Advanced Materials - 2019 - Sun - Self Supported Transition Metal Based Electrocatalysts For Hydrogen and Oxygen Evolution

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PROGRESS REPORT
Water Electrolysis www.advmat.de
Self-Supported Transition-Metal-Based Electrocatalysts

for Hydrogen and Oxygen Evolution
Hongming Sun, Zhenhua Yan, Fangming Liu, Wence Xu, Fangyi Cheng,* and Jun Chen
selenides, phosphides, carbides, nitrides,

Electrochemical water splitting is a promising technology for sustainable alloys, oxides, hydroxides/oxyhydroxides,
conversion, storage, and transport of hydrogen energy. Searching for earth- phosphates, etc.[6,7] However, the activity
abundant hydrogen/oxygen evolution reaction (HER/OER) electrocatalysts and durability of most noble-metal-free
with high activity and durability to replace noble-metal-based catalysts plays electrocatalytic materials remain far from
satisfactory.
paramount importance in the scalable application of water electrolysis. Nanostructuring is a widely adopted
A freestanding electrode architecture is highly attractive as compared to strategy to enhance the performance of
the conventional coated powdery form because of enhanced kinetics and transition-metal-based electrocatalysts.[2,8,9]
stability. Herein, recent progress in developing transition-metal-based However, practical applications of nano-
HER/OER electrocatalytic materials is reviewed with selected examples of structured catalysts suffer from several
issues. On the one hand, nanoparticles
chalcogenides, phosphides, carbides, nitrides, alloys, phosphates, oxides,
need to be casted on the current collector
hydroxides, and oxyhydroxides. Focusing on self-supported electrodes, the using polymeric binder (e.g., polytetra-
latest advances in their structural design, controllable synthesis, mechanistic fluoroethylene or nafion), which inevitably
understanding, and strategies for performance enhancement are presented. increases the resistance, buries the active
Remaining challenges and future perspectives for the further development of sites, and inhibits mass transport,[10] as
self-supported electrocatalysts are also discussed. 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
1. Introduction condition, the carbon additive is prone to oxidized and etched
at high potential, which deteriorates electrode performance.[12]
Electrochemical water splitting is an attractive hydrogen On the other hand, owing to the low adhesive force between the
generation technology with advantages including zero catalytically active phase and substrate, the loading mass of the
carbon emission, high-purity product, and the ability to nanocatalysts is usually less than 1 mg cm−2, providing limited
store intermittent renewable energy (i.e., wind and solar catalytically active sites. Furthermore, coated catalysts could be
energy).[1,2] As a strongly uphill reaction, water electrolyzers easily peeled off from the substrate during long-term or large-
usually operate at a much larger voltage of 1.8–2.0 V relative current electrocatalysis.[13] Thus, the powdery electrodes work
to the theoretical limit of 1.23 V. The use of efficient electro- well only at small current densities (<100 mA cm−2) for dozens
catalysts for hydrogen/oxygen evolution reactions (HER/OER) of hours and cannot meet the requirements of practical indus-
can effectively improve the sluggish kinetics of HER/OER trial electrolyzers that usually operate at high current densities
and therefore decrease the overpotential.[3] Up to now, the above 500 mA cm−2 for thousands of hours.[2,14]
state-of-the-art HER and OER electrocatalysts are Pt-based Compared with conventional powdery electrocatalysts, the
materials and the oxides of Ru or Ir, respectively; but the scar- self-supported electrodes with catalytically active phase in situ
city and high cost hinder their widespread deployment.[4,5] grown on the conductive substrates are more desirable as they
Extensive efforts have been devoted to nonprecious electrocata- are characterized with the following merits (Figure 1b). First, the
lysts including transition-metal compounds such as sulfides, 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
Dr. H. Sun, Dr. Z. Yan, F. Liu, Dr. W. Xu, Prof. F. Cheng, Prof. J. Chen lowers the cost.[15] Second, the substrate materials can rivet and
Key Laboratory of Advanced Energy Materials Chemistry
(Ministry of Education)
disperse catalysts, resulting in high loading of active components
College of Chemistry and thus providing abundant catalytic sites.[16] Third, the
Renewable Energy Conversion and Storage Center binding of catalytic materials and substrates is more intimate
Nankai University without additional binder. The seamless contact ensures rapid
Tianjin 300071, China charge transfer while the tight integration prevents catalyst
E-mail: [email protected]
shedding. Finally, the preparation of self-supported electrode is
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201806326.
easier to realize surface hydrophilic/hydrophobic engineering
by purposefully adjusting the morphology and microstructure.
DOI: 10.1002/adma.201806326 Hydrophilic electrode could accelerate the bubble detachment,
Adv. Mater. 2020, 32, 1806326 1806326 (1 of 18) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
15214095, 2020, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201806326 by Technische Universitat Darmstadt, Wiley Online Library on [24/02/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advmat.de
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
Figure 1. Schematic illustration of the structural and electrochemical a visiting scholar at UCLA
features of: a) conventional powdery catalysts coated on current collectors in 2015–2016. His research
with polymer binder and carbon additives, and b) self-supported electrode interests cover the design
with in situ grown catalysts on the substrates.
and synthesis of advanced
materials for energy conver-
enhance the electrocatalyst/electrolyte contact, and promote
sion and storage applica-
charge and ion transfer.[17,18] All these advantages favor boosting
tions, particularly focusing on nonstoichiometric electrode
the catalytic activity and long-term stability of self-supported
materials for electrocatalysis and batteries.
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, target catalyst component. At present, transition metal elements
we intend to provide an overview on recent advance in self- of Fe, Co, Ni, Mn, Zn, Ti, Cu, V, Mo, and W are the most widely
supported transition-metal-based HER/OER electrocatalysts, investigated to construct self-supported transition-metal-based
with focus on their structure design, electrode preparation, and electrocatalysts due to the low cost and unique physicochemical
catalytic performance. After a brief introduction of the widely properties (Figure 2). Common substrates are mainly focused
employed synthetic strategies, a review is presented on presenta- on metal, carbon, and a few other conductive materials in
tive self-supported electrocatalysts separately for HER, OER, different forms, including carbon fiber papers (CFP), carbon
and overall water electrolysis. The selected electrocatalytic mate- cloth (CC), graphite plate, metal foam (e.g., Ni/Cu foam),
rials include sulfides, selenides, phosphides, carbides, nitrides, metal mesh (e.g., Ti/Cu mesh), metal plate/foil (e.g., Ti plate
alloys, hydroxides/oxyhydroxides, oxides, and phosphates and W/Mo/Cu foil), fluorine-doped tin oxide (FTO), and so on.
of transition metals. Finally, the challenges and prospects Featuring with mechanical strength and flexibility, graphene
are discussed in future developments of the self-supported and carbon nanotubes can be coupled with nanocatalysts to
transition-metal-based electrocatalysts. form freestanding film electrode via post-treatments. In addi-
tion, some monolithic substrate-free alloy materials can directly
function as self-supported electrocatalysts.
2. Design and Preparation of Self-Supported The hydro/solvothermal method is an effective strategy to
prepare inorganic catalytic materials such as metal oxides and
Electrode
hydroxides/oxyhydroxides at modest temperature in a pressure-
To prepare self-supported electrode, the catalytically active phase tight reactor.[20–22] In hydro/solvothermal reaction, the surface
is in situ grown on the substrate during the synthesis process. defects and oxyl groups on the substrates serve as sites for the
Typical synthetic strategies include hydro/solvothermal, elec- nucleation and conformal growth of active materials, resulting
trodeposition, vapor deposition, vacuum filtration, freeze in a uniform deposition of nanostructure on the substrates.
drying, and the combination of different methods. The applied For example, a hydrothermal method was applied to prepare
approach depends on the selective substrate material and the a series of coralloid trimetallic WCoFe oxyhydroxides with a
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]
Figure 2. Substrate materials and transition-metal elements that
are used to build self-supported electrodes for electrocatalytic water
Moreover, alloying/dealloying is another robust method to fab-
splitting. ricate porous self-supported monolithic electrodes without sub-
strates. In a dealloying process, the more reactive component
sponge-like structure, adjustable composition, and homoge- is selectively dissolved or etched and the remaining component
neous distribution on nickel foams (NF) (Figure 3a).[22] The syn- reorganizes into a 3D porous network. This versatile and scalable
thesized transition metal oxy-compounds can be directly used method has been successfully applied to obtain transition metal
as electrocatalysts or act as the precursors to synthesize other phosphide and alloy electrocatalysts, such as amorphous metallic
compounds such as sulfides, selenides, phosphides, carbides, NiFeP, nanoporous (Co1−xFex)2P, and Cu–Ti bimetallic alloy.[33–35]
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 3. Self-Supported Electrocatalysts for HER
prepared by one-pot hydro/solvothermal route.
Electrodeposition is another versatile technique to prepare The electrochemical HER involves multiple steps.[2] In acidic
self-supported electrodes. The electrodeposition process is electrolyte, the first step (Volmer reaction) is reducing protons
generally carried out in a three-electrode electrochemical cell on catalytic sites (M) to form adsorbed hydrogen (Hads).
with selected conductive substrates as working electrodes, on At low coverage of Hads on the catalyst surface, Hads will
which target materials are uniformly and rapidly deposited under preferably combine with a proton and an electron to generate
applied electric field.[26] Most transition-metal-based materials a H2 molecule (Heyrovsky reaction). In the case of high Hads
including oxides, hydroxides, oxyhydroxides, sulfides, selenides, coverage, two adjacent Hads atoms bind to form H2 (Tafel reac-
phosphides, and alloys can be electrodeposited on a conducting tion). Mechanistic studies suggest that molecular H2 forms
substrate. Figure 3b shows an example of electrodeposited 3D via Volmer–Heyrovsky or Volmer–Tafel pathway. Similarly,
Ni–Mo electrocatalysts supported on Cu foam.[27] The deposi- the HER proceeds through similar pathways under alkaline
tion was realized by implementing a constant current density condition. Differently, the Volmer reaction is facile in acid
between 2 and 200 mA cm−2 in an electrolyte solution containing due to abundant available protons while it is kinetically more
nickel sulfate, sodium citrate, ammonium molybdate, sodium sluggish in alkaline media as it involves water dissociation
chloride, and ammonium hydroxide. In addition to rapid syn- prior to H absorption. The HER process can be described using
thesis, another advantage of electrodeposition is the controllable the following elementary steps[4,6]
catalyst loading on the substrate by adjusting deposition time
and applied potential/current density.[16] Volmer reaction : H+ + M + e − → MHads ( in acid ) (1)
In combination with hydrothermal and electrodeposition
methods, chemical vapor deposition (CVD) has been widely H2 O + M + e − → MHads + OH− ( in alkali ) (2)
used to synthesize self-supported transition-metal-based elec-
Heyrovsky reaction : MHads + H+ + e − → M + H2 ( in acid ) (3)
trocatalysts. Under sintering at high temperature, some metal
substrates or metal oxides/hydroxides/oxyhydroxides grown on MHads + H2 O + e − → M + OH− + H2 ( in alkali ) (4)
substrates can react with the gas phase of nonmetal precursors
such as phosphorus (PH3 or P), sulfur, selenium, carbon (CH4 Tafel reaction : 2MHads → 2M + H2 (5)
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 As bioinspired HER electrocatalysts, transition metal sulfides
of merit to predict/estimate the activities of HER catalysts. have gained extensive interest over a decade. Among them,
An ideal catalytic site for the HER should have a ΔGH* near MoS2 is the most extensively developed because of its unique
zero. The ΔGH* is closely associated with the inherent surface structural and electronic properties. Both experimental and
chemistry and electronic structure of the materials. In recent computational studies have shown that the catalytic activity
years, extensive efforts have been put forward to developing of bulk MoS2 is poor and highly dependent on the number
highly active HER catalysts such as transition metal sulfide, of exposed edge sites.[36] Thus, it is desirable to design and
selenide, nitride, phosphide, carbide, nitride, and alloy. Next, modulate MoS2 catalysts with maximum exposed edge sites.
we focus our discussion on those electrocatalysts with self- In this regard, Cui’s group prepared a MoS2 thin film with
supported structure. vertically aligned layers on a flat substrate.[37] The obtained
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- Besides Mo and W, Co-based sulfides are demonstrated to
mance to the bulk counterpart. Afterward, MoS2 nanosheet be active for the HER. Particularly, extensive interest has been
arrays vertically aligned on NF and edge-oriented MoS2 films directed to the pyrite-phase CoS2 with metallic conduction
loaded on Mo substrate were also developed as self-supported and long-term stability in both acidic and alkaline conditions.
HER catalyst.[38,39] Besides simply increasing the number of Notably, Jin’s group synthesized CoS2 with different shapes
exposed edge sites, attention was also paid on tailoring the of film, microwire, and nanowire on a graphite disk substrate
MoS2 edge surface. Recently, a stepped edge surface-termi- by adjusting synthesis parameters (Figure 4a).[41] Compared
nated MoS2 sheet array (se-MoS2) was fabricated on CFP by a with planar film electrode, nanostructured CoS2 exhibited not
microwave hydrothermal method.[40] Compared with a flat edge only superior catalytic activities but also increased stability due
surface-terminated sheet array and randomly grown MoS2, to facilitated release of gas bubbles from electrode surface,
se-MoS2 showed a lower overpotential because of the optimal as shown in Figure 4b. The catalytic activity of CoS2 can be
hydrogen adsorption energy (ΔGH) value. further improved by partly substituting S by P to form a ternary
Similar with MoS2, WS2 adopts a layered structure with pyrite-type cobalt phosphosulfide (CoPS) as the introduction of
adjustable electrical properties and exposed edge sites being the P atom could optimize the GH* of hydrogen adsorption at the
active HER centers. Likewise, studies on WS2 are mainly focused Co site.[42]
on synthesizing nanostructured WS2 with more edge sites. An Compared with Co, Ni and Fe are cheaper and more
exemplified 3D self-supported film electrode through coupling abundant and logically the related sulfides have been widely
2D 1T-WS2 nanolayers and P-, N-, and O-doped graphene sheets investigated as HER catalysts. Remarkably, 3D hierarchically
was recently fabricated via a vacuum-filtration process.[31] The porous Ni3S2 film on a nanoporous copper substrate was syn-
edge-rich 1T WS2 nanosheets and the synergistic effect between thesized via an unusual galvanic replacement approach using
the WS2 nanolayers and heteroatom-doped graphene sheets the nanoporous copper substrate as the template and nickel
were proposed to boost the HER activity of the integrated film chloride and thiourea as the starting materials.[43] Such in situ
electrode, which attained a current density of 10 mA cm−2 at an homogeneous growth of active phase on the restructuring
overpotential of 125 mV. nanoporous copper skeleton enhanced accessible active sites.
Additionally, the unique architecture accelerated the mass electrode surface and diminish the bubble shielding effect,
transport and favored more efficient utilization of active sites. surface modulating and structure engineering have been
In acidic media, the self-supported Ni3S2 electrode displayed attested to enhance and stabilize the electrocatalytic per-
high HER catalytic activities with a high turnover frequency formance. For selenides, a hydrophilic Ni3Se2 nanoforest/
(TOF) of 0.052 s−1 (@η100 mV) and a large exchange current NF electrode and a hydrophobic microsphere-like Ni3Se2/
density (j0) of 0.492 mA cm−2. In alkaline solution, the self- NF electrode were reported recently.[50] During the HER
supported Ni3S2 electrode also exhibited superior HER catalytic process, in situ videos showed that the bubbles adhered on
ability with a large exchange current density of 0.786 mA cm−2, the surface of Ni3Se2 nanoforest/NF electrode have weaker
higher than that in acidic condition. There are rarely any non- adhesive force and smaller size than those attached on the
precious catalysts that could exhibit comparable HER activity in microsphere-like Ni3Se2/NF electrode. As a result of accel-
both acidic and alkaline media. For iron sulfides, Hu’s group erated gas-bubble detachment, the Ni3Se2 nanoforest/NF
reported a novel strategy of in situ loading FeS2 nanoparticle electrode exhibited a much better catalytic performance
on RGO by a current-induced high-temperature rapid thermal compared with the microsphere-like counterpart. Besides
shock of iron pyrite.[32] The embedding of ultrafine FeS2 nano- binary metal selenides, ternary metal selenides with doping
particles in RGO resulted in a freestanding FeS2–RGO film element were attractive HER electrocatalysts as well. Novel
electrode, which achieved a current density of 10 mA cm−2 at 3D Ni0.89Co0.11Se2 mesoporous nanosheet networks on NF
an overpotential of 139 mV. 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-
3.2. Transition Metal Selenides viding high electrical conductivity and integrated electrode
structure that jointly enhanced the catalytic performance
Generally, transition metal selenides have a higher intrinsic of Ni0.89Co0.11Se. Notably, the 3D Ni0.89Co0.11Se electrode
catalytic activity in comparison to the corresponding sulfides.[45,46] showed remarkable HER catalytic activities in acidic, neutral,
Accordingly, there is an increase interest to develop the transition and alkaline media with low overpotentials of 52, 82, and
metal selenide-based HER electrocatalysts. Owing to the homol- 85 mV at −10 mA cm−2, respectively. Another example is
ogous structure of MoS2 and MoSe2, strategies investigated ternary MoS2(1−x)Se2x particles, which were demonstrated to
for improving the HER activities of MoS2 such as increasing surpass the binary MoS2 due to the lower Gibbs free energy
conductivity by phase transformation, exposing active sites by for hydrogen adsorption.[51]
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- 3.3. Transition Metal Phosphides
flake arrays on CC act as an advanced self-supported HER
electrode.[48] The N doping and introduction of 1T phase into In 2005, Rodriguez’s group performed density functional
2H-MoSe2 improved the electrical conductivity and favored the theory (DFT) calculation to demonstrate that the (001) sur-
exposure of more active edge sites of MoSe2. Furthermore, the face of Ni2P possesses the favorable H binding in hydroge-
porous graphene coupled with the preferential thin nanoflakes nase systems.[52] The high intrinsic activity together with the
of MoSe2 effectively accelerated electronic and ionic transfer. In thermostability, high conductivity, and low cost makes Ni2P a
the 0.5 m H2SO4 solution, the composite delivered a small onset promising alternative to Pt-based electrocatalyst for HER. Later
overpotential of 45 mV and a low Tafel slope of 49 mV decade−1. on, Lewis and co-workers experimentally validated the respect-
The Co-based selenide catalysts are more frequently reported able performance of Ni2P.[8] Since then, Ni2P and related
selenide HER catalysts. Nanoparticulate CoSe2 with cubic transition metal phosphides (e.g., CoP, FeP, Cu3P, and MoP)
pyrite–type phase on CFP is a representative example in case.[44] have stimulated increasing interest as earth-abundant
The synthesis followed a two-step process: drop-casting and HER catalysts.[4] Moreover, unlike metal sulfides of which
pyrolysis of the precursor ink to form cobalt oxide nanoparticles the electrocatalytic activity is limited to the edges, metal
on CFP, and post selenizaiton in Se vapor. As shown in phosphides are found active in the bulk form. Thus, the metal
Figure 4c–e, a layer of CoSe2 nanoparticles was conform- phosphides outperform the transition metal sulfide-based
ably covered on carbon fibers. The CFP-supported CoSe2 catalysts (e.g., MoS2).[8,53] Logically, self-supported metal phos-
nanoparticle film gave a current density of 100 mA cm−2 at an phide nanostructures in situ grown on 3D substrates have
overpotential of ≅180 mV (Figure 4f). Aside from cubic-pyrite- been widely exploited. Along this line, Sun’s group developed
type phase, CoSe2 can also crystallizes into an orthorhombic a two-step synthetic strategy to prepare several metal phos-
macarsite-type structure. Xie’s group purposively prepared phide electrocatalysts. First, transition metal oxide/hydroxide/
the cubic-pyrite-type and orthorhombic macarsite phase of oxyhydroxide-based precursors are in situ grown on the
CoSe2 on a flexible CC.[49] Experimental and computational substrates by hydrothermal or electrodeposition reactions.
results unveiled that the metallic cubic pyrite CoSe2 possessed Then, the precursors are chemically converted into the cor-
higher electrical conductivity, optimal water adsorption energy, responding metal phosphides by a low-temperature topotactic
and faster transformation efficiency of Hads into molecular phosphidation reaction using NaH2PO2 as P source. Rep-
hydrogen, thus outperforming the orthorhombic phase. resentatively, nanoporous CoP nanowire arrays on CC were
Considering the importance of hydrophilic/aerophobic obtained by low-temperature phosphidation of the Co(OH)
electrode surface that facilitates gas release from the F/CC precursor.[54] The CoP nanowires uniformly coated on
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 arrays, which were fabricated via a potentiostat electrodeposi-
resulting CoP/CC electrode showed exceptionally high catalytic tion technique in a three-electrode mode.[26]
performance, giving a high TOF of 0.725 s−1 at an overpotential For the binary metal phosphides, the hydrogen adsorption free
of 75 mV, a low overpotential of 67 mV at 10 mA cm−2, and a energy, which is closely linked to the intrinsic catalytic activity,
small Tafel slope of 51 mV decade−1 (Figure 5b,c). Compared is often either too strong or too weak. Cation or anion doping
with that in acidic electrolyte, the CoP/CC electrode displayed could optimize the electronic structure and improve the catalytic
a relatively high overpotential of 209 mV to approach a current performance.[58] In this regard, ternary FexCo1−xP nanowire
density of 10 mA cm−2 in basic media. In addition, FeP nanoarrays supported on CC were synthesized and investigated.[59]
wire array/Ti plate, Fe-doped Ni2P nanosheet arrays/NF, and DFT calculations predicted that the ternary FexCo1−xP has a
Cu3P nanowire arrays/CF were also prepared as self-supported more favorable free energy of hydrogen adsorption than does
HER electrocatalysts.[20,55,56] binary CoP. The optimized Fe0.5Co0.5P electrode afforded an HER
Straightforward one-step approaches were also developed by catalytic current density of 10 mA cm−2 at a low overpotential of
direct phophorization of a commercially available metal sub- 37 mV. Another example is self-supported NiCo2Px in situ grown
strate under sintering or solvothermal conditions. For instance, on carbon felt, which outperformed the binary CoPx and NiPx.[60]
a self-supported electrode composed of biphasic Ni5P4–Ni2P Besides bimetal synergistic effect in phosphides, the inclusion of
nanosheet arrays was synthesized by phosphorizing NF metalloid also exerts positive effect. Our recent studies on ternary
with phosphorus vapor.[57] This 3D HER electrode showed a Co–B–P indicated that the synergistic effect of P and B favors
low HER onset potential of 54 mV and a low Tafel slope of dissociate of H2O, weakens surface H absorption, and suppresses
79.1 mV decade−1 in acidic medium. Besides, a self-supported Co oxidation.[13] A typical Co2.9B0.73P0.27 nanosheet array was syn-
Ni2P nanorods/NF HER electrode was also fabricated via phos- thesized on nickel foam (Co–B–P/NF; Figure 5d) via a facile room-
phorization of the NF substrate under a solvothermal reaction temperature one-pot electroless method. The obtained Co–B–P/
with red phosphorus.[25] These one-step strategies avoid the NF electrode, which combines advantages of B/P synergistic
complicated precursor synthesis and post-treatment steps, effect and superhydrophilic surface properties, resulted in signifi-
but are often limited by the selection of corresponding metal cantly higher HER catalytic activity than that of binary Co–P and
substrates, especially in the case of preparing multimetal Co–B as well as the hydrophobic Co–B–P (Figure 5e,f). Further-
phosphides. Alternatively, electrodeposition was attempted more, the 3D self-supported architecture contributed to remark-
to prepare metal phosphide-based binder-free electrodes. A able performance at high current densities up to 2000 mA cm−2
recent example is the NF-supported CoP mesoporous nanorod with a nearly 100% Faradaic efficiency of HER.
3.4. Transition Metal Carbides and Nitrides optimized V-doped Co4N nanosheet arrays showed a lower
overpotential of 37 mV at 10 mA cm−2, lower than the Co4N
Metal carbides and nitrides have been widely investigated as counterpart. Besides, the V-doped Co4N nanosheet displayed
a possible alternative to platinum due to the Pt-like electronic excellent stability for more than 27 h. However, the use of NH3
behavior, high conductivity, and considerable stability in a wide in the synthesis of metal nitrides is environmentally unfriendly.
pH range.[6] The synthesis of metal carbides usually requires a Alternatively, 3D porous NiMoN on CC was prepared by
high-temperature (above 700 °C) carbonization process, which N2 plasma treating the electrodeposited NiMo alloy films at
inevitably leads to sintering and agglomeration of catalysts.[61] 450 °C.[65] In this synthesis, Ni not only played a crucial role in
Self-supported electrode assembly is an effective strategy to the formation of high-purity NiMoN phase but also promoted
address this problem. Along this direction, Zou and co-workers the formation of porous structure. By integrating advantages of
in situ synthesized Mo2C microislands on a flexible CC as high roughness factor, fast electron transfer, facile mass trans-
a self-supported HER electrode.[62] Benefiting from the rich port, and the synergistic effect of ternary Ni/Mo/N, the self-
catalytic sites of inland-like Mo2C, high electrical conductivity, supported NiMoN electrode was highly active for HER with an
and intimate connection of the catalyst and substrate, the as- exchange current density of 0.92 mA cm−2 and an overpotential
prepared binder-free electrode showed respectable HER electro- of 109 mV to drive a current density of 10 mA cm−2.
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 3.5. Transition Metal Alloys
showed an inferior HER catalytic properties.[63] Even so, some
metal nitride-based HER catalysts have been exploited by cation Transition metal alloys with optimized ΔGH* and high intrinsic
doping, which could significantly improve the performance catalytic activity have been extensively investigated as the most
by redistributing the charge to activate the catalytic sites. For active non-noble-metal HER catalysts under alkaline condi-
example, V-doped Co4N nanosheets were recently synthesized tion. For example, a MoNi4 electrocatalyst embedded in MoO2
by growing the V-doped Co(OH)2 nanowires on NF via a hydro- cuboids and supported on nickel foam (MoNi4/MoO2@Ni)
thermal reaction followed by a nitridation treatment in an NH3 was prepared by reducing a NiMoO4 cuboids precursor at
atmosphere.[64] The V doping caused downshift of the d-band high temperature (Figure 6a,b).[66] The MoNi4 electrocatalyst
center, which favors the H desorption. In alkaline media, features a rapid Tafel-step-decided HER catalytic mechanism
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.
with a zero onset overpotential, an overpotential of 15 mV at to form a self-supported electrode. Taking the most widely inves-
10 mA cm−2 and a low Tafel slope of 30 mV decade−1 in 1 m tigated NiFe LDH as an example, amorphous mesoporous NiFe
KOH, which was highly comparable to the benchmark Pt/C hydroxide sheets were supported on NF substrate by a facile,
(Figure 6c,d). Recently, the in situ topotactic reduction method one-step electrodeposition route.[73] The synthesized electrode
was also applied to prepare binder-free MoNi4/MoO3−x nanorod enabled a current density of 200 mA cm−2 at an overpotential
array/NF electrode for catalyzing HER.[67] In addition to the of 240 mV and a TOF of 0.075 s−1 at an overpotential of 400 mV,
Ni–Mo-based alloy, some other transition metal alloys were also almost threefold that of Ir/C (0.027 s−1).
demonstrated highly active for HER under alkaline condition, To further improve the electrocatalytic performance of LDH
such as Cu–Ti bimetallic alloy and Al7Cu4Ni@Cu4Ni core/shell materials, fabricating nanocomposite or cation doping has been
nanocrystals.[35,68] 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
4. Self-Supported Electrode for OER in Fe3+-containing aqueous solution (Figure 7a).[74] In the
obtained Ni–Fe–OH@Ni3S2, a rough Ni–Fe hydroxide film was
Compared with the HER, the OER involving complex reaction grown on the surface of Ni3S2 nanosheets (Figure 7b). Advan-
pathways is more sluggish and generally considered as the ther- tageous structural features including the high intrinsic activity
modynamically and kinetically demanding process in water of amorphous Ni–Fe hydroxide, the high conductivity of the
electrolysis. Essentially, oxygen evolution is the result of the Ni3S2 array and their strongly coupled interface endow the self-
oxidation of a hydroxyl group in alkaline solution or a water supported Ni–Fe–OH@Ni3S2/NF electrode superior yet stable
molecule under acid condition. A proposed four sequential OER activity (165 mV overpotential at 10 mA cm−2; Figure 7c).
proton-coupled electron-transfer steps of OER in alkaline solu- Furthermore, V-doped Ni–Fe LDH nanosheet array were grown
tion can be described below, which is similar to that for the on NF.[75] Electrochemical analysis and DFT + U calculation
acidic case[7] revealed that vanadium doping significantly boosted the OER
activity by modifying the electronic structure and narrowing the
M + OH− → MOH + e − (6) bandgap. Besides the Ni–Fe bimetal family, there are reports on
other transition metal hydroxide-based self-supported OER elec-
MOH + OH− → MO + H2 O + e − (7) trocatalysts, such as Ni–Co LDH nanosheets/carbon paper,[76]
Co–Al LDH nanosheets/3D graphene network[77] and Co–Zn
MO + OH− → MOOH + e − (8) nanosheets/zinc foils.[78]
Although most reported LDHs exhibit high gravimetric
MOOH + OH− → M + O2 + H2 O + e − (9) activity, they usually cannot afford large current density and long-
term stability due to low catalyst loading and limited adhesion
The four steps of OER are all thermodynamically uphill on the current collector. To address this issue, we have recently
processes, and the rate-limiting step has the highest energy developed a versatile and easily scalable electrosynthesis of metal
barrier. In the OER process, the intermediates of MOH, MO, and hydroxides/oxides on graphitic substrates.[16] As illustrated in
MOOH are generated in turn as a result of concomitant electron Figure 7d, the cathodic reduction of nitrate ion generates OH−
and proton transfer, and the bonding interactions (M–O) within to form metal hydroxide. Meanwhile, the preinsertion of nitrate
these intermediates are crucial for the catalytic activity. The ion in graphene layers prominently enhances the electrode-
adsorption energies of intermediates are widely used as descrip- posit-support interface and results in a seamless contact of the
tors for the electrocatalytic ability. In acidic solution, the oxides catalysts and substrate (Figure 7e). Using this strategy, a hybrid
of Ru/Ir are the best for OER, while the catalysts derived from containing nanocrystalline cerium dioxide and amorphous nickel
transition metal catalyze the OER more favorably in alkaline hydroxide (NiCeOxHy) was co-electrodeposited on graphite. This
media.[69] Transition-metal-based OER catalysts mainly include self-supported electrode exhibited an unexpectedly low OER
hydroxides/oxyhydroxide, oxides, phosphates, etc. 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
4.1. Transition Metal Hydroxides/Oxyhydroxides for 300 h. The superb catalytic activity and long-term stability
make the NiCeOxHy electrode highly viable for application in
Layered double hydroxides are widely studied electrochemical practical electrolyzer devices.
catalysts, in particular for the OER.[70] The composition and It is now widely recognized that during the OER process
structure of LDHs are easily tunable by adjusting either there is phase conversion from the hydroxides to oxyhydrox-
positively charged layers (e.g., Ni2+, Co2+, Cu2+, Mg2+, Zn2+, Ca2+, ides, which act as the real active sites. Much interest concerns
and Mn2+) or interlayer anions (e.g., CO32−, NO3−, SO42−, Cl−, direct synthesis of the metal oxyhydroxides OER catalysts,
and Br−), leading to unique redox features. However, the poor which however suffer from poor electrocatalytic performance.
electrical conductivity of LDHs limits the catalytic performance. Hybridizing oxyhydroxides with other functional compo-
Hybridizing LDHs with conductive carbon or exfoliating bulk nent and 3D conductive materials is an effective strategy for
LDHs to ultrathin nanosheets is widely employed to address this improvement. For example, FeOOH/CeO2 heterolayered
issue.[71,72] To simply the synthesis and improve the long-term nanotubes grown on NF (FeOOH/CeO2 HLNTs-NF)
stability, LDHs are often in situ grown on conductive substrate were employed as a self-supported OER catalyst.[79]
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 Owing to the low cost, high abundance, and considerable anti-
capability could absorb evolved oxygen, thus promoting the corrosion properties in an alkaline environment, transition
OER. The FeOOH/CeO2 hybrid manifested an onset over- metal oxides were widely developed as OER catalysts.[82] Spinel
potential of 210 mV, lower than those of FeOOH/NF and type oxide (AB2O4, A and B are 3d transition metals such as
CeO2/NF. A sandwiched FeOOH/Co/FeOOH hybrid nano- Ni, Fe, Co, Cu, Zn, and Mn) is a family of composite oxides
tube array grown on NF was also demonstrated to be an attracting extensive interest.[83–85] As an example of self-sup-
advanced self-supported electrocatalyst for OER.[80] Further- ported oxide electrode, Co3O4–carbon porous nanowire arrays
more, Fe-substituted CoOOH (i.e., Fe0.33Co0.67OOH) porous on Cu foil were prepared by carbonization of the Co-based metal
nanosheet arrays grown on CC, which were synthesized organic framework (Co-MOF) precursor in N2 (Figure 8c,d).[86]
by in situ anodic oxidation of CC supported α-Co(OH)2 in The periodic arrangement of Co nodes in the MOF scaf-
(NH4)2Fe(SO4)2, showed improved activity over CoOOH.[81] fold led to a homogeneous distribution of Co3O4 within the
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 10 mA cm−2.[91] In another notable study, cation (Fe, V, Co, and Ni)
configuration resulted in large active surface area, high struc- doped γ-MnO2 ultrathin nanosheet supported on CFP was dem-
tural stability, and enhanced charge transport, affording an onstrated to efficiently catalyze the OER.[92]
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 4.3. Transition Metal Phosphates
and moderate electrical conductivity. One-step pyrolysis of the
Co/Fe-MOF nanorod arrays grown on NF generated 3D porous In 2008, Nocera’s group reported a cobalt phosphate (Co–Pi)
CoFe2O4/C nanorod arrays, which featured abundant oxygen catalyst that exhibited unexpected OER catalytic activity in neu-
defects and endowed high OER activity.[87] In addition, other tral solution.[94] After that, earth-abundant and low-cost metal
bimetal spinel oxide-based self-supported catalysts including phosphates have stimulated particular interest. In the context
NiCo2O4 nanowall arrays/CC and sulfur-incorporated NiFe2O4 of self-supported OER electrode, amorphous FePO4 nanosheets
nanosheets/NF were also proved highly active for catalyzing the were in situ grown on NF by a solvothermal method.[95] Com-
OER.[88,89] pared with crystalline FePO4, the amorphous FePO4 nanosheets
Apart from the spinel oxides, other types of metal oxides with disordered structure possess low-energy level of d band
were also developed as self-supported OER catalysts. For center and smaller Gibbs free energy, which plays a positive
example, nanostructured MoO2 and MnO2 have been widely role in enhancing the catalytic activity. In addition to ferrous
investigated and supported on 3D substrates such as nickel phosphate, Fe(PO3)2 catalyst also showed high efficiency in
foam and carbon paper.[90–92] The intrinsically high conduc- catalyzing water oxidation.[96] Fe(PO3)2 in situ grown on the
tivity of MoO2 and porous nanosheet structures with abun- surface of a conductive Ni2P/NF scaffold generated a robust
dant active sites resulted in a low overpotential of 260 mV at electrode. During the OER electrocatalysis, the Fe(PO3)2 phase
10 mA cm−2 for MoO2 electrode.[90] Manganese dioxide mate- was converted to amorphous FeOOH, which was proposed as
rials are also active for the OER but are plagued by low con- the real catalytic sites. Benefiting from the more active FeOOH
ductivity and high overpotential, which could be well addressed and the 3D conductive Ni2P/NF substrate, the electrode yielded
by engineering of Mn/O vacancies and cation doping.[91–93] current density of 500 mA cm−2 at overpotentials of 265 mV
Calculation of the density of states (DOS) of oxygen-deficient and a TOF value around 0.12 s−1 per 3d Fe atom at an overpo-
MnO2 nanosheet revealed half-metallicity property. As a result tential of 300 mV, along with high durability in 1 m KOH. Sim-
of enhanced charge transfer, NF-supported ultrathin δ-MnO2 ilar to the case of NiFe-based hydroxide catalysts, the synergistic
nanosheet arrays with abundant oxygen vacancies afforded effect of Fe and Ni in phosphate gives rise to enhanced OER
a high OER performance with an overpotential of 320 mV at performance.[97] Not surprisingly, iron-doped nickel phosphate
in situ grown on nickel foam is promising OER catalyst in neu- at overpotentials of 223 and 260 mV for HER and OER,
tral or alkaline electrolyte. 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%
5. Self-Supported Bifunctional Electrocatalysts Faradaic yield. The respectable catalytic performance of Ni3S2
nanosheet arrays was attributed to the metallicity, binder-free
for Overall Water Splitting
architecture and high-index facets with high intrinsic activity.
For practical electrolysis of water, the HER and OER catalysts Because of different catalytic mechanism for HER and OER,
are operated in the same electrolyte, which is strongly acidic integrating the advantages of the HER and OER catalysts to
or basic solution to minimize the overpotential. Generally, construct a novel heterostructure is beneficial for enhancing
most nonprecious-metal-based HER catalysts (e.g., chalcoge- the overall electrochemical water-splitting performance. In
nides, phosphides, carbides, and nitrides) show highest cat- this regard, recent studies reported interface engineering
alytic activity in acidic media, while the OER catalysts such of MoS2/Ni3S2 and MoS2/Fe5Ni4S8 heterostructures.[103,104]
as transition metal oxy/hydroxides and oxides only perform Interestingly, the abundant interfaces in MoS2/Ni3S2 hetero-
well in alkaline electrolytes. Table 1 lists and compares the structure and the in situ formed MoS2/NiO hybrid during the
catalytic performance of some typical self-supported electro- OER enhanced the chemisorption of hydrogen and oxygen-
catalysts. The mismatching of working conditions imposes containing intermediates. Alkali electrolyzer composed of the
difficulty in searching for two electrocatalysts that couple well in self-supported MoS2/Ni3S2 electrode as both the anode and
a single electrolyzer for overall water splitting (OWS). Devel- cathode required a remarkably low voltage of 1.56 V to deliver
oping a bifunctional electrocatalyst that could simultaneously 10 mA cm−2 for overall water splitting in alkaline media.[103]
catalyze HER and OER effectively is preferable to simplify the An analogous hybrid catalyst composed of MoS2/Fe5Ni4S8 het-
electrolyzer design, avoid detrimental crossover effect of dif- erostructures on FeNi alloy substrate was also reported for effi-
ferent electrocatalysts at two electrodes, and decrease the cost cient bicatalysis of HER and OER.[104]
in device fabrication.[98,99] Therefore, extensive efforts have There is also much interest in the use of selenide-based
been devoted to developing high-performance bifunctional bifunctional electrocatalysts for overall water splitting. Recently,
catalysts for water electrolysis, mainly focusing on creating the water electrolyzer assembled with NF-supported NiSe nano-
the bifunctionality within the currently developed HER and wire film as both anode and cathode achieved a current density
OER catalysts. of 10 mA cm−2 at a cell voltage of 1.63 V.[99] Besides, Co and
The past a few years has witnessed solid progress in Fe co-doped NiSe2 nanosheets (with an optimized composition
developing transition metal sulfides, selenides, phosphides, of Fe0.09Co0.13NiSe2) supported on CC were fabricated as a self-
nitrides and carbides (collectively abbreviated as TMXs, where supported bifunctional catalyst.[105] The dual-cation incorpora-
TM = transition metal and X = S, Se, P, N, and C) as bifunc- tion in NiSe2 induced lattice distortion and strong electronic
tional HER/OER electrocatalysts. For most TMXs, the real interaction, which increased active site exposure and optimized
active sites are different between the HER and OER electroca- adsorption energy of reaction intermediates. Remarkably, the
talysis. Taking nickel phosphide as an example, Ni2P remains fabricated electrode displayed low overpotentials of 92 and
essentially unchanged on cathodic HER cycling but a NiOOH 251 mV for HER and OER respectively at 10 mA cm−2, ena-
layer was identified on the surface of Ni2P during anodic bling operation of a water electrolyzer at voltage of 1.52 V to
OER polarization (Figure 9a–c).[100] The generated NiOOH reach current of 10 mA cm−2.
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 5.2. Transition Metal Phosphides
exhibited unexpected OER catalytic properties superior to the
benchmark RuO2 (Figure 9d). In another typical example, the On account of the high activity, self-supported transition metal
HER active Co4N functions as efficient OER electrocatalyst phosphide electrodes have emerged as another family of attrac-
after formation of CoO2/Co4N species (Figure 9e–g).[101] In tive bifunctional catalysts for overall water splitting. Representa-
this section, we discuss the HER/OER bifunctional application tively, Ni5P4 with a 3D hierarchical structure on a Ni foil was
of self-supported electrodes based on TMXs and hydroxides/ prepared for HER/OER electrocatalysis.[106] After anodic cycling,
oxyhydroxides. 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
5.1. Transition Metal Chalcogenides water splitting, the electrode delivered current of 10 mA cm−2
below 1.7 V. Aside from monometallic metal phosphides, bime-
Transition metal chalcogenides are among the most widely tallic (Co1−xFex)2P with controllable composition and porosity
investigated HER/OER bifunctional electrocatalysts. Nickel was synthesized via an alloy/dealloying method.[34] The opti-
sulfides are particularly attractive because of low cost, high mized (Co0.52Fe0.48)2P with bicontinuous nanoporous structure
conductivity and considerable electrocatalytic activities. was obtained after tailoring the Co/Fe ratio (Figure 10a). The
Zou and co-workers synthesized high-index faceted Ni3S2 resultant self-supported (Co0.52Fe0.48)2P mono lithic electrode
nanosheet arrays on NF as a self-supported bifunctional elec- exhibited higher catalytic activities for both HER and OER than
trocatalyst, which delivered a current density of 10 mA cm−2 the binary Co2P, allowing the assembly of an electrolyzer that
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
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 Transition metal LDHs are known as advanced OER catalysts,
overall water splitting, Xiao and co-workers reported the prep- and they are recently demonstrated to be applicable in cata-
aration of hierarchical FeNi3N nanostructures in situ grown lyzing the HER when composing with a metallic component.
on a surface-redox-etching NF (FeNi3N/NF).[108] The obtained A presentative example is NiFe LDH nanosheets catalyst grown
FeNi3N/NF electrode was highly active to catalyze both HER on the CF-supported Cu nanowire (Cu@NiFe LDH).[109] In this
and OER in basic media, with low overpotentials of 75 and unique 3D core–shell electrode, the Cu nanowires core rooted
202 mV at current density of 10 mA cm−2, respectively. A low into CF ensures good electrical contact and mechanical stability,
cell voltage of 1.62 V was required for driving the FeNi3N/ while the few-layer NiFe LDH shell exposes abundant catalyti-
NF-based electrolyzer at working current of 10 mA cm−2. It is cally active sites. As a result, the freestanding Cu@NiFe LDH
challenging to build a bifunctional electrode for acidic water catalyst manifested remarkable HER and OER performance in
splitting since most metal oxides/oxyhydroxides in situ formed alkaline electrolyte. Water electrolyzer assembled with Cu@
on the surface of TMXs during OER process are unstable in NiFe LDH as both anode and cathode could attain current den-
strong acids. Encouragingly, Sun’s group have demonstrated a sities of 10 and 100 mA cm−2 at voltages of 1.54 and 1.69 V,
nitrogen-doped tungsten carbide (N-WC) nanoarray grown on respectively.
CFP substrate (Figure 10d), which promises overall water split- Besides LDHs, water-splitting bifunctionality of metal oxy-
ting in acid.[107] Water splitting catalyzed by the bifunctional hydroxides was recently reported by Liu et al.[110] Specifically,
N-WC nanoarray electrode offered an onset voltage of ≈1.4 V ultrathin δ-FeOOH nanosheets with rich Fe vacancies were
and a voltage of 1.7 V to attain 30 mA cm−2 (Figure 10e). Fur- synthesized by a wet-chemistry approach. Computational and
thermore, the assembled electrolyzer could be powered by a experimental results revealed that the presence of second
commercial AA battery (Figure 10f). It should be mentioned neighboring Fe to Fe vacancies could create catalytic sites for
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 performance under alkaline condition. For the OER, the most
an increased electrical conductivity of δ-FeOOH. Remarkably, a promising non-noble-metal electrocatalysts are based on LDHs,
two-electrode electrolyzer employing the δ-FeOOH nanosheets/ which often outperform the benchmark noble-metal catalysts
NF as both the anode and cathode sustained a current density (i.e., Ir and Ru compounds) in alkaline media. For OWS, the
of 10 mA cm−2 at a low driven voltage of 1.62 V, together with bimetallic phosphides and selenides are promising due to
favorable long-term durability. 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
5.5. Conclusion and Perspective self-supported electrodes.
First, the catalytic activity and stability of nonprecious cata-
Exploiting cheap, efficient and robust HER/OER catalysts is of lysts can hardly meet the requirement of practical electrolyzers,
crucial importance in water-splitting technology for hydrogen which call for competent electrocatalysts to afford a large current
energy. Compared with conventional electrode in powdery paste density above 500 mA cm−2 at overpotentials under 300 mV.[96]
form, self-supported electrodes integrating in situ grown cata- The main bottleneck is the sluggish kinetics. Improvement
lytically active phase benefit simplification of electrode prepa- should simultaneously resort to strategies such as: 1) increasing
ration, decrease of interface resistance, exposure of abundant the intrinsic activity and density of catalytically active sites by
active sites and enhancement of stability, promising practical compositional modulation, downsizing, active facet exposure, or
applications in electrolyzers. In the past decade, there has been using single site catalysis; and 2) enhancing the charge transfer
solid developments in self-supported transition-metal-based and mass transport via cation/anion doping, defect control, inter-
electrocatalytic materials that range from alloys, chalcogenides, face engineering, porosity design, and so on. The stability of the
phosphides, carbides and nitrides for HER to phosphates, most reported catalysts is far from satisfactory, which generally
hydroxides and oxides for OER, and to a few of their hybrids operate well at a low current density (<100 mA cm−2) for dozens
for overall water electrolysis. Table 1 lists a comparison of the of hours. Electrodes for practical use should sustain large cur-
electrochemical performances of some representative self- rent density well above 500 mA cm−2 for thousands of hours.[2,14]
supported transition metal electrocatalysts by benchmarking To obtain robust self-supported electrode, we should identify
overpotential at 10 mA cm−2, Tafel slop and stability. In acidic and control the stability affecting factors like catalyst composi-
electrolytes, transition metal phosphides (the bimetallic in par- tion/phase, substrate material, catalyst-substrate interface, elec-
ticular) exhibit higher HER catalytic activity and stability than trode-electrolyte wettability, mechanical property and so on. The
other compounds, while metal alloys show the remarkable intrinsic stability of most transition-metal-based electrocatalysts
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15214095, 2020, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201806326 by Technische Universitat Darmstadt, Wiley Online Library on [24/02/2023].

Self-Supported Transition-Metal-Based Electrocatalysts

selenides, phosphides, carbides, nitrides,

Hongming Sun received his

Fangyi Cheng is a Professor

or CO), and nitrogen (NH3 or N2) to form the corresponding

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

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

Catalyst Substrate Loading Electrolyte/reactions Overpotential η Tafel slope Stability

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