structure that jointly enhanced the catalytic performance
of Ni0.89Co0.11Se. Notably, the 3D Ni0.89Co0.11Se electrode
showed remarkable HER catalytic activities in acidic, neutral,
and alkaline media with low overpotentials of 52, 82, and
85 mV at −10 mA cm−2, respectively. Another example is
ternary MoS2(1−x)Se2x particles, which were demonstrated to
surpass the binary MoS2 due to the lower Gibbs free energy
for hydrogen adsorption.[51]
3.3. Transition Metal Phosphides
In 2005, Rodriguez’s group performed density functional
theory (DFT) calculation to demonstrate that the (001) sur-
face of Ni2P possesses the favorable H binding in hydroge-
nase systems.[52] The high intrinsic activity together with the
thermostability, high conductivity, and low cost makes Ni2P a
promising alternative to Pt-based electrocatalyst for HER. Later
on, Lewis and co-workers experimentally validated the respect-
able performance of Ni2P.[8] Since then, Ni2P and related
transition metal phosphides (e.g., CoP, FeP, Cu3P, and MoP)
have stimulated increasing interest as earth-abundant
HER catalysts.[4] Moreover, unlike metal sulfides of which
the electrocatalytic activity is limited to the edges, metal
phosphides are found active in the bulk form. Thus, the metal
phosphides outperform the transition metal sulfide-based
catalysts (e.g., MoS2).[8,53] Logically, self-supported metal phos-
phide nanostructures in situ grown on 3D substrates have
been widely exploited. Along this line, Sun’s group developed
a two-step synthetic strategy to prepare several metal phos-
phide electrocatalysts. First, transition metal oxide/hydroxide/
oxyhydroxide-based precursors are in situ grown on the
substrates by hydrothermal or electrodeposition reactions.
Then, the precursors are chemically converted into the cor-
responding metal phosphides by a low-temperature topotactic
phosphidation reaction using NaH2PO2 as P source. Rep-
resentatively, nanoporous CoP nanowire arrays on CC were
obtained by low-temperature phosphidation of the Co(OH)
F/CC precursor.[54] The CoP nanowires uniformly coated on
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Figure 5.  Self-supported cobalt phosphide electrodes for the HER. a) SEM images, b) polarization curves and c) Tafel plots of CoP on carbon cloth
and the comparative electrodes. a–c) Reproduced with permission.[54] Copyright 2015, American Chemical Society. d) SEM image, and e,f) polarization
curves of Co–B–P supported on nickel foam and the comparative catalysts. Insets of (d) and (f) show the digital images of wetting ability test and
bubble release test, respectively. d–f) Reproduced with permission.[13] Copyright 2018, Royal Society of Chemistry.

the entire surface of the CC (Figure  5a). In 0.5 m H2SO4, the
resulting CoP/CC electrode showed exceptionally high catalytic
performance, giving a high TOF of 0.725 s−1 at an overpotential
of 75 mV, a low overpotential of 67 mV at 10 mA cm−2, and a
small Tafel slope of 51 mV decade−1 (Figure 5b,c). Compared
with that in acidic electrolyte, the CoP/CC electrode displayed
a relatively high overpotential of 209 mV to approach a current
density of 10 mA cm−2 in basic media. In addition, FeP nano-
wire array/Ti plate, Fe-doped Ni2P nanosheet arrays/NF, and
Cu3P nanowire arrays/CF were also prepared as self-supported
HER electrocatalysts.[20,55,56]
Straightforward one-step approaches were also developed by
direct phophorization of a commercially available metal sub-
strate under sintering or solvothermal conditions. For instance,
a self-supported electrode composed of biphasic Ni5P4–Ni2P
nanosheet arrays was synthesized by phosphorizing NF
with phosphorus vapor.[57] This 3D HER electrode showed a
low HER onset potential of 54 mV and a low Tafel slope of
79.1 mV decade−1 in acidic medium. Besides, a self-supported
Ni2P nanorods/NF HER electrode was also fabricated via phos-
phorization of the NF substrate under a solvothermal reaction
with red phosphorus.[25] These one-step strategies avoid the
complicated precursor synthesis and post-treatment steps,
but are often limited by the selection of corresponding metal
substrates, especially in the case of preparing multimetal
phosphides. Alternatively, electrodeposition was attempted
to prepare metal phosphide-based binder-free electrodes. A
recent example is the NF-supported CoP mesoporous nanorod
arrays, which were fabricated via a potentiostat electrodeposi-
tion technique in a three-electrode mode.[26]
For the binary metal phosphides, the hydrogen adsorption free
energy, which is closely linked to the intrinsic catalytic activity,
is often either too strong or too weak. Cation or anion doping
could optimize the electronic structure and improve the catalytic
performance.[58] In this regard, ternary FexCo1−xP nanowire
arrays supported on CC were synthesized and investigated.[59]
DFT calculations predicted that the ternary FexCo1−xP has a
more favorable free energy of hydrogen adsorption than does
binary CoP. The optimized Fe0.5Co0.5P electrode afforded an HER
catalytic current density of 10 mA cm−2 at a low overpotential of
37 mV. Another example is self-supported NiCo2Px in situ grown
on carbon felt, which outperformed the binary CoPx and NiPx.[60]
Besides bimetal synergistic effect in phosphides, the inclusion of
metalloid also exerts positive effect. Our recent studies on ternary
Co–B–P indicated that the synergistic effect of P and B favors
dissociate of H2O, weakens surface H absorption, and suppresses
Co oxidation.[13] A typical Co2.9B0.73P0.27 nanosheet array was syn-
thesized on nickel foam (Co–B–P/NF; Figure 5d) via a facile room-
temperature one-pot electroless method. The obtained Co–B–P/
NF electrode, which combines advantages of B/P synergistic
effect and superhydrophilic surface properties, resulted in signifi-
cantly higher HER catalytic activity than that of binary Co–P and
Co–B as well as the hydrophobic Co–B–P (Figure 5e,f). Further-
more, the 3D self-supported architecture contributed to remark-
able performance at high current densities up to 2000 mA cm−2
with a nearly 100% Faradaic efficiency of HER.

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3.4. Transition Metal Carbides and Nitrides
Metal carbides and nitrides have been widely investigated as
a possible alternative to platinum due to the Pt-like electronic
behavior, high conductivity, and considerable stability in a wide
pH range.[6] The synthesis of metal carbides usually requires a
high-temperature (above 700 °C) carbonization process, which
inevitably leads to sintering and agglomeration of catalysts.[61]
Self-supported electrode assembly is an effective strategy to
address this problem. Along this direction, Zou and co-workers
in situ synthesized Mo2C microislands on a flexible CC as
a self-supported HER electrode.[62] Benefiting from the rich
catalytic sites of inland-like Mo2C, high electrical conductivity,
and intimate connection of the catalyst and substrate, the as-
prepared binder-free electrode showed respectable HER electro-
catalytic performance in terms of a low overpotential of 140 mV
at a current of 10 mA cm−2.
Compared to metal carbides, the metal nitrides usually
showed an inferior HER catalytic properties.[63] Even so, some
metal nitride-based HER catalysts have been exploited by cation
doping, which could significantly improve the performance
by redistributing the charge to activate the catalytic sites. For
example, V-doped Co4N nanosheets were recently synthesized
by growing the V-doped Co(OH)2 nanowires on NF via a hydro-
thermal reaction followed by a nitridation treatment in an NH3
atmosphere.[64] The V doping caused downshift of the d-band
center, which favors the H desorption. In alkaline media,
Figure 6.  Self-supported alloy electrode for the HER. a,b) SEM images, c) polarization curves, and d) Tafel plots of MoNi4/MoO2@Ni. a–d) Reproduced
with permission.[66] Copyright 2017, Nature Publishing Group.
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optimized V-doped Co4N nanosheet arrays showed a lower
overpotential of 37 mV at 10 mA cm−2, lower than the Co4N
counterpart. Besides, the V-doped Co4N nanosheet displayed
excellent stability for more than 27 h. However, the use of NH3
in the synthesis of metal nitrides is environmentally unfriendly.
Alternatively, 3D porous NiMoN on CC was prepared by
N2 plasma treating the electrodeposited NiMo alloy films at
450 °C.[65] In this synthesis, Ni not only played a crucial role in
the formation of high-purity NiMoN phase but also promoted
the formation of porous structure. By integrating advantages of
high roughness factor, fast electron transfer, facile mass trans-
port, and the synergistic effect of ternary Ni/Mo/N, the self-
supported NiMoN electrode was highly active for HER with an
exchange current density of 0.92 mA cm−2 and an overpotential
of 109 mV to drive a current density of 10 mA cm−2.
3.5. Transition Metal Alloys
Transition metal alloys with optimized ΔGH* and high intrinsic
catalytic activity have been extensively investigated as the most
active non-noble-metal HER catalysts under alkaline condi-
tion. For example, a MoNi4 electrocatalyst embedded in MoO2
cuboids and supported on nickel foam (MoNi4/MoO2@Ni)
was prepared by reducing a NiMoO4 cuboids precursor at
high temperature (Figure  6a,b).[66] The MoNi4 electrocatalyst
features a rapid Tafel-step-decided HER catalytic mechanism
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with a zero onset overpotential, an overpotential of 15 mV at
10 mA cm−2 and a low Tafel slope of 30 mV decade−1 in 1 m
KOH, which was highly comparable to the benchmark Pt/C
(Figure 6c,d). Recently, the in situ topotactic reduction method
was also applied to prepare binder-free MoNi4/MoO3−x nanorod
array/NF electrode for catalyzing HER.[67] In addition to the
Ni–Mo-based alloy, some other transition metal alloys were also
demonstrated highly active for HER under alkaline condition,
such as Cu–Ti bimetallic alloy and Al7Cu4Ni@Cu4Ni core/shell
nanocrystals.[35,68]
4. Self-Supported Electrode for OER
Compared with the HER, the OER involving complex reaction
pathways is more sluggish and generally considered as the ther-
modynamically and kinetically demanding process in water
electrolysis. Essentially, oxygen evolution is the result of the
oxidation of a hydroxyl group in alkaline solution or a water
molecule under acid condition. A proposed four sequential
proton-coupled electron-transfer steps of OER in alkaline solu-
tion can be described below, which is similar to that for the
acidic case[7]
M + OH− → MOH + e − (6)
MOH + OH− → MO + H2 O + e − (7)
MO + OH− → MOOH + e − (8)
MOOH + OH− → M + O2 + H2 O + e − (9)
The four steps of OER are all thermodynamically uphill
processes, and the rate-limiting step has the highest energy
barrier. In the OER process, the intermediates of MOH, MO, and
MOOH are generated in turn as a result of concomitant electron
and proton transfer, and the bonding interactions (M–O) within
these intermediates are crucial for the catalytic activity. The
adsorption energies of intermediates are widely used as descrip-
tors for the electrocatalytic ability. In acidic solution, the oxides
of Ru/Ir are the best for OER, while the catalysts derived from
transition metal catalyze the OER more favorably in alkaline
media.[69] Transition-metal-based OER catalysts mainly include
hydroxides/oxyhydroxide, oxides, phosphates, etc.
4.1. Transition Metal Hydroxides/Oxyhydroxides
Layered double hydroxides are widely studied electrochemical
catalysts, in particular for the OER.[70] The composition and
structure of LDHs are easily tunable by adjusting either
positively charged layers (e.g., Ni2+, Co2+, Cu2+, Mg2+, Zn2+, Ca2+,
and Mn2+) or interlayer anions (e.g., CO32−, NO3−, SO42−, Cl−,
and Br−), leading to unique redox features. However, the poor
electrical conductivity of LDHs limits the catalytic performance.
Hybridizing LDHs with conductive carbon or exfoliating bulk
LDHs to ultrathin nanosheets is widely employed to address this
issue.[71,72] To simply the synthesis and improve the long-term
stability, LDHs are often in situ grown on conductive substrate
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to form a self-supported electrode. Taking the most widely inves-
tigated NiFe LDH as an example, amorphous mesoporous NiFe
hydroxide sheets were supported on NF substrate by a facile,
one-step electrodeposition route.[73] The synthesized electrode
enabled a current density of 200 mA cm−2 at an overpotential
of 240 mV and a TOF of 0.075 s−1 at an overpotential of 400 mV,
almost threefold that of Ir/C (0.027 s−1).
To further improve the electrocatalytic performance of LDH
materials, fabricating nanocomposite or cation doping has been
adopted. Recently, Zou’s group reported a ultrafast synthesis of
amorphous Ni–Fe bimetallic hydroxide films on NF-supported
Ni3S2 nanosheet arrays through an interfacial reaction of Ni3S2
in Fe3+-containing aqueous solution (Figure  7a).[74] In the
obtained Ni–Fe–OH@Ni3S2, a rough Ni–Fe hydroxide film was
grown on the surface of Ni3S2 nanosheets (Figure 7b). Advan-
tageous structural features including the high intrinsic activity
of amorphous Ni–Fe hydroxide, the high conductivity of the
Ni3S2 array and their strongly coupled interface endow the self-
supported Ni–Fe–OH@Ni3S2/NF electrode superior yet stable
OER activity (165 mV overpotential at 10 mA cm−2; Figure 7c).
Furthermore, V-doped Ni–Fe LDH nanosheet array were grown
on NF.[75] Electrochemical analysis and DFT + U calculation
revealed that vanadium doping significantly boosted the OER
activity by modifying the electronic structure and narrowing the
bandgap. Besides the Ni–Fe bimetal family, there are reports on
other transition metal hydroxide-based self-supported OER elec-
trocatalysts, such as Ni–Co LDH nanosheets/carbon paper,[76]
Co–Al LDH nanosheets/3D graphene network[77] and Co–Zn
nanosheets/zinc foils.[78]
Although most reported LDHs exhibit high gravimetric
activity, they usually cannot afford large current density and long-
term stability due to low catalyst loading and limited adhesion
on the current collector. To address this issue, we have recently
developed a versatile and easily scalable electrosynthesis of metal
hydroxides/oxides on graphitic substrates.[16] As illustrated in
Figure 7d, the cathodic reduction of nitrate ion generates OH−
to form metal hydroxide. Meanwhile, the preinsertion of nitrate
ion in graphene layers prominently enhances the electrode-
posit-support interface and results in a seamless contact of the
catalysts and substrate (Figure 7e). Using this strategy, a hybrid
containing nanocrystalline cerium dioxide and amorphous nickel
hydroxide (NiCeOxHy) was co-electrodeposited on graphite. This
self-supported electrode exhibited an unexpectedly low OER
overpotential of 177 mV at 10 mA cm−2 (Figure 7f), high mass
activity (34.6 A g−1 at an overpotential of 270 mV) and a robust
long-term durability at a large current density of 1000 mA cm−2
for 300 h. The superb catalytic activity and long-term stability
make the NiCeOxHy electrode highly viable for application in
practical electrolyzer devices.
It is now widely recognized that during the OER process
there is phase conversion from the hydroxides to oxyhydrox-
ides, which act as the real active sites. Much interest concerns
direct synthesis of the metal oxyhydroxides OER catalysts,
which however suffer from poor electrocatalytic performance.
Hybridizing oxyhydroxides with other functional compo-
nent and 3D conductive materials is an effective strategy for
improvement. For example, FeOOH/CeO2 heterolayered
nanotubes grown on NF (FeOOH/CeO2 HLNTs-NF)
were employed as a self-supported OER catalyst.[79]
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Figure 7.  Self-supported LDH electrocatalysts for the OER. a) Schematic preparation, b) SEM image, and c) polarization curves of Ni–Fe–OH@Ni3S2/
NF electrode. a–c) Reproduced with permission.[74] Copyright 2017, Wiley-VCH. d) Schematic two-step electrochemical synthesis, e) cross-section
SEM image, and f) electrocatalytic performance of NiCeOxHy deposited on graphite. d–f) Reproduced with permission.[16] Copyright 2018, Nature
Publishing Group.

The heterolayered nanotubes vertically arranged on NF 4.2. Transition Metal Oxides

(Figure  8a,b) could provide efficient diffusion channel
for electrolyte while the CeO2 with high oxygen-storage
capability could absorb evolved oxygen, thus promoting the
OER. The FeOOH/CeO2 hybrid manifested an onset over-
potential of 210 mV, lower than those of FeOOH/NF and
CeO2/NF. A sandwiched FeOOH/Co/FeOOH hybrid nano-
tube array grown on NF was also demonstrated to be an
advanced self-supported electrocatalyst for OER.[80] Further-
more, Fe-substituted CoOOH (i.e., Fe0.33Co0.67OOH) porous
nanosheet arrays grown on CC, which were synthesized
by in situ anodic oxidation of CC supported α-Co(OH)2 in
(NH4)2Fe(SO4)2, showed improved activity over CoOOH.[81]
Owing to the low cost, high abundance, and considerable anti-
corrosion properties in an alkaline environment, transition
metal oxides were widely developed as OER catalysts.[82] Spinel
type oxide (AB2O4, A and B are 3d transition metals such as
Ni, Fe, Co, Cu, Zn, and Mn) is a family of composite oxides
attracting extensive interest.[83–85] As an example of self-sup-
ported oxide electrode, Co3O4–carbon porous nanowire arrays
on Cu foil were prepared by carbonization of the Co-based metal
organic framework (Co-MOF) precursor in N2 (Figure 8c,d).[86]
The periodic arrangement of Co nodes in the MOF scaf-
fold led to a homogeneous distribution of Co3O4 within the

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Figure 8.  Self-supported arrays of 1D oxyhydroxide and oxide nanostructures for the OER. a) Microstructural advantage and b) SEM image of FeOOH/
CeO2 HLNTs-NF electrode. a,b) Reproduced with permission.[79] Copyright 2016, Wiley-VCH. c) Schematic fabrication and d) SEM image of Co3O4C
nanowires arrays grown on Cu foil. c,d) Reproduced with permission.[86] Copyright 2014, American Chemical Society.

in situ formed porous carbon matrix. The unique electrode
configuration resulted in large active surface area, high struc-
tural stability, and enhanced charge transport, affording an
onset overpotential of 250 mV and delivering a current den-
sity of 10 mA cm−2 at 290 mV. Recently, bimetal spinel oxides
attracted increasing attention due to their rich redox reactions
and moderate electrical conductivity. One-step pyrolysis of the
Co/Fe-MOF nanorod arrays grown on NF generated 3D porous
CoFe2O4/C nanorod arrays, which featured abundant oxygen
defects and endowed high OER activity.[87] In addition, other
bimetal spinel oxide-based self-supported catalysts including
NiCo2O4 nanowall arrays/CC and sulfur-incorporated NiFe2O4
nanosheets/NF were also proved highly active for catalyzing the
OER.[88,89]
Apart from the spinel oxides, other types of metal oxides
were also developed as self-supported OER catalysts. For
example, nanostructured MoO2 and MnO2 have been widely
investigated and supported on 3D substrates such as nickel
foam and carbon paper.[90–92] The intrinsically high conduc-
tivity of MoO2 and porous nanosheet structures with abun-
dant active sites resulted in a low overpotential of 260 mV at
10 mA cm−2 for MoO2 electrode.[90] Manganese dioxide mate-
rials are also active for the OER but are plagued by low con-
ductivity and high overpotential, which could be well addressed
by engineering of Mn/O vacancies and cation doping.[91–93]
Calculation of the density of states (DOS) of oxygen-deficient
MnO2 nanosheet revealed half-metallicity property. As a result
of enhanced charge transfer, NF-supported ultrathin δ-MnO2
nanosheet arrays with abundant oxygen vacancies afforded
a high OER performance with an overpotential of 320 mV at
10 mA cm−2.[91] In another notable study, cation (Fe, V, Co, and Ni)
doped γ-MnO2 ultrathin nanosheet supported on CFP was dem-
onstrated to efficiently catalyze the OER.[92]
4.3. Transition Metal Phosphates
In 2008, Nocera’s group reported a cobalt phosphate (Co–Pi)
catalyst that exhibited unexpected OER catalytic activity in neu-
tral solution.[94] After that, earth-abundant and low-cost metal
phosphates have stimulated particular interest. In the context
of self-supported OER electrode, amorphous FePO4 nanosheets
were in situ grown on NF by a solvothermal method.[95] Com-
pared with crystalline FePO4, the amorphous FePO4 nanosheets
with disordered structure possess low-energy level of d band
center and smaller Gibbs free energy, which plays a positive
role in enhancing the catalytic activity. In addition to ferrous
phosphate, Fe(PO3)2 catalyst also showed high efficiency in
catalyzing water oxidation.[96] Fe(PO3)2 in situ grown on the
surface of a conductive Ni2P/NF scaffold generated a robust
electrode. During the OER electrocatalysis, the Fe(PO3)2 phase
was converted to amorphous FeOOH, which was proposed as
the real catalytic sites. Benefiting from the more active FeOOH
and the 3D conductive Ni2P/NF substrate, the electrode yielded
current density of 500 mA cm−2 at overpotentials of 265 mV
and a TOF value around 0.12 s−1 per 3d Fe atom at an overpo-
tential of 300 mV, along with high durability in 1 m KOH. Sim-
ilar to the case of NiFe-based hydroxide catalysts, the synergistic
effect of Fe and Ni in phosphate gives rise to enhanced OER
performance.[97] Not surprisingly, iron-doped nickel phosphate

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in situ grown on nickel foam is promising OER catalyst in neu-
tral or alkaline electrolyte.
5. Self-Supported Bifunctional Electrocatalysts
for Overall Water Splitting
For practical electrolysis of water, the HER and OER catalysts
are operated in the same electrolyte, which is strongly acidic
or basic solution to minimize the overpotential. Generally,
most nonprecious-metal-based HER catalysts (e.g., chalcoge-
nides, phosphides, carbides, and nitrides) show highest cat-
alytic activity in acidic media, while the OER catalysts such
as transition metal oxy/hydroxides and oxides only perform
well in alkaline electrolytes. Table  1 lists and compares the
catalytic performance of some typical self-supported electro-
catalysts. The mismatching of working conditions imposes
difficulty in searching for two electrocatalysts that couple well in
a single electrolyzer for overall water splitting (OWS). Devel-
oping a bifunctional electrocatalyst that could simultaneously
catalyze HER and OER effectively is preferable to simplify the
electrolyzer design, avoid detrimental crossover effect of dif-
ferent electrocatalysts at two electrodes, and decrease the cost
in device fabrication.[98,99] Therefore, extensive efforts have
been devoted to developing high-performance bifunctional
catalysts for water electrolysis, mainly focusing on creating
the bifunctionality within the currently developed HER and
OER catalysts.
The past a few years has witnessed solid progress in
developing transition metal sulfides, selenides, phosphides,
nitrides and carbides (collectively abbreviated as TMXs, where
TM = transition metal and X = S, Se, P, N, and C) as bifunc-
tional HER/OER electrocatalysts. For most TMXs, the real
active sites are different between the HER and OER electroca-
talysis. Taking nickel phosphide as an example, Ni2P remains
essentially unchanged on cathodic HER cycling but a NiOOH
layer was identified on the surface of Ni2P during anodic
OER polarization (Figure  9a–c).[100] The generated NiOOH
shell was the catalytically active phase for the OER, while
the metallic Ni2P core permitted facile electron conduction.
The in situ generated Ni2P/NiOOH heterojunction structure
exhibited unexpected OER catalytic properties superior to the
benchmark RuO2 (Figure 9d). In another typical example, the
HER active Co4N functions as efficient OER electrocatalyst
after formation of CoO2/Co4N species (Figure 9e–g).[101] In
this section, we discuss the HER/OER bifunctional application
of self-supported electrodes based on TMXs and hydroxides/
oxyhydroxides.
5.1. Transition Metal Chalcogenides
Transition metal chalcogenides are among the most widely
investigated HER/OER bifunctional electrocatalysts. Nickel
sulfides are particularly attractive because of low cost, high
conductivity and considerable electrocatalytic activities.
Zou and co-workers synthesized high-index faceted Ni3S2
nanosheet arrays on NF as a self-supported bifunctional elec-
trocatalyst, which delivered a current density of 10 mA cm−2
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at overpotentials of 223 and 260 mV for HER and OER,
respectively.[102] Serving as both the anode and cathode of an
electrolyzer, the Ni3S2/NF electrode afforded 13 mA cm−2 cur-
rent density at an applied voltage of 1.76 V with a near 100%
Faradaic yield. The respectable catalytic performance of Ni3S2
nanosheet arrays was attributed to the metallicity, binder-free
architecture and high-index facets with high intrinsic activity.
Because of different catalytic mechanism for HER and OER,
integrating the advantages of the HER and OER catalysts to
construct a novel heterostructure is beneficial for enhancing
the overall electrochemical water-splitting performance. In
this regard, recent studies reported interface engineering
of MoS2/Ni3S2 and MoS2/Fe5Ni4S8 heterostructures.[103,104]
Interestingly, the abundant interfaces in MoS2/Ni3S2 hetero-
structure and the in situ formed MoS2/NiO hybrid during the
OER enhanced the chemisorption of hydrogen and oxygen-
containing intermediates. Alkali electrolyzer composed of the
self-supported MoS2/Ni3S2 electrode as both the anode and
cathode required a remarkably low voltage of 1.56 V to deliver
10 mA cm−2 for overall water splitting in alkaline media.[103]
An analogous hybrid catalyst composed of MoS2/Fe5Ni4S8 het-
erostructures on FeNi alloy substrate was also reported for effi-
cient bicatalysis of HER and OER.[104]
There is also much interest in the use of selenide-based
bifunctional electrocatalysts for overall water splitting. Recently,
the water electrolyzer assembled with NF-supported NiSe nano-
wire film as both anode and cathode achieved a current density
of 10 mA cm−2 at a cell voltage of 1.63 V.[99] Besides, Co and
Fe co-doped NiSe2 nanosheets (with an optimized composition
of Fe0.09Co0.13NiSe2) supported on CC were fabricated as a self-
supported bifunctional catalyst.[105] The dual-cation incorpora-
tion in NiSe2 induced lattice distortion and strong electronic
interaction, which increased active site exposure and optimized
adsorption energy of reaction intermediates. Remarkably, the
fabricated electrode displayed low overpotentials of 92 and
251 mV for HER and OER respectively at 10 mA cm−2, ena-
bling operation of a water electrolyzer at voltage of 1.52 V to
reach current of 10 mA cm−2.
5.2. Transition Metal Phosphides
On account of the high activity, self-supported transition metal
phosphide electrodes have emerged as another family of attrac-
tive bifunctional catalysts for overall water splitting. Representa-
tively, Ni5P4 with a 3D hierarchical structure on a Ni foil was
prepared for HER/OER electrocatalysis.[106] After anodic cycling,
the in situ formed Ni5P4/NiOOH heterojunction featured modi-
fied electronic configuration, leading to a low OER overpotential
of 290 mV at 10 mA cm−2. As a bifunctional catalyst for overall
water splitting, the electrode delivered current of 10 mA cm−2
below 1.7 V. Aside from monometallic metal phosphides, bime-
tallic (Co1−xFex)2P with controllable composition and porosity
was synthesized via an alloy/dealloying method.[34] The opti-
mized (Co0.52Fe0.48)2P with bicontinuous nano­porous structure
was obtained after tailoring the Co/Fe ratio (Figure  10a). The
resultant self-supported (Co0.52Fe0.48)2P mono­ lithic electrode
exhibited higher catalytic activities for both HER and OER than
the binary Co2P, allowing the assembly of an electrolyzer that
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Table 1.  Comparison of the electrocatalytic activities of self-supported transition metal catalysts for HER, OER, and OWS.

Catalyst Substrate Loading Electrolyte/reactions Overpotential η Tafel slope Stability

[mg cm−2] [mV] at 10 mA cm−2 [mV decade−1] [V or mA cm−2 @ h]
se-MoS2 sheet arrays[40] Carbon paper 2.1 0.5 m H2SO4/HER 104 56 10 mA cm−2 @ 24 h
CoS2 nanowires[41] Graphite 25 ± 2 0.5 m H2SO4/HER 145 51.6 10 mA cm−2 @ 40 h
[30]
CoS2 nanosheets RGO–CNT 1.15 0.5 m H2SO4/HER 142 51 500 cycles
FeS2 nanoparticles[32] RGO 1.0 0.5 m H2SO4/HER 139 66 500 cycles
CoSe2 nanoparticles[44] Carbon paper 2.8 0.5 m H2SO4/HER 137 40 −0.185 V @ 60 h
Ni3Se2 nanoforest[50] Ni foam 8.87 1 m KOH/HER 203 79 −0.2 V @ 200 h
Ni0.89Co0.11Se2[21] Ni foam 2.16 1 m KOH/HER 85 52 −0.15/0.1 @ 12 h
MoS2(1−x)Se2x particles[51] NiSe2 foam 4.5 0.5 m H2SO4/HER 42.1 69 −0.121 mV @ 16 h
[54]
CoP nanowire arrays Carbon cloth 0.29 0.5 m H2SO4/HER 67 51 5000 cycles
CoP nanowire arrays[54] Carbon cloth 0.29 1 m KOH/HER 209 129 1000 cycles
FeP nanowire array[20] Ti plate 3.2 0.5 m H2SO4/HER 57 38 90 mA cm−2 @ 15 h
Cu3P nanowire arrays[56] Cu foam 15.2 0.5 m H2SO4/HER 143 67 −0.2 V @ 25 h
Ni5P4–Ni2P nanosheets[57] Ni foam 68.2 0.5 m H2SO4/HER 120 79.1 10 mA cm−2 @ 72 h
CoP nanorod arrays[26] Ni foam 0.92 0.5 m H2SO4/HER 67 51 5000 cycles
Fe0.5Co0.5P nanowire[59] Carbon cloth 2.2 0.5 m H2SO4/HER 37 30 100 mA cm−2 @ 100 h
NiCo2Px nanowires[60] Carbon felt 5.9 0.5 m H2SO4/HER 104 59.6 −0.1 V @ 30 h
NiCo2Px nanowires[60] Carbon felt 5.9 1 m KOH/HER 58 34.3 −0.1 V @ 30 h
NiCo2Px nanowires[60] Carbon felt 5.9 1.0 m PBS/HER 63 63.3 −0.1 V @ 30 h
Co–B–P nanosheet Ni foam 5.0 1 m KOH/HER 42 42.1 1000 mA cm−2 @ 20 h
arrays[13]
Mo2C microislands[62] Carbon cloth 1.4 0.5 m H2SO4/HER 140 124 10 mA cm−2 @ 15 h
NiMoN film[65] Carbon cloth 2.5 1 m KOH/HER 109 95 50 mA cm−2 @ 36 h
MoNi4/MoO2 [66]
Ni foam 43.4 1 m KOH/HER 15 30 200 mA cm−2 @ 10 h
MoNi4/MoO3−x [67] Ni foam 8.7 1 m KOH/HER 17 36 20−30 mA cm−2 @ 20 h
NiFe hydroxide sheets[73] Ni foam 0.023 1 m KOH/OER 270 (η80) 28 100 mA cm−2 @ 10 h
NiFeV LDHs [75]
Ni foam 2.8 1 m KOH/OER 195 (η20) 42 1.47 V @ 18 h
NiCo LDH nanoplates[76] Carbon paper 0.17 1 m KOH/OER 367 40 20 mA cm−2 @ 6 h
CoAl LDH nanosheets[77] 3D graphene 0.05 1 m KOH/OER 252 36 0.28 V @ 18 h
NiCeOxHy [16] Graphite 10 1 m KOH/OER 177 22 1000 mA cm−2 @ 300 h
FeOOH/CeO2 nanotube [79]
Ni foam 0.44 1 m NaOH/OER 250(η31.3) 92.3 0.4 V @ 50 h
FeOOH/Co/FeOOH[80] Ni foam 0.5 1 m NaOH/OER 250 (η20) 32 200 mA cm−2 @ 50 h
CoFe2O4/C nanorod Ni foam 1.03 1 m KOH/OER 240 45 10 mA cm−2 @ 30 h
arrays[87]
NiCo2O4 nanowall Carbon cloth 0.60 1 m KOH/OER 340 72 0.34 V @ 20 h
arrays[88]
porous MoO2 Ni foam 3.4 1 m KOH/OER 260 54 5000 cycles
nanosheets[90]
FePO4 nanosheets[95] Ni foam 0.285 1 m KOH/OER 218 42.7 10 mA cm−2 @ 15 h
Fe(PO3)2/Ni2 P[96] Ni foam 8 1 m KOH/OER 177 51.9 500 mA cm−2 @ 20 h
Ni3S2 nanosheet Ni foam 1.6 1 m KOH/OWS 530(η13) – 13 mA cm−2 @ 150 h
arrays[102]
MoS2/Ni3S2[103] Ni foam 9.7 1 m KOH/OWS 420 – 10 mA cm−2 @ 10 h
NiSe nanowires [99]
Ni foam 2.8 1 m KOH/OWS 400 – 20 mA cm−2 @ 20 h
N-WC nanoarrays[107] Carbon paper 10 0.5 m H2SO4/OWS 170 – –
Cu@NiFe LDH [109]
Cu foam 2.2 1 m KOH/OWS 310 – 10 mA cm−2 @ 48 h
δ-FeOOH nanosheets[110] Ni foam 0.16 1 m KOH/OWS 390 – 1.76 V @ 60 h

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Figure 9.  Phase transformation of HER electrocatalyst for OER. a) Elemental mapping, b) HRTEM image after OER stability test, c) in situ Raman
spectra during a linear sweep voltammetry scan, and d) OER polarization curves of multishelled Ni2P. a–d) Reproduced with permission.[100] Copyright
2017, American Chemical Society. e) HRTEM image after cycling, f) Fourier transformed EXAFS spectroscopies after cycling, and g) OER polarization
curves of Co4N. e–g) Reproduced with permission.[101] Copyright 2015, Wiley-VCH.

could operate at current density of 10 mA cm-2 and voltage of that the long-term durability of metal carbides for OER under
1.53 V in 1.0 m KOH electrolyte (Figure 10b,c). acidic condition requires further evaluation.

5.3. Transition Metal Nitrides and Carbides 5.4. Transition Metal Hydroxides and Oxyhydroxides

In developing metal nitride- and carbide-based catalysts for
overall water splitting, Xiao and co-workers reported the prep-
aration of hierarchical FeNi3N nanostructures in situ grown
on a surface-redox-etching NF (FeNi3N/NF).[108] The obtained
FeNi3N/NF electrode was highly active to catalyze both HER
and OER in basic media, with low overpotentials of 75 and
202 mV at current density of 10 mA cm−2, respectively. A low
cell voltage of 1.62 V was required for driving the FeNi3N/
NF-based electrolyzer at working current of 10 mA cm−2. It is
challenging to build a bifunctional electrode for acidic water
splitting since most metal oxides/oxyhydroxides in situ formed
on the surface of TMXs during OER process are unstable in
strong acids. Encouragingly, Sun’s group have demonstrated a
nitrogen-doped tungsten carbide (N-WC) nanoarray grown on
CFP substrate (Figure 10d), which promises overall water split-
ting in acid.[107] Water splitting catalyzed by the bifunctional
N-WC nanoarray electrode offered an onset voltage of ≈1.4 V
and a voltage of 1.7 V to attain 30 mA cm−2 (Figure 10e). Fur-
thermore, the assembled electrolyzer could be powered by a
commercial AA battery (Figure 10f). It should be mentioned
Transition metal LDHs are known as advanced OER catalysts,
and they are recently demonstrated to be applicable in cata-
lyzing the HER when composing with a metallic component.
A presentative example is NiFe LDH nanosheets catalyst grown
on the CF-supported Cu nanowire (Cu@NiFe LDH).[109] In this
unique 3D core–shell electrode, the Cu nanowires core rooted
into CF ensures good electrical contact and mechanical stability,
while the few-layer NiFe LDH shell exposes abundant catalyti-
cally active sites. As a result, the freestanding Cu@NiFe LDH
catalyst manifested remarkable HER and OER performance in
alkaline electrolyte. Water electrolyzer assembled with Cu@
NiFe LDH as both anode and cathode could attain current den-
sities of 10 and 100 mA cm−2 at voltages of 1.54 and 1.69 V,
respectively.
Besides LDHs, water-splitting bifunctionality of metal oxy-
hydroxides was recently reported by Liu et al.[110] Specifically,
ultrathin δ-FeOOH nanosheets with rich Fe vacancies were
synthesized by a wet-chemistry approach. Computational and
experimental results revealed that the presence of second
neighboring Fe to Fe vacancies could create catalytic sites for

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Figure 10.  Self-supported electrode as HER/OER bifunctional catalyst for water electrolysis. a) SEM images, b) electrocatalytic water splitting perfor-
mance, and c) schematic electrolyzer application of nanoporous (Co0.52Fe0.48)2P. a–c) Reproduced with permission.[34] Copyright 2016, Royal Society
of Chemistry. d) SEM images, e) performance of water electrolysis, and f) electrolyzer application of nitrogen-doped tungsten carbide nanoarrays.
d–f) Reproduced with permission.[107] Copyright 2018, Nature Publishing Group.

both the HER and OER while the Fe vacancies could lead to
an increased electrical conductivity of δ-FeOOH. Remarkably, a
two-electrode electrolyzer employing the δ-FeOOH nanosheets/
NF as both the anode and cathode sustained a current density
of 10 mA cm−2 at a low driven voltage of 1.62 V, together with
favorable long-term durability.
5.5. Conclusion and Perspective
Exploiting cheap, efficient and robust HER/OER catalysts is of
crucial importance in water-splitting technology for hydrogen
energy. Compared with conventional electrode in powdery paste
form, self-supported electrodes integrating in situ grown cata-
lytically active phase benefit simplification of electrode prepa-
ration, decrease of interface resistance, exposure of abundant
active sites and enhancement of stability, promising practical
applications in electrolyzers. In the past decade, there has been
solid developments in self-supported transition-metal-based
electrocatalytic materials that range from alloys, chalcogenides,
phosphides, carbides and nitrides for HER to phosphates,
hydroxides and oxides for OER, and to a few of their hybrids
for overall water electrolysis. Table 1 lists a comparison of the
electrochemical performances of some representative self-
supported transition metal electrocatalysts by benchmarking
overpotential at 10 mA cm−2, Tafel slop and stability. In acidic
electrolytes, transition metal phosphides (the bimetallic in par-
ticular) exhibit higher HER catalytic activity and stability than
other compounds, while metal alloys show the remarkable
performance under alkaline condition. For the OER, the most
promising non-noble-metal electrocatalysts are based on LDHs,
which often outperform the benchmark noble-metal catalysts
(i.e., Ir and Ru compounds) in alkaline media. For OWS, the
bimetallic phosphides and selenides are promising due to
superior catalytic activities for both HER and OER. In spite of
substantial progress in materials design/synthesis and proper-
ties investigation, challenges remain in further development of
self-supported electrodes.
First, the catalytic activity and stability of nonprecious cata-
lysts can hardly meet the requirement of practical electrolyzers,
which call for competent electrocatalysts to afford a large current
density above 500 mA cm−2 at overpotentials under 300 mV.[96]
The main bottleneck is the sluggish kinetics. Improvement
should simultaneously resort to strategies such as: 1) increasing
the intrinsic activity and density of catalytically active sites by
compositional modulation, downsizing, active facet exposure, or
using single site catalysis; and 2) enhancing the charge transfer
and mass transport via cation/anion doping, defect control, inter-
face engineering, porosity design, and so on. The stability of the
most reported catalysts is far from satisfactory, which generally
operate well at a low current density (<100 mA cm−2) for dozens
of hours. Electrodes for practical use should sustain large cur-
rent density well above 500 mA cm−2 for thousands of hours.[2,14]
To obtain robust self-supported electrode, we should identify
and control the stability affecting factors like catalyst composi-
tion/phase, substrate material, catalyst-substrate interface, elec-
trode-electrolyte wettability, mechanical property and so on. The
intrinsic stability of most transition-metal-based electrocatalysts

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in acid/alkaline electrolyte is not yet fully understood. Evaluation
of the chemical and structural durability upon long-term ageing
and polarizing in strong acidic/alkaline condition deserves fur-
ther studies. Note that most transition-metal-based OER catalysts
are applied in alkaline electrolyzers due to low stability in acidic
media. Particular interest would be paid to developing acid-stable
electrocatalysts applicable in acidic electrolyzer equipped with
commercial proton exchange membrane.[111] Besides, current
preparation of self-supported electrocatalysts usually involves
tedious procedures or suffer from low yield. It is desirable to
develop facile and easily scalable synthetic strategies.
In searching for advanced HER and OER catalysts, fundamental
mechanistic understanding is necessary. New electrocatalyst
development often relies on the activity-oriented trial-and-
error methods, but can be more effective based on in-depth
understanding the water splitting reactions at multiscale level.
Computational modeling and in situ spectroscopic study are
powerful tools to unravel the catalysis mechanism and struc-
tural evolution of electrodes,[112] particularly for the OER elec-
trocatalysts, which generally involve complex surface structural
reconstruction at different redox steps.[113] Operando analytic
techniques such as X-ray absorption spectroscopy, Raman and
Fourier-transform infrared spectroscopy have been success-
fully applied to track the surface species in OER, which helps
to uncover the real catalytic active sites and catalytic mecha-
nism.[114] Furthermore, more attention should be paid on a
reliable evaluation of the catalytic performance of different
electrocatalysts. Simply comparing the current density based
on geometric electrode area might mask important influential
factors such as catalyst size, mass loading, substrate effect and
testing condition.[115,116] Therefore, an assessment of compre-
hensive indexes including overpotential, Tafel slope, exchange
current density, TOF value, specific activity based on mass and
electrochemically active surface area, and Faradaic efficiency
should be taken into account for convincing comparison.
Acknowledgements
The authors acknowledge financial support from NSFC (No. 21871149
and 51571125), MOST (No. 2017YFA0206700), Tianjin Project
(No. 18JCZDJC31100), MOE (B12015), and the Fundamental Research
Funds for the Central Universities.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
electrocatalysis, hydrogen evolution, oxygen evolution, self-supported
electrodes, transition metals
Received: September 30, 2018
Revised: January 22, 2019
Published online: April 1, 2019
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