REVIEW

Nanoarray Architectures www.afm-journal.de

Rational Design of Nanoarray Architectures

for Electrocatalytic Water Splitting
Jungang Hou,* Yunzhen Wu, Bo Zhang, Shuyan Cao, Zhuwei Li, and Licheng Sun*

thoroughly resolving ecological deterio-

Electrochemical water splitting is recognized as a practical strategy for impel- ration status in the premise of sustained
ling the transformation of sustainable energy sources such as solar energy society development.[2,3] Carbon-free
from electricity to clean hydrogen fuel. To actualize the large-scale hydrogen hydrogen fuel as an ideal candidate has
production, it is paramount to develop low-cost, earth-abundant, efficient, attracted widespread attention around the
world, which can be directly produced
and stable electrocatalysts. Among those electrocatalysts, alternative archi-
without any incidental contamination
tectural arrays grown on conductive substrates have been proven to be highly through electrochemical water split-
efficient toward water splitting due to large surface area, abundant active ting driven by clean electricity generated
sites, and synergistic effects between the electrocatalysts and the substrates. directly or indirectly from sustainable
Herein, the advancement of nanoarray architectures in electrocatalytic appli- energy sources.[4] For example, combining
cations is reviewed. The categories of different nanoarrays and the reliable electrochemical devices with photovoltaic
cells, the intermittent solar energy can be
and versatile synthetic approaches of electrocatalysts are summarized. A fully utilized and transferred into stor-
unique emphasis is highlighted on the promising strategies to enhance the able and valuable hydrogen as a clean
electrocatalytic activities and stability of architectural arrays by component chemical fuel.[5] Although it is very prom-
manipulation, heterostructure regulation, and vacancy engineering. The ising to produce high-purity hydrogen
intrinsic mechanism analysis of electronic structure optimization, intermedi- as the energy carrier by means of elec-
trocatalysis, steam reforming reaction
ates’ adsorption facilitation, and coordination environments’ amelioration
with carbonated pollution still dominates
is also discussed with regard to theoretical simulation and in situ identifica- the hydrogen manufacturing in large-
tion. Finally, the challenges and opportunities on the valuable directions and scale industrial application considering
promising pathways of architectural arrays toward outstanding electrocata- the high cost of electrocatalytic water
lytic performance are provided in the energy conversion field, facilitating the splitting.[6] Hence, the central task has
development of promising water splitting systems. been focused on exploring economic and
robust electrocatalysts for actualizing sus-
tainable energy conversion presently and
in the future research.
1. Introduction In general, the electrocatalytic water splitting consists of
two half reactions, namely, oxygen evolution reaction (OER)
The sustainable development of human society has been sig- and hydrogen evolution reaction (HER). However, the poor
nificantly hindered by increasingly serious problems of envi- electrochemical performance was mainly due to the sluggish
ronmental issues and climate change due to the combustion kinetics and high overpotential of HER and OER, indicating
of traditional fossil fuels and the population growth.[1,2] The the major significance of exploring electrocatalysts.[7,8] To mini-
increasing concerns of global energy demand are driving mize the overpotential, the state-of-the-art electrocatalysts are
the development of clean and renewable energy systems for all based on expensive and scarce noble metals such as Pt, IrO2,
and RuO2, particularly under acidic and neutral conditions,
Prof. J. Hou, Y. Wu, B. Zhang, S. Cao, Z. Li, Prof. L. Sun to accelerate reaction kinetics for commercial electrochemical
State Key Laboratory of Fine Chemicals applications.[9,10] However, high cost and scarcity of precious
DUT-KTH Joint Education and Research Center on Molecular Devices electrocatalysts seriously prohibit the large-scale application.
Institute of Energy Science and Technology
Dalian University of Technology (DUT)
Thus, it is essential to explore low-cost, earth-abundant, effi-
Dalian 116024, China cient, and stable electrocatalysts for the realization of clean
E-mail: jhou@dlut.edu.cn; lichengs@kth.se energy conversion.
Prof. L. Sun Remarkable advances have been made to develop earth-
Department of Chemistry abundant transitional metal–based electrocatalysts. Among
KTH Royal Institute of Technology the candidates, various transition metal–based electrocatalysts
10044 Stockholm, Sweden
have been highlighted owing to rational electronic configura-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201808367.
tion, high electronic conductivity, and excellent electrochemical
activities and durability.[11–16] Despite remarkable accomplish-
DOI: 10.1002/adfm.201808367 ment achieved in electrocatalytic activity enhancement, the

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usage of polymer binder during the electrode preparation pro-

cedure not only largely increases charge transfer resistance, Jungang Hou is currently
but also brings out catalyst delamination under aggressive a full professor at the
bubble formation circumstance, thus leading to the limitation Dalian University of
of electrocatalysis performance promotion and deterioration of Technology. He received his
stability.[15,16] Instead of employing the binder, electrocatalysts Ph.D. degree (2010) from
can be directly grown on conductive substrates, such as copper Tianjin University. He joined
foam, nickel foam, carbon cloth or paper (CC or CP), and fluo- the faculty of University of
rine-doped tin oxide (FTO). Nevertheless, it is a big challenge to Science and Technology
produce the active electrocatalysts on conductive substrates. By Beijing and was promoted
virtue of in situ growth strategies, rational design of nanoarray to associate professor in
architectures is able to boost HER and OER performance 2013. He worked in Tohoku
based on several features: i) in situ growth strategy guaran- University as a fellow of the
tees the intimate interfacial contact, thus facilitating the rapid Japan Society for the Promotion of Science from 2014 to
charge transfer from materials to the collectors and preventing 2015. His recent research interests focus on the develop-
the catalyst delamination[10,13]; ii) architectural arrays are ben- ment of photocatalysts and electrocatalysts, photocatalytic
eficial for electrolyte’s access to active sites and expansion of and electrocatalytic water splitting, CO2/N2 conversion
specific area compared to planar structure, thereby dramatically to valuable chemicals, and synthesis and applications of
increasing the effective active sites[8,16]; iii) crystal structure and nanostructured materials.
morphology of architectural arrays could be regulated through
the optimization of reliable and versatile synthetic strategies, Yunzhen Wu received his
promoting exposure of active sites and charge transfer[15–18]; iv) B.S. degree from Guangxi
in the case of hierarchical support, it can not only greatly accel- University in 2011, majoring
erate mass diffusion, but also expedite release of accumulated in light chemical engineering.
gas bubbles especially for high current density state[19–21]; and v) He is currently pursuing
the selection of appropriate substrate for catalyst cultiva- his Ph.D. degree under the
tion may play a synergistic role between the substrates and supervision of Prof. Jungang
nanoarray architectures, thus enhancing the electrocatalytic Hou at the Dalian University
activities.[17–22] of Technology. His research
Based on the above-mentioned advantages, it is of great signif- interests are focused on elec-
icance to build architectural array electrodes for realizing highly trocatalytic water splitting and
efficient and durable water splitting reaction. Although impres- electroreduction of CO2/N2 to
sive progress has been made in electrocatalytic water splitting valuable chemicals.
by integrating vertically aligned nanoarrays with applicable sup-
ports,[11–22] there are few reviews systemically summarizing the Licheng Sun received his
recent progress of nanoarray architectures for electrocatalytic Ph.D. degree in 1990 from
water splitting in detail. More importantly, the in-depth deci- the Dalian University of
pherment of activity modulation was rarely reported. Especially, Technology. He went to
the scientists all over the world have devoted efforts to design Germany as a postdoc at
and fabricate different nanoarrays; however, it is complicated the Max-Planck-Institut
to control the sizes, components, and micro/nanostructures für Strahlenchemie
of architectural arrays by tunable synthetic approaches, which with Dr. Helmut Görner
is different from the production of nanocrystals without any (1992–1993), and then as
support. It is worth constructing the concept and the strategy an Alexander von Humboldt
as well as the comprehensive comparison of the advances and fellow at Freie Universität
limitations of the tunable synthetic routes for the generation of Berlin (1993–1995) with
architectural arrays. To boost the electrocatalytic performance Prof. Harry Kurreck. He moved to the KTH Royal Institute
of nanoarrays, substantial chemical and engineering strategies of Technology, Stockholm, in 1995 and became an
have been adopted. From a scalable and sustainable perspective, assistant professor in 1997, an associate professor in
it is evident to summarize the development of nanoarray archi- 1999 (at Stockholm University), and a full professor in
tectures, building the relationship of the synthetic approaches 2004 (KTH). His research interests cover artificial photo­
and the electrocatalytic activities. synthesis, molecular catalysts for water oxidation and
Herein, the categories of architectural arrays have been sum- hydrogen generation, functional devices for total water
marized (Figure  1), presenting a large number of low-cost, splitting, and solar cells.
earth-abundant, high-performance, and stable electrocatalysts.
With regard to the design and synthesis of architectural arrays,
the concepts and versatile synthetic strategies of how to fabri- transition metal architectural arrays toward outstanding per-
cate architectural arrays have been evaluated in this review, formance. A unique emphasis is highlighted on the promising
paving promising insights into the development of nonprecious strategies to enhance the electrocatalytic activities and stability

Adv. Funct. Mater. 2019, 29, 1808367 1808367  (2 of 39) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 1. Schematic illustration of nanoarray architectures for robust
energy conversion applications.
of architectural arrays by component manipulation, hetero-
structure regulation, and defect engineering. The intrinsic
mechanism analysis of electronic structure optimization,
intermediates’ adsorption facilitation, and coordination envi-
ronments’ amelioration has also been discussed by theoretical
simulation and in situ identification. Notably, by virtue of theory
calculations and sophisticated characterizations, the fine struc-
ture of architectural arrays was anatomized and activity optimi-
zation was systematically expounded based on the manipulation
of active sites and electron transfer, providing deep insights into
the intrinsic reaction mechanisms. Finally, we offer the chal-
lenges and opportunities on the valuable directions and prom-
ising pathways of nonprecious transition metal architectural
arrays toward outstanding performance. This review may not
only give the guidelines to comprehensively grasp the quintes-
sence of design and regulation strategies for architectural arrays,
but also enlighten us to delicately create desirable electrocata-
lysts for actualizing energy conversion systems in the future.
2. Principles of Electrocatalytic Water Splitting
2.1. Hydrogen Evolution Reaction
Hydrogen evolution reaction with two-electron transfer is gen-
erally recognized as one intermediates’ adsorption–desorp-
tion process.[22] In acidic media, one proton adsorbs on the
surface of electrocatalyst followed by one electron deduction,
thus forming the adsorbed intermediate H* (* represents the
adsorbed active site). This step is known as the Volmer step
(Equation (1)).[23] Sequentially, the adsorbed H* combines with
another H+ and removes one electron, leading to the generation
of one hydrogen molecule; this step is known as the Heyrovsky
step (Equation (2)).[23] Alternatively, the adsorbed H* tends to
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unite with another H* to form hydrogen molecule under high
coverage of surrounding H*; this step is known as the Tafel
step (Equation (3))[2]
H+ + e − → H* (1)
H* + H+ + e − → H2 (2)
2H* → H2 (3)
Regardless of Volmer–Heyrovsky or Volmer–Tafel mecha-
nism, the hydrogen adsorption free energy (ΔGH*) is extensively
acknowledged as the criterion of hydrogen evolution activity.[24]
Differing from two-step path in acidic media, adsorbed H2O
molecule on surface starts to dissociate at the initiation
of HER, due to the absence of proton in alkaline medium
(Equation (4)).[25] Accordingly, hydrogen molecule can be pro-
duced via combination of H* with water molecule (Equation (5))
or coupling of intermediates (Tafel step)[26]
H2O + e − → H* + OH− (4)
H* + H2 O + e − → H2 + OH− (5)
Consequently, it is essential to strike a balance between
favored water dissociation and moderate hydrogen adsorp-
tion energy, implying sluggish kinetics of HER in alkaline
condition.[27]
2.2. Oxygen Evolution Reaction
Oxygen evolution reaction undergoes four-step electron transfer
procedure with multiple intermediates as illustrated in Equa-
tions (6)–(13).[28,29]
In acidic media
2H2 O → *OH + H2 O + H+ + e − (6)
*OH + H2 O → *O + H2 O + H+ + e − (7)
*O + H2 O → *OOH + H+ + e − (8)
*OOH → O2 + H+ + e − (9)
In basic media:
4OH− → *OH + 3OH− + e − (10)
*OH + 3OH− → *O + 2OH− + H2 O + e − (11)
*O + 2OH− + H2 O → *OOH + OH− + H2 O + e − (12)
*OOH + OH− + H2 O → O2 + 2H2 O + e − (13)
The total free energy variation of OER is determined to be
4.92 eV,[30,31] which can be distributed equally among the four
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elemental steps with different adsorbates (*OH, *O, *OOH, O2)
for thermodynamically ideal electrocatalyst. If it is so, equilib-
rium potential should be sufficient for driving oxygen evolution
reaction. However, constant adsorption free energy difference
between *OH and *OOH is estimated to be 3.2 eV, which is
applicable for all oxides considered.[32] The desirable placement of
*O between *OH and *OOH is able to lower the free energy vari-
ation as much as possible. Correspondingly, the minimum value
of overpotential is evaluated as 0.4–0.2 V, implying the much
more unfavorable dynamics of OER in comparison with HER.[32]
2.3. Overall Water Splitting
Overall water splitting refers to the simultaneous occurrence of
hydrogen evolution and oxygen evolution. Generally speaking,
the electrochemical measurements are performed in a three-
electrode system, which are utilized to evaluate half reaction
activities (namely, HER and OER) of water splitting reaction,
consisting of working electrode (cathode for HER or anode for
OER), reference electrode, and auxiliary electrode (counter elec-
trode). However, only cathode and anode are assembled to form
one integrated circuit in practical application, that is, a two-elec-
trode system, where HER and OER can be catalyzed by cathode
and anode, respectively. To actualize overall water splitting, suf-
ficient applied voltage is required to conquer the overpotential
summation of cathode and anode. Hence, careful selection of
prominent HER and OER electrocatalysts plays a dominant role
in lowering the electricity consumption of overall water split-
ting. In particular, there are some unique electrocatalysts being
competent to efficiently catalyze not only HER but also OER,
which are defined as bifunctional electrocatalysts. This type of
catalysts can function as both cathode and anode for integrating
an entire overall water splitting system. Consequently, the prep-
aration procedure may be considerably simplified; meanwhile,
manufacturing cost is largely reduced. Therefore, it is exceed-
ingly promising to develop decent bifunctional electrocatalysts
for realizing large-scale hydrogen fuel production in future.
3. Fundamental Parameters for Evaluating
Electrochemical Water Splitting
3.1. Overpotential
In theory, water splitting reaction can proceed with a voltage
(equilibrium potential) of 1.23 V. However, extra electricity
energy is imperative to conquer intrinsic activation barriers
of electrocatalysis, namely, overpotential (η). Therefore, it
is self-evident that the decreasing overpotential should be
regarded as the priority task of electrocatalyst design, bringing
about the efficiency promotion of energy conversion systems.
Overpotential can be recorded by linear scan voltammetry (LSV)
curves measured with iR-correction, which is utilized for com-
pensating resistance of electrolyzer. Normally, overpotential at
current density of 10 mA cm−2 is deemed as the benchmark
of assessing electrocatalysts, corresponding to 10% solar-to-fuel
efficiency of integrated photoelectrochemical water splitting
devices.[33]
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3.2. Tafel Slope and Exchange Current Density
The relationship of overpotential (η) and current density (j)
is determined via Tafel slope, which is elicited through loga-
rithmic transformation of LSV curves. Acquired Tafel plot
can be linearly fitted according to the following equation:
η  = a  + b log j, where b refers to Tafel slope. A smaller Tafel
slope value signifies more rapid ascent of current density as
the applied potential increases; as a result, the applied voltage
can be greatly reduced at high current. Interestingly, Tafel slope
is usually employed as a valid tool to analyze reaction mecha-
nism.[23,24] Exchange current density (j0) can also be obtained
on condition that value of overpotential is set as zero, reflecting
the inherent activity of electrocatalysts at equilibrium potential.
Apparently, small Tafel slope and large exchange current den-
sity should both be taken into account when scheming robust
electrocatalysts.[7]
3.3. Turnover Frequency
Turnover frequency (TOF) is defined as the number of product
molecules converted from reagent per active site per unit time,
demonstrating the genuine activity of electrocatalysts. It can
be calculated based on the following equation: TOF = jA/zFn,
where j is current density, A is working area of electrode, z is
electron transfer number per molecule generated, F is Far-
aday constant, and n is amount of material (mol). It is worth
mentioning that not all active atoms are involved in catalysis
reaction and the value of n cannot be precisely calculated
accordingly, implying the inaccuracy of TOF value. Neverthe-
less, it can still play a constructive role in electrocatalytic activity
comparison between different materials.
3.4. Stability
For the practical application, stability is considered as an
important parameter for evaluating electrocatalysts. Gener-
ally, it is measured by recording current change vs reaction
time at fixed potential or carrying out chronopotentiometry
experiment with potential variation. Moreover, durability can
be comprehensively assessed with the help of multicurrent
step chronopotentiometry technique measured ranging from
10 mA cm−2 to hundreds and even thousands of milliam-
peres per square centimeter. The other impactful method for
stability test is comparing the LSV curves before and after elec-
trochemical reaction and any evident decay of stability will be
easily detected.
3.5. Faradaic Efficiency
Faradaic efficiency depicts the efficiency of electrons used for
catalyzing desired water reduction/oxidation reaction instead
of unwanted reaction such as electrode redox reaction. Spe-
cifically, it is quantified as the molar ratio of actual amount of
hydrogen/oxygen generated to the quantity of hydrogen/oxygen
produced in theory.
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4. Electrocatalyst Categories
Generally, precious metal–based materials have been regarded
the benchmark electrocatalysts. Nevertheless, large-scale
application has been hindered by the high cost and scarcity
of noble materials in renewable energy field. Notably, high-
performance electrocatalysts have emerged as a promising
candidate for electrocatalytic water splitting. Generally, various
transition metal oxides, hydroxides, oxyhydroxides, phosphides,
chalcogenides, phosphates, borides, nitrides, carbides, metal−
organic frameworks (MOFs), and molecular nanoarrays grown
on conductive substrates as typical HER and OER electro-
catalysts (Tables  1 and 2) have been developed for functional
applications in energy conversion.
4.1. Transition Metal Arrays
Generally, noble metals and noble metal oxides are most
efficient electrocatalysts for electrochemical water splitting.
Compared to noble metal–based catalysts, transition metal
arrays have been extensively investigated in energy conver-
sion applications. It is worth noting that Ni-based materials
are efficient and stable electrocatalysts in industrial hydrogen
production field.[34] 3D hierarchically porous Ni microspheres
on nickel foam have been designed as a nonprecious metal
bifunctional electrocatalyst for hydrogen production and oxida-
tive upgrading of various alcohols under ambient conditions.[34]
Compared to pure nickel, an enhancement in the intrinsic elec-
trocatalytic activity in the HER has been achieved by use of Ni-
based alloys integrated with, e.g., W, Mo, and Fe.[35–40] Among
various alloys, porous nickel–molybdenum (NiMo) arrays
grown on 3D Ni foam have been fabricated through thermal
reduction process by use of NiMoO4 precursors.[37,38] After
turning to Cu foam and nanowires as the substrates, NiMo/
Cu arrays with the optimal Ni/Mo ratio modulated by the depo-
sition current density exhibited the composition-dependent
enhanced activity and excellent electrochemical stability for
HER in alkaline electrolyte.[39,40] However, it is hard to sustain
in acidic solutions for the catalytic activity of nickel-based alloys
owing to Ni dissolution.[41] To address this point, metal nickel
foam was chosen for robust HER, requiring a low overpoten-
tial at current density of 10 mA cm−2 and a small Tafel slope
(100.6 mV per decade) in acidic media.[41] Although various
NiMo alloys have been proved as excellent HER electrocatalysts
in alkaline electrolyte, Ni–Mo–Fe alloys in comparison with dif-
ferent Ni–Mo–M (M = Fe, Cu, Zn, W, Co, or Cr) alloys showed
the highest HER performance.[42] Generally, the higher electro-
catalytic activity of transition metal arrays is simply due to the
fact that architectural arrays possess much more active sites
than noble metals. However, it is hard to evaluate the intrinsic
activity of nanoarray electrocatalysts since the active sites could
not be precisely determined. It is essential to rely on the analysis
of theoretical calculations and in situ/operando characteriza-
tions, exploring the real catalytic process and mechanism of
transition metal electrocatalysts. To enhance the electrocata-
lytic activity of electrocatalysts, it is important to increase the
number of active sites through the regulation of nanostructures
(e.g., 1D nanowires, 2D nanosheets, and 3D architectures) or
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catalyst loading and enhance the intrinsic activity of each active
site by doping strategy.[2] Based on the above analysis, the simul-
taneous optimization of the active sites and the intrinsic activity
makes significant contribution for guiding the development of
promising electrocatalysts in acidic and alkaline electrolytes.
4.2. Transition Metal Oxide Arrays
To fulfill industrial demands of water electrolysis, it is critical
to develop high-performance electrocatalysts. Among various
electrocatalysts, transition metal (i.e., Ni, Co, Fe, Mn, W, and
Mo) oxides have emerged as promising candidates for elec-
trocatalytic water oxidation reaction in alkaline medium.[43,44]
For example, Co3O4 nanosheet arrays on Ni foam owing to the
unique nanosheet structure and the interconnected configu-
ration reached current density of 10 mA cm−2 at a low over-
potential (190 mV) for OER in KOH solution.[45] Encouraged
by the advance of efficient mass transfer and abundant active
sites from micro/nanostructures, hollow Co3O4 microtube
array has been fabricated by electrochemical self-templating
approach for catalyzing OER, HER, and overall water elec-
trolysis with high activity due to high surface area, hierar-
chical porosity, and hollow structure (Figure  2a).[46] NiO/Ni
arrays owing to the 3D well-connected Ni foam skeleton and
the intact contact of the NiO/Ni domains have been produced
through in situ thermal oxidation of Ni foam in air instead
of using a large amount of liquid solvent, requiring current
density of 10 mA cm−2 at a low overpotential (345 mV) and a
low Tafel slope (53 mV per decade) in 1 m KOH electrolyte.[47]
Beyond transition metal (Co, Ni)-based electrocatalysts, self-
supported Cu-based nanowire arrays including Cu(OH)2, CuO,
Cu2O, and CuOx in situ grown on Cu foil have been produced
as active and robust OER electrocatalysts.[48] Porous WO2 hexa-
hedral networks supported on nickel foam required the over-
potentials of 300 and 48 mV at current density of 10 mA cm−2
for the OER and HER, respectively, and even a low cell voltage
of 1.59 V at 10 mA cm−2 for overall water splitting in alkaline
media.[49] As metallic transition metal oxide, Cui and coworkers
reported porous MoO2 nanosheets supported on commercial Ni
foam owing to high surface area and abundant active sites from
porous nanostructures, achieving zero onset potential and over-
potential of 27 mV at current density of 10 mA cm−2 as well as a
small Tafel slope (41 mV per decade) for HER, while low onset
potential (1.43 V) and potential of 1.49 V at current density of
10 mA cm−2 as well as a small Tafel slope (54 mV per decade)
for OER. Based on the inspiration of robust HER and OER, a
two-electrode system using MoO2 array as a bifunctional elec-
trocatalyst required a low cell voltage (1.53 V) at current density
of 10 mA cm−2, still effectively splitting water into hydrogen
and oxygen by a conventional AA battery (1.5 V) in basic media
(Figure 2b).[50] Compared to single-metal oxides, binary metal
oxides offered a greatly increased OER activity. For example,
NiFeOx as benchmarking heterogeneous OER electrocata-
lyst presented nearly ten times higher specific activity than
the electrocatalysts of CoOx, CoPi, CoFeOx, NiOx, NiCeOx,
NiCoOx, NiCuOx, and NiLaOx in alkaline solution.[51] To
address the problem of low conductivity of NiFe-based oxides/
hydroxides, Ni2Fe1–O networks grown on conductive Ni foam
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Table 1.  Brief summaries of nanoarray architectures for HER.

Catalyst Electrolyte Electrode Overpotential at Tafel slope [mV per decade] Catalyst loading [mg cm−2] Ref.
10 mA cm−2 [mV]
Hollow Co3O4 tube 1 m KOH NF 190 (η20) 98 [46]
MoO2 nanosheets 1 m KOH NF 27 41 2.9 [50]
Porous NiCoFe LTH 1 m KOH CFC 200 70 0.4 [59]
Cu@NiFe LDH 1 m KOH Cu foam 116 58.9 2.2 [61]
3D porous Co2P 0.5 m H2SO4 Freestanding 80 44 [67]
3D porous Co2P 1 m KOH Freestanding 60 40 [67]
CoP nanowires 0.5 m H2SO4 CC 67 51 0.92 [68]
CoP nanowires 1 m PBS CC 65 (η2) 93 0.92 [68]
CoP nanowires 1 m KOH CC 209 129 0.92 [68]
Cu3P nanowires 0.5 m H2SO4 Co foam 143 67 15.2 [69]
Porous CoFe–P 0.5 m H2SO4 Freestanding 64 45 0.419 [70]
Porous CoFe–P 1 m KOH Freestanding 79 40 0.419 [70]
NiSe 1 m KOH NF 96 120 2.8 [84]
Co3Se4 1 m KOH Co foam 262 (η100) 72 2.6 [86]
V–Co4N 1 m KOH NF 37 44 [96]
N–WC 0.5 m H2SO4 CF 89 75 10.0 [105]
Ni–P 1 m KOH CFC 117 85.4 0.3 [140]
ZnSe/MoSe2 0.5 m H2SO4 FTO 68 73 0.15 [65]
CoNi(OH)x tubes 1 m KOH Cu foil 150 130 [154]
CP/CTs/Co–S 1 m KOH CP 250 131 0.32 [156]
NiCoS/GDY/Ni,Co–MoS2 0.5 m H2SO4 CFC 124 64.3 [158]
Ni@CoO@CoNC 1 m KOH NF 190 98 4.0 [160]
CoP nanowires 1 m KOH GC 146 (η100) 42.8 10.0 [173]
NiCo2Px nanowires 1 m KOH Carbon felt 58 34.3 5.9 [180]
F0.25C1CH 1 m KOH NF 77 99 4.17 [187]
(Ni0.33Fe0.67)2P 1 m KOH NF 84 73.2 2 [189]
FeCo–NiSe2 1 m KOH CFC 92 89 [195]
N–MoSe2/VG flake 0.5 m H2SO4 CC 98 49 [200]
FeCoNi-HNTAs 1 m KOH NF 58 37.5 1.0 [201]
Se-enriched NiSe2 0.5 m H2SO4 CF 117 32 [91]
Ni5P4–Ni2P-NS 0.5 m H2SO4 NF 120 79.1 0.283 [205]
CoP-MNA 1 m KOH NF 54 51 6.2 [206]
Porous H–CoSe|P 1 m KOH GF 150 83 2.1 [209]
Pyrite-type CoPS 0.5 m H2SO4 CFP 48 56 [210]
Pt–CoS2 nanosheet 1 m KOH CC 24 82 0.5 [221]
Cu nanodots/Ni3S2 nanotubes 1 m KOH CF 128 76.2 0.52 [222]
MoNi4/MoO2 1 m KOH NF 15 30 43.4 [223]
NC/CuCo/CuCoOx 1 m KOH NF 112 55 1.5 [226]
NC–NiCu–NiCuN 1 m KOH NF 93 55 1.5 [228]
FLNPC@MoP- NC/MoP–C 1 m KOH CC 69 52 2.42 [124]
FLNPC@MoP- NC/MoP–C 1 m PBS CC 106 73 2.42 [124]
FLNPC@MoP-NC/MoP–C 0.5 m H2SO4 CC 74 50 2.42 [124]
O–CoMoS 1 m KOH CF 97 70 1.0 [234]
MoS2/Mo2C 0.5 m H2SO4 CF 63 53 1.67 [235]
MoS2/Ni3S2 1 m KOH NF 110 83.1 9.7 [237]
CuCoO nanowires 1 m KOH NF 85 108 1.2 [240]

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Table 1. Continued.

Catalyst Electrolyte Electrode Overpotential at Tafel slope [mV per decade] Catalyst loading [mg cm−2] Ref.
10 mA cm−2 [mV]
NiCo2O4/CuS 0.5 m H2SO4 CF 72.3 41 [243]
Co(OH)2@PANI 1 m KOH NF 88 91.6 0.74 [244]
PANI/CoP 0.5 m H2SO4 CF 57 34.5 0.80 [245]

Abbreviations: CC, carbon cloth; CF, carbon fiber; CFC, carbon fiber cloth; CP, carbon paper; FTO, fluorine-doped tin oxide; GC, glassy carbon; GF, graphene foil; LTH, lay-
ered triple hydroxide; NF, nickel foam; PBS, phosphate buffer solution; MNA, mesoporous nanorod arrays; FLNPC, few layered N,P dual-doped carbon.

Table 2.  Brief summaries of nanoarray architectures for OER.

Catalyst Electrolyte Electrode Overpotential at 10 mA cm−2 [mV] Tafel slope [mV per decade] Catalyst loading [mg cm−2] Ref.
Hollow Co3O4 tube 1 m KOH NF 360 (η150) 84 [46]
MoO2 nanosheets 1 m KOH NF 260 54 2.9 [50]
3D NiFe LDH 1 m KOH NF 270 (η80) 28 0.032 [56]
NiCo hydroxide tube 0.1 m KOH ITO 460 65 [57]
Porous NiCoFe LTH 1 m KOH CFC 239 32 0.4 [59]
FeOOH/CeO2 tube 1 m NaOH NF 250 (η31.3) 92.3 0.44 [60]
Cu@NiFe LDH 1 m KOH Cu foam 199 27.8 2.2 [61]
FeOOH/Co/FeOOH 1 m NaOH NF 250 (η21) 32 [65]
Porous CoFe–P 1 m KOH Freestanding 270 30 0.419 [70]
FeNiP-NP 1 m KOH NF 180 76 4.12 [72]
Am-FePO4 1 m KOH NF 218 42.72 0.285 [76]
NiSe 1 m KOH NF 270 64 2.8 [84]
Co3Se4 1 m KOH Co foam 320 (η397) 44 2.6 [86]
Co4N 1 m KOH CC 257 44 0.82 [93]
CoN 1 m KOH NF 290 70 1.5 [94]
FeS 1 m KOH FF 238 82.7 1.38 [129]
Co–Se/NiFe LDH 1 m KOH GF 270 (η150) 57 4.0 [130]
Ni-P 1 m KOH CFC 180 (η20) 73 0.3 [140]
FeCoOOH 1 m KOH CFC 266 30 1.394 [141]
CoNi(OH)x tubes 1 m KOH Cu foil 280 77 0.72 [154]
CP/CTs/Co–S 1 m KOH CP 300 72 0.32 [156]
3D-OMNiSA 0.1 m KOH GC 254 39 0.2 [157]
Hollow NiCo2O4 2 m KOH CC 340 72 0.6 [161]
Co3O4@CoP 1 m KOH Ni foil 238 51.4 0.7–1 [162]
P–CoSe2/N–C flake arrays 1 m KOH CC 230 36 2 [163]
CoFe2O4/C nanorod 1 m KOH NF 240 45 1.03 [164]
Co–Nx/C nanorod 0.1 m KOH GC 300 62.3 5.0 [165]
Cu2S nanosheet 1.0 m KOH Cu foam 490 (η20) 101 4.0 [172]
Co1Mn1CH 1 m KOH NF 294 (η20) 5.6 [186]
F0.25C1CH 1 m KOH NF 228 42 4.0 [187]
(Ni0.33Fe0.67)2P 1 m KOH NF 230 (η50) 55.9 2 [189]
NPCoO-UCSs 0.1 m KOH Ti foil 172 34 0.45 [191]
Porous FeCo–NiSe2 1 m KOH CFC 251 63 [195]
NiFeV LDHs 1 m KOH NF 192 42 2.8 [197]
FeCoNi-HNTAs 1 m KOH NF 184 49.9 1.0 [201]
NixFe1−xSe2-DO 1 m KOH NF 195 28 4.1 [202]
CoP-MNA 1 m KOH NF 290 65 [206]
(FexNi1−x)2P 1 m KOH NF 156 66 3.34 [207]

Abbreviations: CC, carbon cloth; CF, carbon fiber; CFC, carbon fiber cloth; CP, carbon paper; FF, Fe foam; GC, glassy carbon; GF, graphene foil; ITO; indium tin oxide; LTH,
layered triple hydroxide; NF, nickel foam; OMNiSA, ordered mesoporous Ni sphere arrays; UCS, unit-cell-thick sheet.

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Figure 2.  Scanning electron microscopy (SEM) images of transition metal–based arrays. a) Hollow Co3O4 microtube array. Reproduced with permis-
sion.[47] Copyright 2017, The Royal Society of Chemistry. b) Porous MoO2 nanosheet array. Reproduced with permission.[50] Copyright 2016, John Wiley
and Sons. c) NiCo LDH nanosheet array. Reproduced with permission.[58] Copyright 2015, Elsevier Science Ltd. d) FeOOH/Co/FeOOH nanotube array.
Reproduced with permission.[65] Copyright 2016, Wiley-VCH. e) 3D porous cobalt phosphide alloy. Reproduced with permission.[70] Copyright 2016,
John Wiley and Sons. f) FePO4 nanosheet array. Reproduced with permission.[76] Copyright 2017, Wiley-VCH.

as OER catalysts due to synergistic effects of 1D mesoporous
feature of Ni2Fe1–O nanowires and the integrated 3D porous
nanostructure array of Ni2Fe1–O nanowires on 3D foam pre-
sented a low overpotential (244 mV) at current density of
10 mA cm−2 and a small Tafel slope (39 mV per decade) as well
as outstanding durability over 60 h in alkaline electrolyte.[52]
Interestingly, robust HER activity has also been observed in
these special Ni2Fe1–O nanowires on 3D foam. Considering
the OER and HER properties of Ni2Fe1–O catalysts, a two-
electrode system using mesoporous Ni2Fe1–O nanowires on
3D foam achieved current density of 10 mA cm−2 at a low cell
voltage (1.64 V).[52] It is well known that Li-inserted transition
metal oxides as Li-ion battery cathode materials have gained
noticeable popularity as OER catalysts due to the commonality
of the electrochemical reactions through the redox reaction of
the transition metal.[53] Furthermore, perovskite-type oxides as
efficient bifunctional oxygen catalysts have also presented out-
standing OER electrocatalytic performance and stability in an
alkaline solution.[54] However, there are few reports about archi-
tectural arrays using Li-inserted transition metal oxides and
perovskite-type oxides for OER and HER applications. Based
on these reports, the efficient and high-quality energy storage
and conversion systems have been explored by use of transi-
tion metal oxides because several oxidation states are favorable
for rapid redox reactions in transition metal oxides. Unfortu-
nately, metal oxides generally suffer from low electrical con-
ductivity, which significantly limits the electron transport and
consequently degrades the electrochemical performance. Thus,
it is an advisable strategy to produce active transition metal
oxide arrays on conductive substrates with high electrochem-
ical performance and robust stability.
4.3. Transition Metal Hydroxide/Oxyhydroxide Arrays
Owing to surprising electrochemical performance as electroac-
tive materials, transition metal hydroxide/oxyhydroxide arrays
as possible water oxidation catalysts have gained widespread
attention. Among layered metal hydroxides, a large number
of layered double hydroxides (LDHs) as promising 2D layered
OER electrocatalysts, such as binary MgAl, NiAl, ZnAl, CoAl,
MgGa, NiGa, ZnGa, ZnCo, CoCo, CoFe, NiCo, NiFe, and
LiFe, and ternary FeNiCo and NiFeMn systems, have attracted
extensive attention toward water oxidization activities.[55–65]
What should be mentioned above all is that transition metal
hydroxide/oxyhydroxide arrays grown on conductive substrates
act as the excellent electrocatalysts. For industrial application
with high current density (≥500 mA cm−2) at a low overpo-
tential (≤300 mV) of OER catalysts, high current densities of
500 and 1000 mA cm−2 have been obtained at the low over-
potentials of 240 and 270 mV, respectively, by use of 3D hier-
archical array as inexpensive and excellent electrocatalyst with
the integration of amorphous nickel–iron nanosheets and
3D Ni foam.[56] Benefitting from nanostructured Ni and Co
oxides, 3D Ni@[Ni(2+/3+)Co2(OH)6–7]x nanotube arrays due to
sandwich-like nanostructure, high electronic conductivity, and
synergistic effects from electron interactions between conduc-
tive CoOOH and NiOOH species achieved current density of
10 mA cm−2 at a small overpotential of 460 mV in alkaline
media.[57] Beyond binary LDH arrays, triple NiCoFe hydrox-
ides on carbon fiber cloth (CFC) presented a low onset poten-
tial (1.45 V), a small potential (1.46 V) at current density of
10 mA cm−2, and a small Tafel slope (32 mV per decade) for
OER, while a small onset potential (0.18 V), a low overpotential

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(0.2 V) at current density of 10 mA cm−2, and a small Tafel
slope (70 mV per decade) for HER. Inspired by robust OER
and HER performance, a two-electrode system using NiCoFe/
CFC array as a bifunctional electrocatalyst delivered current
density of 10 mA cm−2 at a small voltage of 1.51 V and excellent
durability toward overall water splitting.[59] Enlightened by the
advantages of 2D layered materials and 3D porous substrates,
NiFe LDH/Cu nanowire on Cu foams owing to 3D core–shell
nanoarchitectures displayed high current densities of 500
and 1000 mA cm−2 at the overpotentials of 311 and 315 mV,
respectively, and a small Tafel slope (27.8 mV per decade) for
OER, while high current densities of 10 and 100 mA cm−2
at the overpotentials of 116 and 192 mV, respectively, and a
small Tafel slope (58.9 mV per decade) for HER. Considering
excellent OER and HER activities, a two-electrode system
using Cu@NiFe LDH architectural array as a bifunctional elec-
trocatalyst required low cell voltages of 1.53 and 1.69 V at cur-
rent densities of 10 and 100 mA cm−2, respectively, toward full
water splitting.[61] However, Jin highlighted that most OER cata-
lysts can be easily oxidized to the corresponding metal oxides/
hydroxides, especially the formation of OER-active oxyhydroxide
under relevant potentials in the aqueous and strongly oxidative
environments of OER.[62] For instance, CoOOH, NiOOH, and
FeOOH catalysts have been extensively explored in energy con-
version field. CoOOH and Ni- or Mn-modified CoOOH nano-
wire arrays have been grown on stainless steel mesh, presenting
the best OER activity of CoOOH nanowire arrays with 9.7% Ni
incorporation and no effect on OER property with Mn modifica-
tion.[63] Although Ni and Fe species played a pivot role in the
enhancement of OER performance,[56–62] it is a challenge to
understand the role of Fe in the OER optimization of NiOOH.
To elucidate the relationship between structure and activity in
Ni1−xFexOOH OER catalysts, Boettcher and coworkers reported
Ni1−xFexOOH OER catalyst as a typical model to capture in-
depth relationship of structure and electrocatalytic activity.[64] The
enhancement of Ni(OH)2/NiOOH is ascribed to the increased
conductivity by the introduction of Fe based on Fe-induced par-
tial charge transfer mechanism. Notably, superior activity of
Ni1−xFexOOH OER electrocatalysts originated from the increased
conductivity and the real active sites owing to the Fe incorpora-
tion.[64] With regard to the poor electrical conductivity of FeOOH,
as-synthesized FeOOH/Co/FeOOH nanotube arrays grown
on Ni foam through the integration of FeOOH and conduc-
tive material as a promising electrocatalyst showed outstanding
OER activity owing to strong electron interactions between Co
and FeOOH (Figure 2d).[65] Thus, it is of great significance to
produce active transition metal hydroxide/oxyhydroxide arrays
toward electrocatalytic application.
4.4. Transition Metal Phosphide Arrays
Transition metal phosphides have been regarded as robust
HER catalysts based on density functional theory (DFT)
calculations from Rodriguez’s group in 2005.[66] Until now,
various metal phosphides have been adopted for electro-
chemical hydrogen evolution. For example, 3D nanoporous
metal phosphide alloy has been synthesized by single-roller
melt spinning toward efficient electrochemical hydrogen
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production.[67] As interesting catalysts of Co-based mate-
rials,[6] cobalt phosphide arrays as robust HER catalysts from
the facile phosphidation treatment of Co(OH)F precursor
owing to 3D configuration of CoP nanowires on carbon cloth
presented a small onset overpotential (38 mV), current densi-
ties of 10, 20, and 100 mA cm−2 at low overpotentials of 67,
100, and 204 mV, respectively, and a low Tafel slope (51 mV
per decade).[68] Beyond Ni2P, FeP, and CoP catalysts,[6] Cu3P
arrays on Cu foam as typical HER electrocatalysts exhibited a
small overpotential (143 mV) at current density of 10 mA cm−2,
a low onset overpotential (62 mV), and a small Tafel slope
(67 mV per decade) in acidic water.[69] Beyond single-metal
phosphides, bimetallic (Co1−xFex)2P phosphide array with
controllable regulation of Co/Fe ratio and porosity showed
a low onset potential (12 mV), a low overpotential (64 mV)
at current density of 10 mA cm−2, and a small Tafel slope
(45 mV per decade) for HER in H2SO4 electrolyte, while a
low onset potential (225 mV), a small overpotential (270 mV)
at current density of 10 mA cm−2, and a small Tafel slope
(30 mV per decade) for OER in KOH solution. Based on
outstanding OER and HER performance, a two-electrode
system using (Co1−xFex)2P arrays as bifunctional electrocata-
lysts showed a low cell voltage of 1.49 V at current density
of 10 mA cm−2 toward overall water splitting.[70] Owing to
hierarchical nanostructures and synergistic effect, porous
molybdenum tungsten phosphide nanosheet arrays by facile
phosphidation of molybdenum tungsten oxide as 3D hierar-
chical electrocatalysts achieved a low overpotential (138 mV)
at high current density (100 mA cm−2) and a low Tafel slope
(52 mV per decade) in 0.5 m H2SO4 solution.[71] Interestingly,
bimetallic iron–nickel phosphide solid-solution nanoplate
arrays demonstrated a very low overpotential (180 mV) at
current density of 10 mA cm−2, a small Tafel slope (76 mV
per decade), and remarkable stability in alkaline media.[72]
Therefore, it is essential to design and fabricate active tran-
sition metal phosphide arrays for superior electrocatalytic
water splitting.
4.5. Transition Metal Phosphate Arrays
Owing to structural stability, metal phosphate is also a prom-
ising candidate as electrocatalyst. The phosphate groups not
only act as proton acceptors facilitating the oxidation of metal
atoms, but also induce distorted local metal geometry favoring
water adsorption and oxidation.[55,56] A significant effort has
been made in the field of transition metal phosphates to pro-
duce transition metal phosphate catalysts such as Na2CoP2O7,
NaCoPO4, Li2CoP2O7, LiCoPO4, and Mn3(PO4)2·3H2O as the
efficient water oxidation catalysts with understanding of the
interplay between atomic structure and catalytic activity.[73,74]
To promote the electrocatalytic activity, Ni2P4O12 nanocrystals
grown on carbon cloth achieved a significantly low overpoten-
tial (270 mV) at current density of 10 mA cm−2 and outstanding
durability over 100 h.[75] 2D amorphous FePO4 nanosheets on
Ni foam displayed a low onset potential (225 mV), small over-
potentials of 218 and 270 mV at current densities of 10 and
300 mA cm−2, respectively, and a small Tafel slope (42.72 mV
per decade) for OER, while near-zero onset potential, a small
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Figure 3.  a) Cross-sectional SEM image of MoS2 array. Reproduced with permission.[78] Copyright 2012, Nature Publishing Group. b) SEM image of
W(SexS1−x)2 on tungsten foil. Reproduced with permission.[79] Copyright 2017, American Chemical Society. c,d) Schematic depiction and HER perfor-
mance of CoS2 arrays. Reproduced with permission.[81] Copyright 2014, American Chemical Society. e) Nickel–cobalt diselenide nanosheets. Repro-
duced with permission.[87] Copyright 2017, Wiley-VCH.

overpotential (123 mV) at current density of 10 mA cm−2, and
a small Tafel slope (104.49 mV per decade) for HER in alkaline
solution. Motivated by robust OER and HER activities, a two-
electrode system using FePO4/Ni arrays as bifunctional electro-
catalysts achieved low cell voltages of 1.54 and 1.72 V at current
densities of 10 and 100 mA cm−2, respectively, toward overall
water splitting in alkaline media.[76] 3D porous hierarchical
Ni–Fe phosphate film/Ni foam delivered current density of
10 mA cm−2 at the overpotential of 87 mV for HER and current
density of 20 mA cm−2 at the overpotential of 204 mV for OER
as well as current density of 10 mA cm−2 at the overpotential of
326 mV for overall water splitting.[77]
4.6. Transition Metal Chalcogenide Arrays
As promising electrocatalysts of transition metal chalcoge-
nides, it is of great fundamental importance to understand the
in-depth mechanism of electrocatalytic HERs. Among these
catalysts, molybdenum disulfide (MoS2) is one of the first to
emerge as a prototypical material. For example, by regulating
morphology of MoS2 catalyst, 3D ordered MoS2 thin film
with preferentially exposed edge sites and twisted network
nanostructure presented excellent HER activity (Figure  3).[78]
W(SexS1−x)2 nanoporous architectural arrays showed a small
onset overpotential of 45 mV and a low Tafel slope of 59 mV

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per decade in H2SO4 aqueous solution owing to defect struc-
tures and abundant active sites (Figure 3).[79] Based the anal-
ysis of pyrite-phase electrocatalysts, metal dichalcogenides
(MX2, M = Fe, Co, or Ni and X = S or Se) as common min-
erals have been proposed as efficient HER catalysts.[80] For
example, transition metal pyrites (FeS2, CoS2, NiS2, and their
alloys) with the regulated morphology and composition have
been investigated (Figure 3), presenting robust HER perfor-
mance owing to pyrite-type crystal structure and active surface
sites.[81] However, it is necessary to capture the relationship of
structure and activity and understand the in-depth mechanism
of the improved performance for these pyrites. Compared to
the conventional nanoparticle and nanostructured film, CoS2
micro- and nanostructuring arrays grown on conducting sub-
strate have boosted HER activity due to high surface area,
presenting a small overpotential (145 mV) at current density
of 10 mA cm−2 and outstanding durability.[82] High-index fac-
eted Ni3S2 nanosheets, NiSe nanowires, Ni3Se2 nanoforests,
Co3Se4 nanowires, Ni1−xCoxSe2 nanosheet networks, hollow
Ni3S2 microspheres, and cobalt–manganese sulfide nanosheet
arrays on conducting foam showed remarkable HER and OER
activities and outstanding stability.[83–89] Hierarchical Ni–Mo–S
nanosheets and selenium-enriched nickel selenide nanosheet
arrays also exhibited excellent electrocatalytic performance and
robust stability.[14c,90,91]
4.7. Transition Metal Nitride Arrays
Among various electrocatalysts, transition metal nitrides
have attracted enormous attention as a result of distinct
electronic structure, low electrical resistance, and high chem-
ical stability.[92] For example, porous Co4N nanowire arrays
for oxygen evolution reaction required a low overpotential
(257 mV) at current density of 10 mA cm−2 and a small Tafel
slope (44 mV per decade) in an alkaline medium.[93] To verify
the stability, the CoN/O and CoCo bonds have been proven
by ex situ X-ray absorption fine structure (XAFS) spectra, indi-
cating the stable OER activity owing to the stable structure of
Co4N layer as major phase. Especially, the combined analysis
of XAFS, X-ray photoelectron spectroscopy (XPS), and X-ray
absorption near-edge structure (XANES) spectra confirmed
the formation of cobalt oxide/hydroxide as active phases.[93]
Compared to conventional nitridation route using ammonia,
cobalt nitride nanowire arrays derived from cobalt oxide arrays
through convenient N2 radio frequency plasma treatment
achieved current density of 10 mA cm−2 at a low overpoten-
tial of 290 mV and a small Tafel slope of 70 mV per decade
in alkaline electrolyte.[94] Although nickel nitride has been
proven to be a promising electrocatalyst, to further optimize
the catalytic activity, Ni3N nanosheets/carbon microfibers/
Ni3N nanosheets as the integrated arrays revealed a small over-
potential of 270 mV at current density of 10 mA cm−2 and a
small Tafel slope (41.54 mV per decade) for OER, while a small
overpotential (115 mV) at current density of 10 mA cm−2 and a
small Tafel slope (40 mV per decade) for HER in alkaline solu-
tion. Motived by excellent OER and HER performance, a two-
electrode system using Ni3N/CMFs/Ni3N arrays as bifunctional
electrocatalysts owing to excellent electrical conductivity and
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abundant active sites achieved a low cell voltage of 1.652 V at
current density of 20 mA cm−2 toward overall water splitting.[95]
Vanadium-doped Co4N nanosheet arrays grown on a Ni foam
owing to the downshift of the d-band center on neutralizing
the electron densities of cobalt by vanadium doping and the
beneficial H desorption enabled an overpotential of 37 mV at
10 mA cm−2 (Figure 4a,b).[96] Although significant efforts have
been made in single-metal nitride arrays, binary metal catalysts
have been further developed owing to a synergistic effect of var-
ious available metal nitrides. Particularly, copper–nickel nitride
(Figure 4c), iron–nickel nitride, and nickel–molybdenum
nitride arrays achieved excellent HER and OER activities and
stability.[97–99] Although different metal nitride catalysts have
been made, more efficient transition metal nitride arrays could
be further explored and it is also of great benefit to uncover the
intrinsic modulation mechanism of metal nitrides for electro-
catalytic application.
4.8. Transition Metal Carbide Arrays
Among non–noble metal HER catalysts, metal carbides have
been proved to be active and stable HER catalysts.[100] For
instance, macroporous inverse opal-like MoxC structures and
3D hierarchically porous Mo2C frameworks exhibit significantly
enhanced HER electrocatalytic performance with good stability
owing to appropriate hydrogen binding energy, large exposed
surface, fast mass/charge transport of protons, and lower over-
potential.[101,102] Ni-doped Mo2C nanowire arrays displayed the
enhanced catalytic activity toward hydrogen production owing
to a synergistic function of Ni and Mo2C.[103] The high HER
activity of 1D Ni-doped Mo2C array is ascribed to better expo-
sure and enhanced utilization of the active sites. To clarify the
in-depth mechanism, DFT calculations have been performed
upon hydrogen binding energy, Bader charge, and Gibbs free
energies on Mo2C and Ni–Mo2C surfaces, facilitating the des-
orption of bound adsorbates (Hads) and their release from the
active sites in Ni–Mo2C, thus enhancing catalytic activity toward
hydrogen production.[103] Single nanocrystalline tungsten
carbides grown on the tips of vertically aligned carbon nano-
tube (CNT) arrays without corrosion and oxidation presented
an excellent catalytic activity for HER owing to high quality,
sufficient active sites, and the relatively low resistance of the
electrode.[104] Due to the instability of Ni foam in acid, nitrogen-
doped tungsten carbide arrays grown on carbon fiber paper
(CFP) exhibited high stability and OER and HER activities in
acid.[105] Mo2C nanocrystals anchored on vertically aligned gra-
phene nanoribbon arrays as efficient HER catalysts showed a
low onset potential (39 mV), a small overpotential (152 mV) at
current density of 10 mA cm−2, and a small Tafel slope (65 mV
per decade) in acidic media, corresponding to a low onset poten-
tial (53 mV), a small overpotential (121 mV) at current density
of 10 mA cm−2, and a small Tafel slope (54 mV per decade) in
alkaline solution.[106] To build the highway of rapid electron
transfer in metal carbide system, the integration of carbon and
metal carbides has been extensively explored for HER activities.
For example, Mo2C nanoparticles in 3D N-doped carbon (NC)
nanofiber networks (N-CNFs) as the hybrid (Mo2C@N-CNFs)
showed high HER activities in acidic, neutral, and basic media
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Figure 4.  a) Geometric configuration of vanadium-doped Co4N. b) DOS plots of Co4N and V–Co4N as well as schematic illustration of bond formation.
Reproduced with permission.[96] Copyright 2018, Wiley-VCH. c) Schematic illustration of the synthesis of copper–nickel nitride array. Reproduced with
permission.[97] Copyright 2017, The Royal Society of Chemistry.

owing to a strong synergistic effect between Mo2C nanoparti-
cles and N-CNFs.[107] Vertically aligned graphene nanoribbon–
supported iron group metal carbide M3C (M = Fe, Co, Ni)
nanocrystals presented a remarkable HER activity and excellent
stability in acidic media due to the synergistic effect between
M3C with graphitic shells and graphene nanoribbons.[108]
4.9. Metal–Organic Framework Arrays
Compared to various electrocatalysts, MOFs with well-ordered tun-
able porous structure, high internal surface area, and good thermal
and chemical stability have also attracted attention as prom-
ising electrocatalysts. For instances, 3D well-aligned cobalt MOF
nanosheet arrays on the carbon cloth revealed a low overpoten-
tial and good durability toward water oxidation.[109] M-BTC MOF
nanoarrays (M = Fe, Ni; BTC = 1,3,5-benzenetricarboxylic acid)
with tunable metal ions and the regulation of metal contents dem-
onstrated a low Tafel slope (47 mV per decade) and a small overpo-
tential (270 mV) at current density of 10 mA cm−2 and outstanding
stability.[110] Dexter–Silverton polyoxometalate oxygen evolution
catalysts [Co6.8Ni1.2W12O42(OH)4(H2O)8] grown on commercial
nickel foam achieved a current density of 10 mA cm−2 at a low
overpotential of 360 mV, a Tafel slope of 126 mV per decade, and
a Faradaic efficiency of 96% in alkaline solution (Figure  5a).[111]
To maximize the catalytic performance, the highly reactive oxygen
species generated by the low-temperature air plasma activate
the metal sites in the Fe/Co bimetallic cyanide framework for
OER by oxygen bonding to the metal sites in the nanoporous
framework, bringing new opportunity to develop framework-
based electrocatalysts.[112] Co-based metal–organic framework
(Co(bpdc)(H2O)4; bpdc = biphenyl-4,4′-dicarboxylic acid) arrays
for OER reached current density of 10 mA cm−2 at a small over-
potential of 220 mV and a low Tafel slope (72 mV per decade)
in alkaline media.[113] With regard to MOFs as promising elec-
trocatalysts, MOF [{Fe3(µ3-O)(bdc)3}4{Co2(na)4(H2O)2/3(OH)4/3}3]
on Ni foam presented current density of 10 mA cm−2 at a small
overpotential of 225 mV and a low Tafel slope (48 mV per
decade) for excellent and stable OER in alkaline electrolyte.[114] A
metal azolate framework [Co2(µ-OH)2(bbta)] (H2bbta = 1H,5H-
benzo(1,2-d:4,5-d′)bistriazole) functionalized by both open metal
sites and hydroxide ligands drastically improved OER activity,
corresponding to current density of 10 mA cm−2 at a small
overpotential of 292 mV and a low Tafel slope (88 mV per decade)

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Figure 5.  a) Dexter–Silverton polyoxometalate [Co6.8Ni1.2W12O42(OH)4(H2O)8] on Ni foam. Reproduced with permission.[111] Copyright 2017, Wiley-VCH.
b) Framework and pore surface structures and solid–liquid coupling pathway. Reproduced with permission.[115] Copyright 2016, American Chemical Society.

in alkaline media (Figure 5b).[115] Inspired by the advantages of
MOF catalysts and nanostructures, 2D MOF nanosheets on Cu
foam required a low overpotential (189 mV) at current density of
10 mA cm−2 and outstanding stability over 200 h. Especially, the
coordinatively unsaturated metal atoms and the coupling effect
contribute to the enhancement of OER activity by use of the
combined analysis of DFT calculations, XPS spectra, and X-ray
absorption spectra, identifying the relationship between struc-
ture and performance at the molecular level.[116] Compared with
conventional inorganic catalysts, poorer electric conductivity,
stronger structural anisotropy, and more difficult binding with
inorganic electric conducting substances have been observed
in MOFs.[117] Therefore, it is essential to improve the electronic
conductivity inside the MOF crystals and between MOF crystals
and the substances, as a versatile technique to enhance electro-
catalytic performance.
4.10. Other Arrays
Beyond metals, metal oxides, metal hydroxides/oxyhydroxides,
metal phosphides, metal phosphates, metal chalcogenides,
metal nitrides, metal carbides, and MOF arrays, other
electrocatalysts, such as metal phosphate–borate arrays and
sulfhydroxide arrays, were also explored. Owing to low cost,
earth abundance, and less toxicity of Fe in comparison with Co
and Ni, iron phosphate–borate nanosheet arrays as OER cata-
lysts presented a low overpotential (434 mV) at 10 mA cm−2 and
strong stability in 0.1 m KBi.[118] For instance, dual ligand Ni,
Co sulfhydroxides as OER catalysts achieved current density of
10 mA cm−2 at a low overpotential and robust stability owing to
the synergy between S atoms and OH groups (Figure  6a).[119]
Cobalt phosphosulfide (Co2−xSP) nanosheet on carbon fiber
paper substrate by a simple two-step electrodeposition route
showed current density of 10 mA cm−2 at a low overpotential
(279 mV), a low Tafel slope (54 mV per decade), and robust
stability toward remarkable OER activity.[120] Beyond metal-
based arrays, carbon-based electrocatalysts and the integrated
arrays using carbon-based materials and metal-based arrays
have also presented considerably enhanced electrocatalytic per-
formance.[111–116] Although various inorganic material arrays
have been extensively investigated, the integration of inorganic
arrays and carbon-based layers displayed higher electrocata-
lytic performance than single-phase inorganic material array
or carbon-based layers. Notably, the synergistic effect of the
hybrids not only increases active sites but also facilitates the

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Figure 6.  a) Ultimate unity of OER performance of NiCo2(SxOH2−x)y. Reproduced with permission.[119] Copyright 2017, American Chemical Society.
b) SEM image of Co/C array, and c) SEM, d) color mixed inverse fast Fourier transform (FFT), and e) scanning transmission electron microscopy
(STEM) high-angle annular dark-field images of Co–Pt clusters embedded in carbon nanoflake arrays. Reproduced with permission.[125] Copyright 2018,
The Royal Society of Chemistry.

charge transfer in electrocatalytic reactions. For example, 3D 5. Synthesis of Architectural Electrocatalysts

van der Waals heterostructures through artificial assembly of
2D WS2 nanolayers with almost 100% exposed surface atoms
and P-, N-, and O-doped graphene sheets presented current
density of 10 mA cm−2 at a low overpotential (125 mV), a low
Tafel slope (52.7 mV per decade), and robust stability.[121] To
address the low conductivity of iron oxyhydroxide as the major
obstacle, in our group, the hybridization arrays of N-doped
carbon and FeOOH owing to high conductivity, 3D porous
nanostructure, and synergistic effect between N-doped carbon
and FeOOH required a small overpotential (230 mV) at cur-
rent density of 100 mA cm−2 and a low Tafel slope (33.8 mV per
decade), as well as robust stability (>50 h) in alkaline media.[122]
Cu nanoparticle–embedded N-doped carbon nanowire array
on copper foam as cost-effective OER electrocatalyst was pro-
duced by using a simple carbonization process of a Cu(TCNQ)
(TCNQ = 7,7,8,8-tetracyanoquinodimethane) array.[123] N, P
dual-doped carbon-encapsulated MoP/MoP hybrids on carbon
cloth, Co–Pt/carbon arrays (Figure 6b), and cobalt diselenide/
carbon nanotube arrays as the 3D electrodes presented efficient
HER performance.[124–126] To develop the integrated nanoar-
rays as robust electrocatalysts, various metal- and nonmetal-
based compounds grown on conductive substrates could be
further explored as promising candidates for robust water split-
ting owing to natural abundance and potential electrocatalytic
performance.
5.1. Hydrothermal/Solvothermal Synthesis
One of the most popular approaches is hydrothermal/solvo-
thermal synthesis of various arrays with tunable architectures
on self-supported substrates owing to low cost, simple pro-
cessing setup and operations, and desirable growth results by
simple and flexible control of reaction time, stabilizing agent,
pH, precursor concentration, and temperature in aqueous
or nonaqueous solutions.[127–132] A large number of advanced
arrays are available via hydrothermal/solvothermal synthesis,
which are defined as the approaches of synthesis of various
materials depending on the solubility of minerals in hot water
under the pressure. For example, Co(OH)(CO3)0.5 nanowire
array was synthesized through hydrothermal reaction, and then
Co(SxSe1−x)2 array was fabricated by heat treatment of sulfur/
selenium powder in argon atmosphere (Figure 7a).[128] Mackina-
wite FeS nanosheet arrays were grown on iron foam by hydro-
thermal process (Figure 7c).[129] Interestingly, Ni or Fe foam as
the conductive substrate in this process can not only act as the
support for the growth of nanostructured arrays but also offer a
metal source to the desired target. NiFe LDH nanosheets were
grown on the surface of Co0.85Se nanosheet on graphene foil
through hydrothermal method, resulting in the formation of
3D ternary hybrid of EG/Co0.85Se/NiFe LDH array.[130]

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Figure 7.  a) Scheme of synthesis of Co(SxSe1−x)2 nanowire array. Reproduced with permission.[128] Copyright 2015, Elsevier Ltd. b) Schematic illustra-
tion of synthesis of NiMo3S4 nanosheet array. Reproduced with permission.[137] Copyright 2018, Elsevier Ltd. c) Schematic illustration of FeS nanosheet
array for both HER and OER. Reproduced with permission.[129] Copyright 2018, Elsevier Ltd.

By comparing the reaction conditions and results, the tem-
perature has appeared as the pivot parameter toward the regu-
lation of the morphology. Although hydrothermal/solvothermal
route has been adopted in the synthesis of various arrays,
there are still limitations upon the component manipulation.
To address this point, the integration of hydrothermal/solvo-
thermal synthesis and subsequent thermal treatment has been
applied to fabricate a wide range of metal-based materials,
such as oxide/hydroxide/oxyhydroxide arrays,[127–131] phosphide
arrays,[132–135] chalcogenides (Figure 7b),[136,137] etc. This way
arrays are preferentially formed without use of any external
template. However, it is hard to observe the crystal growth
and the expensive autoclaves are always used in this process
as the disadvantages. Notably, the controllable architectural

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electrocatalysts could modulate size-related or morphology-
related electrical or electrocatalytic property to engineer the
regular functions of the architectural arrays. Thus, the hydro-
thermal/solvothermal synthesis is a versatile approach toward
the optimized activity of architectural arrays.
5.2. Electrochemical Deposition Synthesis
The involvement of electrochemical deposition in versatile syn-
thetic chemistry with the advantages of safety, simple require-
ments, low synthesis temperature, and high accessibility as
well as industrial fabrication provides an alternative way to
produce architectural arrays. Electrochemical deposition syn-
thesis is a process to generate a coherent film on an electrode
by electric field–induced electrochemical reactions. However,
the limited chemical precursors and the conductive substrates
are required owing to the involvement of charge transport
during the electrochemical deposition process. Interestingly,
different materials such as molecular catalysts,[156] metal oxides
and hydroxides,[157–161] chalcogenides,[162,163] phosphates,[164,165]
metals, and alloys[166,167] as potential electrocatalysts can also
be produced by the regulation of applied potential during
electrochemical deposition process. For example, hierarchical
Cu2O–Cu array with dendritic nanostructures (Figure  8) has
been synthesized by hydrogen bubble dynamic template syn-
thesis, reaching current density of 10 mA cm−2 at a low over-
potential (350 mV) and excellent stability for OER in alkaline
solution.[138] 3D amorphous nickel–iron hydroxide nanosheets
with interconnected bicontinuous macroscopic porous struc-
ture were deposited on nickel foam by electrochemical deposi-
tion in iron nitrate and nickel nitrate solution as the precursors
(Figure 8), achieving OER current density of 100 mA cm−2 at
a low overpotential (270 mV) and small onset overpotentials

Figure 8.  a–j) SEM and TEM images, STEM image with STEM–energy-dispersive X-ray spectroscopy mapping as well as atomic force microscopy lateral
force and deflection images of 2D Fe–Ni hydroxide array. Reproduced with permission.[139] Copyright 2018, Elsevier Ltd. k) Cu2O–Cu foams. Reproduced
with permission.[138] Copyright 2017, American Chemical Society. l) Nickel phosphide arrays. Reproduced with permission.[140] Copyright 2016, Wiley-VCH.

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(190 mV) in alkaline media.[139] Nickel phosphide electrocata-
lysts were fabricated by electrodeposition of Ni and subsequent
phosphorization treatment. As-synthesized Ni–P arrays as HER
catalysts required small overpotentials of 162 and 250 mV at
current density of 100 mA cm−2 and small Tafel slopes of 58.8
and 85.4 mV per decade in acidic and alkaline media, respec-
tively, while a small overpotential (300 mV) at current density
of 50.4 mA cm−2 and a small Tafel slope (70 mV per decade) for
enhanced OER performance owing to the formation of Ni–P/
NiO/Ni(OH)x heterostructure in alkaline solution. Motived by
excellent OER and HER performance, a two-electrode system
using Ni–P arrays as bifunctional electrocatalysts owing to
excellent electrical conductivity and abundant active sites
achieved low cell voltages of 1.63 and 1.73 V at current densities
of 10 and 20 mA cm−2, respectively, toward overall water split-
ting.[140] α-Co(OH)2 nanosheet array on CFC was produced by
electrochemical deposition, and then iron-substituted CoOOH
porous nanosheet array with a low overpotential of 266 mV at
10 mA cm−2, a small Tafel slope of 30 mV per decade, and high
durability was transferred from α-Co(OH)2 nanosheet array by
in situ anodic oxidation in (NH4)2Fe(SO4)2 solution.[141] Three-
layer hierarchical Ni1−xCoxP films dependent on the Ni/Co
ratio on Ni foam were synthesized by electrodeposition, indi-
cating the best electrocatalytic activity for both HER and OER
in Ni0.51Co0.49P array.[142] Beyond the inorganic precursors for
electrochemical deposition, the organometallic complexes as
the precursors have been electrodeposited on the electrode
­surface; however, the stability as an inherent problem of mole­
cular electrocatalysts existed owing to the inevitable decom-
position during electrolysis. In our group, an ionic copper
complex containing an amine-pyridine-based pentadentate
ligand with five coordinating nitrogen atoms, (Cu(bztpen))2+
(bztpen=N-benzyl-N,N′,N′-tris(2-pyridylmethyl)ethylenedi-
amine), has been studied as a highly active molecular catalyst
for the HER, corresponding to the decomposition of glassy
carbon surface under long-term electrolysis.[143] To overcome
this drawback, in our group, Cu–CuxO–Pt film by uniformly
dispersed small amount of Pt was produced through electro-
chemical deposition by using [Cu(bztpen)]2+ on glassy carbon
electrode in aqueous solution electrolyte at an applied poten-
tial, presenting a small Tafel slope and a large exchange current
density in neutral buffer solution and H2SO4 solution as well as
the outstanding stability after 100 h electrolysis.[144] Comparing
these results, the thickness of architectural arrays is always
related to the electrodeposition time, while the components of
electrodeposited catalysts could be tailored by controlling the
applied potentials under certain ion concentration.[138–144] Thus,
the above-mentioned analysis has proved that electrochemical
deposition is a desired feature to produce hierarchical arrays
with the overwhelming advantages of material selectivity and
morphology controllability. However, the deposited materials
are often amorphous or have a low degree of crystallization by
electrodeposition, limiting the extensive applications.
5.3. Template Synthesis
Template-directed synthesis is a more reliable and versatile syn-
thesis technique to fabricate ordered 1D nanoarrays, such as
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nanorods, nanowires, and nanotubes, by use of soft or hard tem-
plate.[145,146] Most importantly, the template synthesis approach
possesses the significant advantage of the desirable nanogeom-
etry independent of the materials’ lattice preferences. By using
anodic aluminum oxide (AAO) as a typical hard template,[147] Rh
nanowire array as robust catalyst has been produced through
electrodeposition by use of AAO membrane, presenting an
enhanced hydrogen evolution reaction performance.[148] 1D Ni
nanowire array, Cu nanowire array, and Ni–Cu composite nano-
wire arrays were fabricated through deposition technique in
AAO template.[149] After the deposition on the substrates, the
subsequent removal of the template is still required in the AAO
template approach for the synthesis of 1D nanoarrays. Beyond
AAO template, ZnO and Cu2O materials are also common
templates for the synthesis of nanostructured arrays.[150,151] For
example, ZnO nanorod array was deposited on nickel foam by
electrochemical deposition route, and then FeOOH/Co/FeOOH
nanotube array on nickel foam as excellent OER catalyst was
produced by the deposition of Co, the removal of the ZnO tem-
plate, and subsequent deposition of double FeOOH shells.[65] By
using 1D ZnO nanowires as template, a carbon paper/carbon
tube/cobalt–sulfide array with the unique 3D array architec-
ture (Figure  9) has been synthesized by chronoamperometric
and subsequent heat treatment approaches, achieving superior
HER and OER activities in alkaline medium.[156] With regard to
Cu2O template, Co–Ni hydroxide array was transformed from
Cu2O array due to the continuous dissolution of Cu2O.[152–155]
3D ordered mesoporous Ni sphere array was synthesized by
this template approach, reaching current density of 10 mA cm−2
at a low overpotential (254 mV) and a small Tafel slope (39 mV
per decade) in alkaline media.[157] Inspired by hollow micro/
nanostructures with well-defined internal cavities, hollow Co3O4
microtube arrays were fabricated by a facile scalable electro-
chemical self-templating strategy, producing excellent OER,
HER, and overall water splitting performance.[46] However, it
is hard to produce triple-layered hollow nanostructures with
tunable compositions and morphologies owing to the paucity
of self-templates. Wang and coworkers reported triple-layered
NiCoS@HsGDY@Ni,Co–MoS2 nanotube array grown on
carbon paper by a hydrogen-substituted graphdiyne (HsGDY)-
coated self-template as a dual template and subsequent hydro-
thermal reaction (Figure 9), presenting high current density and
a low overpotential over a wide pH range (0–14) in HER.[158]
Owing to the utilization of different templates, this versatile way
achieved a feasible dimension controllability and uniformity of
architectural arrays. However, the crystal quality and purity con-
trol during template filling and removal as the typical drawbacks
are required in this template synthesis approach. Therefore, this
template technique offers the promising features with signifi-
cant advantages and limitations, as novel building approach for
the development of sustainable energy systems.
5.4. MOF-Derived Synthesis
Metal–organic framework is a kind of porous material com-
posed of coordination bonds between organic ligand and transi-
tion metal cation.[159] MOF as the multipurpose precursor has
been used for the preparation of porous metal-based materials
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Figure 9.  a–f) SEM and TEM images, SAED pattern, and element mapping of 3D carbon paper/carbon tube/cobalt–sulfide array. Reproduced with
permission.[156] Copyright 2016, American Chemical Society. g,h) SEM images and elemental mappings of triple-layered NiCoS@HsGDY@Ni,Co–MoS2
array. Reproduced with permission.[158] Copyright 2018, Nature Publishing Group.

(e.g., oxides, chalcogenides, and phosphides) with low cost, and morphology of MOF precursors. For example, hollow
simple setup, and flexible operations as the advantages.[160] NiCo2O4 nanowall arrays derived from uniform 2D cobalt-based
However, the target products are limited by the components MOFs on flexible carbon cloth substrate were produced by an

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ion-exchange and etching reaction and subsequent thermal
treatment.[161] Hierarchically structured Co3O4@X (X = C,
CoS, Co3O4, and CoP) electrocatalysts have been systematically
fabricated through a facile metal–organic framework template-
directed synthesis by use of cobalt carbonate hydroxide@
ZIF-67, displaying current density of 10 mA cm−2 at a low
overpotential of 238 mV in Co3O4@CoP array (Figure  10).[162]
P-doped CoSe2 nanoclusters/carbon flake arrays were syn-
thesized by thermal treatment of Co2Zn1 MOF flake arrays,
exhibiting a low overpotential of 230 mV at 10 mA cm−2 and a
large half-wave potential of 0.87 V toward OER.[163] CoFe2O4/C
porous hybrid nanorod array has been produced by using
[M2(dobdc)](MOF-74-M, M = Mn, Fe, Co, Ni, etc., H2dobdc =
2,5-dioxido-1,4-benzenedicarboxylic acid) as the precursors,
presenting superior OER catalytic activity and remarkable long-
term stability.[164] Beyond MOFs, zeolitic imidazolate frame-
work (ZIF) is also a promising alternative as the precursor. For
instance, Co–Nx/C nanorod array has been synthesized by the
heat treatment of ZIF precursors, requiring a low potential of
1.53 V at current density of 10 mA cm−2 toward OER.[165] Thus,
MOF-derived synthesis is a unique approach of architectural
arrays toward electrocatalytic applications.
5.5. Chemical Vapor Deposition Synthesis
Beyond the common approaches of hydrothermal/solvothermal
synthesis, electrochemical deposition, templated synthesis, and
MOF-derived synthesis, chemical vapor deposition (CVD) is a
deposition method to produce high-quality solid materials on
particular substrates by use of vaporized precursor materials, cor-
responding to the advantages of simple setup, easy access to raw
materials, and suitable fabrication of complex structure.[166–171]
For instance, molybdenum disulfide nanosheets on 3D gra-
phene array were fabricated by a microwave plasma-enhanced
chemical vapor deposition and subsequent simple hydrothermal
reaction, presenting a low onset potential of 50 mV, a small over-
potential of 78 mV at 10 mA cm−2, a low Tafel slope of 53 mV
per decade, and robust stability in acidic solution (Figure 10).[166]
Ultrathin α-Co(OH)2 nanosheets on the substrate of N-doped
carbon nanotubes on nickel foam were synthesized by chemical
vapor deposition and subsequent electrodeposition process,
achieving current density of 10 mA cm−2 at low overpotentials
of 270 and 170 mV for OER and HER, respectively.[167] Cu@
graphdiyne/Co foam was produced by a chemical bath deposi-
tion and chemical reduction of Co2+ salt precursor for OER.[168]

Figure 10.  a) Schematic illustration of the synthesis of molybdenum disulfide nanosheets supported by graphene on carbon cloth. Reproduced with
permission.[166] Copyright 2015, Elsevier Ltd. b,c) FeMnP on graphene-coated nickel foam. Reproduced with permission.[170] Copyright 2017, Elsevier
Ltd. d,e) MoSe2 array. Reproduced with permission.[171] Copyright 2017, IOP publishing.

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FeMnP nanoplatelet array on both nickel

foam and graphene-coated nickel foam by
organometallic FeMn(CO)8(µ-PH2) precursor
has been synthesized by CVD toward robust
electrocatalysts.[170] 3D hierarchical MoSe2
nanoarchitecture array has been fabricated
by CVD for highly efficient electrocatalyst for
hydrogen evolution.[171] With regard to CVD
synthesis, it is effective to regulate the nano-
structure morphology and growth rates by
use of metal–organic precursors; however, it
is limited due to the required harsh reaction
environment, high cost, and toxicity of metal–
organic precursors. Compared to metal–
organic precursors, inorganic precursors have
attracted extensive attention for the synthesis
of various electrocatalysts. Despite the advan-
tages of CVD, the equipment and operation
conditions limited a large-scale technique for
the synthesis of nanoarrays.

5.6. Plasma-Induced Synthesis

Plasma-induced approach is a versatile tech-

nique for rapid and large-scale treatment of
various materials by use of plasma gases under
the appropriate regulation of plasma frequency
and temperature.[172–176] However, the need
of frequency and temperature and high cost
of plasma as the disadvantages are always
required in this plasma-induced process. For
instance, 1T-MoSe2/Mo array on a Mo/glass
substrate as core–shell 3D hierarchical nano-
structures was produced by an integrated
approach of glancing angle deposition followed Figure 11.  a) Schematic of the synthesis of MoSe /Mo core–shell array and schematic of HER
2
by the plasma-assisted selenization process and charge transfer. Reproduced with permission.[175] Copyright 2016, John Wiley and Sons.
(Figure  11), generating current density of b) Schematic illustration of the fabrication of Ni3N1−x/NF on Ni foam. Reproduced with
10 mA cm−2 at a low overpotential of 166 mV permission.[176] Copyright 2015, Elsevier Ltd.
and a Tafel slope as low as 34.7 mV per decade
owing to the increased density of exposed edges and the metallic approach is a promising synthetic route for the construction of
phase of the MoSe2 shell as well as fast charge transfer with opti- nanoarrays with the desired component and architectural mor-
mized free energy of hydrogen (ΔGH*).[172] To develop efficient phology. Aiming to synthesize the architectural arrays, various
hydrogen evolution reaction catalysts, surface reorganization approaches have been explored with the versatile advantages and
of CoP nanowire arrays grown on carbon cloth was conducted limitations (Table 3). Thus, the flexible process and the integrated
by oxygen plasma engraving treatment, triggering moderate approaches under controllable conditions could be adopted for the
CoOx species formation on the surface of CoP nanowires and design and synthesis of promising nanoarrays.
thus enhancing alkaline HER performance.[173] Fe nanostruc-
tures on a substrate with magnetic self-assembly were produced
through a pulsed plasma process by using an external magnetic 6. Strategies of Nanoarray Architectures
field, enabling the efficient H2 production from water splitting.[174]
for Robust Water Splitting
Cu2S nanosheet arrays on Cu foam were also synthesized by a
facile iodine dielectric barrier discharge plasma and an anion- 6.1. Component Manipulation Engineering of Nanoarray
exchange reaction, presenting prominent electrocatalytic activity Architectures
and persistent stability.[175] Nickel nitride nanostructure enriched
with nitrogen vacancies (Ni3N1−x) has been produced by plasma- 6.1.1. Metal Cation Tuning
enhanced nitridation of commercial Ni foam, producing current
density of 10 mA cm−2 at a low overpotential of 55 mV and a low Owing to the adsorption energy optimization triggered by
Tafel slope of 54 mV per decade for HER.[176] Thus, plasma-induced diverse metal (Ni, Co, Fe, W, Mn, V, Cu, Mo, etc.) integration,

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Table 3.  Brief summaries of versatile synthetic approaches of architec- densities of 30 and 10 mA cm−2 at low overpotentials of 294 and
tural electrocatalysts. 180 mV for OER and HER, respectively. To deeply understand
the crucial role of Mn doping, electronic configuration modula-
Synthesis approaches Advantages Disadvantages tion was systemically analyzed by X-ray photoelectron spectra
Hydrothermal/ Low cost Need of expensive autoclaves and theory calculations.[186]
solvothermal synthesis Simple setup Impossibility of observing Inspired by doping strategy, Fe-doped Co carbonate
Flexible operations the crystal growth hydroxide nanosheet array on 3D conductive Ni foam as a mon-
Electrochemical Safe Selective products olithic OER and HER bifunctional electrocatalyst delivered 10
deposition synthesis Inexpensive equipment Low crystallization of and 1000 mA cm−2 at small overpotentials of 77 and 256 mV for
Low synthesis temperature products HER and 228 and 308 mV for OER in KOH solution, respec-
High accessibility tively.[187] DFT calculations of Fe-doped Co carbonate hydroxide
Industrial fabrication
nanosheet array demonstrated that the adsorption of hydrogen
Template synthesis Desirable geometry Template filling is weakened and the different intermediates’ absorption is
Template removal strengthened during four fundamental steps of OER, signifying
MOF-derived synthesis Low cost Expensive MOF precursors the preferable kinetics elicited by Fe doping. Introducing iron
Simple setup Limited target products element into transitional metal phosphide is also beneficial for
Flexible operations
catalytic activity advancement.[188,189] For example, Chen and
CVD synthesis Simple setup Harsh reaction environment coworkers fabricated the Pt-like HER electrocatalyst via iron ele-
Easy access to raw High cost ment into the lattice structure of CoP.[188] Fe0.5Co0.5P integrated
materials Toxicity of metal–organic
with carbon cloth achieved current density of 10 mA cm−2 at a
Fabrication of complex precursors
low overpotential of 37 mV in acidic media. The iron doping
structure
leads to more favorable hydrogen adsorption energy (ΔGH*)
Plasma-induced synthesis Easy operations High cost
of CoP acquired by DFT calculations, confirming that the Fe
Desirable component Need of synthesis frequency
incorporation is of great importance to promote the electrocata-
and temperature
lytic performance.
As a member of transition metals, Zn with low electron neg-
multimetal electrocatalysts usually are more thermodynami- ativity can also be defined as one type of excellent dopants to
cally favorable toward water splitting reaction compared with enhance water splitting performance.[190,191] For instance, Zn-
corresponding single-metal material.[177–197] For example, doped cobalt phosphide was prepared through electrodeposition
the coexistence of Ni and Fe contributed to the enhancement and phosphorization procedures.[190] In Figure 12, Zn0.08Co0.92P
of earth-abundant Ni–Fe compounds, identifying that the nanowall array aligned on Ti mesh generated current density of
highly active sites are Fe sites rather than Ni sites in (Ni, Fe) 10 mA cm−2 at a low overpotential of 39 mV in H2SO4 solution.
oxyhydroxides for water oxidation by operando X-ray absorp- The dramatic improvement of HER performance by means of
tion spectra.[177] Compared to NiFeOOH material, the excellent zinc substitution was ascribed to the low adsorption energy by
OER performance was observed in FeCoW oxyhydroxides with the regulated hydrogen adsorption energy calculation. As a pro-
the lowest overpotential owing to the synergistic effect between moter, the positive effect of Zn was comprehensively verified by
tungsten, iron, and cobalt, presenting the enhanced OER activity experimental data and theoretical calculations.
in alkaline electrolyte (Figure  12).[178] Inspired by oxyhydrox- Owing to the various oxidation states of Cr metal from +1
ides, coralloid W0.5Co0.4Fe0.1 trimetallic oxyhydroxide sponges to +6, it may be suitable for the enhancement of water split-
grown on Ni foam showed current density of 100 mA cm−2 ting.[192,193] A trimetallic NiFeCr LDH array on carbon paper
at a low overpotential (310 mV) and a small Tafel slope (32 mV was produced for robust water oxidation. NiFeCr electro-
per decade).[179] Beyond diverse oxyhydroxide systems, com- catalysts with molar ratio of 6:2:1 displayed the most efficient
pared to NiPx and CoPx arrays, bimetallic-structured NiCo2Px activity toward OER, reaching among active centers (Ni, Fe, Cr).
nanowire arrays exhibited impressive pH-universal catalytic More importantly, Cr cation with high valence state (Cr3+, Cr4+,
performances owing to the synergism of nickel and cobalt.[180] or Cr5+) may mediate the four-electron transfer process, thereby
Similarly, hierarchical CuCo2S4 arrays and NiCoP nanosheet optimizing the intrinsic OER activity.[193] Conjugating rare-earth
arrays also presented excellent activity and good stability.[181,182] element with active host is also valuable for tuning inherent
Nitrogen-doped carbon@CuCo2Nx/carbon fiber (CF) arrays kinetics of water splitting reaction.
in comparison with NC/CuNx/CF and NC/CoNx/CF arrays In contrast with monocation doping, dual-cation incor-
achieved excellent electrocatalytic performance for HER and poration was proven to be more impactful in tailoring water
OER in alkaline solutions with excellent activity and stability dissociation process.[194,195] Co, Fe codoped porous NiSe2
owing to the synergistic effect between CoN and CuN.[183] As (CoFe–NiSe2) nanosheets exhibited efficient activity for overall
we all know, MnOx displayed excellent performance toward water splitting (Figure 13).[195] The crystal distortion of CoFe–
OER,[184] and metal ion (Fe, V, Co, and Ni)-doped MnO2 NiSe2 from external Co, Fe incorporation may bring about the
ultrathin nanosheets electrodeposited on CFP reached current increment of active sites and expedite electrocatalysis accord-
density of 10 mA cm−2 at a low overpotential.[185] Motivated ingly. What’s more, intense electronic interaction was verified
by previous reports, Mn-doped cobalt carbonate hydroxide by negative shift of XPS peaks and it may regulate the electronic
nanosheets grown on hierarchical substrates with equal molar framework of metal center, thereby endowing the optimiza-
ratio of Co and Mn (denoted as Co1Mn1CH) presented current tion of absorption free energy. The optimal Co0.13Fe0.09-NiSe2

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Figure 12.  a) OER pathway and Gibbs free energies. Reproduced with permission.[177] Copyright 2015, American Chemical Society. b) Tuning the ener-
getics of OER activities of Fe, Co oxyhydroxides and W, Fe–doped Co oxyhydroxides, cobalt tungstate, and W oxides. Reproduced with permission.[178]
Copyright 2016, American Association for the Advancement of Science. c) OER and HER polarization curves of Co–Mn carbonate hydroxide arrays.
Reproduced with permission.[186] Copyright 2017, American Chemical Society.

arrays delivered current density of 10 mA cm−2 at low over-
potentials of 251 and 92 mV for OER and HER, respectively,
much superior to undoped and monocation-doped NiSe2,
indicating the synergism of Co, Fe codoping for activity pro-
motion. Furthermore, the acceleration of hydrogen evolu-
tion was well interpreted by DFT calculations and significant
reduction of intermediate absorption energy was noticed
under circumstances of Co, Fe codoping, due to the strong
electronic interaction in complex electrocatalyst. Merging
vanadium into lattice structure of catalyst was also regarded
as an effective way to boost water splitting activity.[194–197]
Fe and V codoped nickel (oxy)hydroxide nanosheet arrays
on CFP presented robust electrocatalytic oxygen evolution
(Figure 13).[194] Among them, Ni3Fe0.5V0.5 possessed the best
water oxidation activity, reaching current densities of 10 and
100 mA cm−2 at low potentials of 200 and 261 mV, respec-
tively. The XAFS spectroscopy was employed for coordination
environment and atom occupation analysis. With regard to Fe
and V codoped nickel (oxy)hydroxide, V K-edge Fourier trans-
form (FT) curves of extended X-ray absorption fine structure
(EXAFS) exhibited two main peaks that are assigned to VO
and VM (M = Ni, Fe, or V) bonds, respectively. Especially,
the operando XAFS spectroscopy implied the formation of
NiOOH during the OER process. Meanwhile, partial electron
may be transferred to 3d orbit of V due to decreased inten-
sity of characteristic peaks in V K-edge plots, contributing to

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Figure 13.  a) SEM image of Zn0.08Co0.92P array, b) polarization curves of ZnxCo1−xP array on titanium mesh, and c) free energy diagram for HER
on pristine CoP(101) and CoP(101) with Zn doping. Reproduced with permission.[190] Copyright 2017, Wiley-VCH. d) Schematic illustration of the
electronic coupling among Ni, Fe, and V in Ni3Fe, Ni3V, and Ni3Fe0.5V0.5. Reproduced with permission.[194] Copyright 2018, Nature Publishing Group.
e) SEM image of dual-cation-doped NiSe2 nanosheet array. f) OER and HER activities of Fe0.09Co0.13–NiSe2, Fe0.2–NiSe2, Co0.2–NiSe2, and NiSe2
nanosheet arrays. Reproduced with permission.[195] Copyright 2018, Wiley-VCH.

facilitated adsorption of oxygenated intermediates. The rather 6.1.2. Nitrogen Incorporation

short VO bond also confirmed the important role of vana-
dium for activity modulation. Moreover, DFT calculations
demonstrated that vanadium carried a big weight in tailoring
water dissociation kinetics of this ternary catalyst. In other
words, the integration of various metal elements is of great
significance in optimizing electronic structure and interme-
diates’ adsorption, leading to the considerable expedition of
water splitting reaction. To further promote the development
of robust multimetal electrocatalysts, theory calculations
should be employed for the preliminary analysis of unex-
ploited polynary systems, providing valuable guidelines for the
exploration of new class of multimetal materials and avoiding
the visionless trial and error to a great degree.
Encouraged by the metallic character of metal nitrides, it is
quite promising to introduce nitrogen atoms into crystal struc-
ture of electrocatalysts for largely expediting the charge transfer,
thus bringing about the remarkable improvement of water
splitting reaction.[198] It has been reported that fully converting
hydroxides or oxides into metal nitrides can lead to the thrilling
performance optimization of water dissociation process.[93,98]
For example, FeNi3N nanoarray on Ni foam was fabricated
by thermal ammonification of NiFe LDH precursor.[98] The
FeNi3N/NF electrode delivered current density of 10 mA cm−2
at the lowest overpotential of 202 mV, far superior to pristine
NiFe(OH)x/NF or NiFeOx/NF. Moreover, FeNi3N/NF also

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Figure 14. a) iR-corrected polarization curves. b) FT-EXAFS spectra of standard Co, Co3O4, and Co4N before and after 1000 potential cycles. Repro-
duced with permission.[93] Copyright 2015, Wiley-VCH. c) LSV curves of N–Ni, Ni framework, Ni-a, and Pt/C; d) Ni K-edge EXAFS spectra and e) Ni
K-edge XANES spectra of N–Ni and Ni framework, together with Ni foil, Ni3N, Ni(OH)2, and NiOOH; and f) N K-edge XANES spectra of N–Ni and
Ni framework. Reproduced with permission.[199] Copyright 2017, American Chemical Society.

showed extraordinary activity toward HER and only overpoten-
tial of 75 mV is able to reach current density of 10 mA cm−2.
The significant promotion of electrocatalytic activities may
derive from the intrinsic metallic property and distinctive elec-
tronic configuration of FeNi3N, as well as the distinct 3D array
structure. A perpendicularly aligned porous Co4N nanowire
array on the surface of carbon cloth has been designed for
electrocatalytic oxygen evolution.[93] The continuous density of
states (DOS) around the Fermi level demonstrate the metallic
character of Co4N. To deeply grasp the catalysis mechanism,
XAFS spectra were employed to analyze structure of electro-
catalysts, corresponding to similarly main peaks of CoN/O
and CoCo bonds before and after electrocatalysis, thus sig-
nifying the surface oxidation of Co4N into oxide or hydroxide
(Figure  14). The positive shift of pre-edge in XANES spectra
after catalysis further corroborated the partial oxidation of Co4N.
Moreover, thin CoOx layer of several nanometers was observed
in high-resolution transmission electron microscopy (HRTEM)
images for partially oxidized Co4N, which is consistent with the
analysis of XAFS spectra. Above all, the surface-oxidized Co4N
with oxide shell and porous 3D architecture may be responsible
for the outstanding performance of Co4N/CC.
Nitrogen modification without disarranging the inherent
atom alignment is also deemed as a practical strategy for the
enhancement of electrocatalytic performance.[199] For instance,
N-modified porous Ni (N–Ni) array on NF achieved highly
efficient water reduction in both neutral and alkaline media,
decreasing the overpotential to 64 mV of N–Ni array in com-
parison with original nickel framework (more than 150 mV) at
benchmark current density of 10 mA cm−2 in neutral solution.
In order to gain more insights into the superb activity of N–
Ni, DFT calculation is used for adsorption process simulation.
The initial water adsorption was facilitated by surface nitrogen
atoms on account of the enhanced adsorption energy of water
molecules. Moreover, energy barrier of water dissociation is
lowered by 0.42 eV, indicating the much favorable reaction
kinetics. As visualized in this report, water molecule is forced
to bend on the surface of pure nickel metal for HOH bond
breaking. However, hydrogen bond can be constructed between
the surface N atom of N–Ni and electron-deficient H atom. In
other words, the water adsorption and sequent dissociation
were both promoted assisted by nitrogen modification, collabo-
ratively resulting in the advancement of hydrogen evolution.
Doping nitrogen into crystal framework of electrocatalysts
can also engender the increment of electrocatalytic perfor-
mance.[16,20,200] For example, nitrogen-doped MoSe2/graphene
nanoflake array was synthesized, and then vertical graphene
(VG) nanoarray on carbon cloth was thickly coated by cross-
linked N-doped MoSe2 nanoflakes. This hierarchical architec-
ture constructed by integration of MoSe2 and VG is beneficial
for active area enlargement and charge transfer, thus leading
to the improvement of electrocatalytic activities. HRTEM
images illustrated the phase transformation of 2H-MoSe2 into
1T-MoSe2 with interplanar distance of 0.69 nm induced by
nitrogen introduction, indicating the coexistence of 2H-MoSe2
and 1T-MoSe2. LSV curves demonstrated that N-doped MoSe2/
vertical graphene (N–MoSe2/VG) with best HER activity is
able to deliver 10 mA cm−2 at a low overpotential of 98 mV,

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Figure 15.  a) Schematic representation of the synthesis of FeCoNi LDH nanotube arrays on Ni foam. b) Field emission SEM image. c) STEM and
EDX elemental mapping spectra. d) TEM image of FeCoNi LDH nanotube arrays. Reproduced with permission.[201] Copyright 2018, Nature Publishing
Group. e) SEM image of NiSe2-450 nanosheet arrays. f) Polarization curves for HER with different CF electrodes. g) Free energy (∆GH*) diagram for
hydrogen adsorbed states. Reproduced with permission.[91] Copyright 2016, Wiley-VCH.

outperforming MoSe2/VG and N-doped VG. DFT calculations
stated that bandgap of 1.22 eV for original MoSe2 was greatly
narrowed to 0.51 eV after N incorporation, indicating the
metallic property of N-doped MoSe2.[200] Consequently, simul-
taneously introducing nitrogen and 1T-phase MoSe2 is of great
significance to facilitate the exposure of active sites as well as
electron transfer, endowing the striking optimization of HER
performance.
6.1.3. Chalcogenide-Based Engineering
It has been extensively reported that transition metal dichalco-
genides such as sulfides and selenides can realize robust elec-
trochemical hydrogen evolution due to their favorable intrinsic
reaction kinetics.[91,201–203] For example, Wang and coworkers
combined 1T-phase MoS2 with Fe, Co, Ni–based sulfides for
exceptionally efficient overall water splitting.[201] In Figure  15,
Fe, Co, Ni–based hybrid nanotube arrays (FeCoNi-HNTAs)
on Ni foam render the increment of specific surface area and
support the exposure of active sites accordingly. The lattice
spacings of 0.29 and 0.27 nm are indexed to (Co, Fe, Ni)9S8 and
MoS2, respectively, confirming the concomitance of two types
of sulfides in this hybrid array. More importantly, the atomic
arrangement with tetragonal symmetry precisely reveals the
1T phase of MoS2 in this hybrid nanostructure by virtue of
aberration-corrected transmission electron microscopy (TEM)
characterizations. Cubic packing mode further determines the
presence of (Co, Fe, Ni)9S8. Adhesive force and contact angle
measurements imply the superhydrophilicity and superaero-
phobicity of FeCoNi-HNTAs, promoting water splitting applica-
tion. This extraordinary performance of FeCoNi-HNTAs with
the overpotentials of 58 and 184 mV to deliver 10 mA cm−2
for HER and OER, respectively, can be accredited to rapid
electron and mass transfer elicited by architectural nanotube
configuration, synergistic effect among the active centers of
(Co, Fe, Ni)9S8, and especially the metallic 1T-MoS2 with enor-
mous active edge sites. In situ XANES spectra determine that
there is no apparent peak shift for MoMo bond regardless of
applied potential, signifying the desirable stability of 1T-MoS2
in FeCoNi-HNTAs.[201]
To optimize electrocatalytic performance, creating active sites
is a promising approach. Especially, the regulation of surface
composition plays a pivot role in the generation of active sites.

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For example, selenium-enriched NiSe2 nanosheet array on
carbon fibers was used for efficient hydrogen generation.[91] As-
grown NiSe2-450 was annealed at 350 °C under argon atmos-
phere to prepare array with low selenium content (ANS350).
Notably, ANS350 array showed high overpotential of 152 mV to
realize 10 mA cm−2, while much lower overpotential (117 mV)
is sufficient for delivering the same current density with regard
to Se-rich NiSe2-450, suggesting that selenium plays a key
role in tuning electrocatalysis performance. More importantly,
the first-principles calculations were utilized for appraising
the performance of samples. Intriguingly, Se atom was settled
as the adsorption site due to its much lower hydrogen adsorp-
tion energy (ΔGH*) relative to that of Ni sites. The atom model
of Se-rich NiSe2-450 was imitated by subtracting one nickel
atom of terminal surface from cubic NiSe2, rendering the dis-
tinct reduction of ΔGH* from 0.13 to 0.08 eV.[91] Therefore, it is
systematically verified that the optimization of HER activity can
be governed via selenium incorporation.
Aside from improvement of hydrogen generation perfor-
mance, selenides can also be adept in catalyzing water oxida-
tion.[202,203] For example, nickel–iron diselenide–derived OER
electrocatalysts reached current density of 10 mA cm−2 at
an exceptionally low overpotential of 195 mV.[202] It is worth
mentioning that selenides tend to be converted into oxides or
(oxy)hydroxides during the electrochemical oxidation process.
Despite the instability of selenides under OER conditions, the
in situ transformation can be advantageous to build oxidized
electrocatalysts with abundant active sites.[202,203] As a regulator,
Se can also be applied for morphology management and lat-
tice structure tailoring of electrocatalysts, contributing to the
acceleration of water splitting reaction.[203,204] 3D Se–(NiCo)Sx/
(OH)x nanosheet array on Ni foam was synthesized for overall
water splitting.[203] 3D ultrathin nanosheets with high surface
area were acquired accompanied by the introduction of sele-
nium. Surprisingly, a great deal of crystal defects and lattice
distortion were created at the same time, bringing about the
significant promotion of water dissociation performance. As
expected, Se–(NiCo)S/OH displayed the greatest oxygen evolu-
tion activity and current density of 10 mA cm−2 was achieved at
a low overpotential of 155 mV, much superior to (NiCo)S/OH
and (NiCo)OH.[203] The conspicuous enhancement of activities
manifested that morphology optimization, lattice distortion,
and defect engineering elicited by Se incorporation played crit-
ical roles in boosting electrochemical water splitting.
6.1.4. Phosphorus Integration
It is demonstrated that combination of nonmetal phosphorus
atom (proton acceptor site) with metal atom can coopera-
tively moderate the interaction between catalyst and hydrogen
species, thus facilitating the generation of hydrogen during
electrochemical reaction.[67–70] Generally, transition metal phos-
phide arrays exhibited high activities toward HER.[204–211] For
instance, Ni5P4–Ni2P nanosheet (Ni5P4-Ni2P-NS) array con-
sisting of hexagonal Ni5P4 and Ni2P phases was fabricated by
direct phosphidation of hierarchical nickel foam for efficient
hydrogen evolution, reaching current density of 10 mA cm−2 at
a low overpotential of 120 mV.[205] The outstanding performance
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of biphasic phosphide array can be ascribed to 3D conductive
substrate integrated with perpendicularly aligned nanosheets,
facilitating the exposure of active sites, infiltration of electro-
lyte, and release of hydrogen bubbles as well as the synergism
of Ni5P4 and Ni2P.[205] Apart from excellent HER performance
of metal phosphides, they can also act as superior OER elec-
trocatalysts.[206–208] For example, mesoporous CoP nanorod
arrays by electrodeposition achieved current densities of 10 and
100 mA cm−2 at particular low overpotentials of 54 and 121 mV
for HER in basic solution, respectively.[206] More importantly,
it also manifests good capacity toward water oxidation, pro-
ducing current density of 10 mA cm−2 at a low overpotential
of 290 mV. Notably, some nanoparticles of several nanometers
were observed after water oxidation, which can be indexed to
the cobalt oxides/(oxy)hydroxides, indicating the leaching of
P from surface during OER process. Similar phenomenon
has been found for other phosphide electrocatalysts such
as single-crystalline cobalt phosphide nanowires and bime-
tallic (FexNi1−x)2P nanosheets.[207] The surface reconstruction
of phosphides tended to result in the formation of core–shell
structure, where the interior metal phosphides were covered
by exterior metal oxide/(oxy)hydroxide thin layer. Such special
configuration can not only satisfy the fast electron transfer in
conductive phosphides core, but also largely expedite the sur-
face reaction kinetics by virtue of oxides/(oxy)hydroxides with
transcendent OER activity, thus collaboratively contributing to
the dramatic enhancement of water oxidation.[206,207]
Besides, intentional introduction of foreign phosphorus
dopant can also greatly ameliorate electrocatalytic perfor-
mance.[208,209] For example, P-doped spinel nanowire arrays
presented current density of 20 mA cm−2 at a low overpoten-
tial of 260 mV for OER owing to the lowered adsorption energy
change of rate-determining steps and the accelerated water oxi-
dation process by phosphorus doping according to theory calcu-
lations.[208] Cobalt phosphoselenide array on exfoliated graphene
(EG) foils by hydrogenation of Co0.85Se nanosheets followed
by phosphidation (H–Co0.85Se|P) gave rise to the construction
of porous nanosheets with selenium vacancies surrounded by
phosphorus atoms.[209] Intriguingly, HER activities of Co0.85Se
and hydrogenated Co0.85Se (H–Co0.85Se) were both greatly
improved triggered by P doping (Figure 16), demonstrating the
positive effect of phosphorus for improved activities. DFT calcu-
lations stated that the hydrogen adsorption energies of Co0.85Se
and H–Co0.85Se were both largely decreased accompanied by
the introduction of phosphorus, indicating the indispensible
role of phosphorus in activity promotion. Moreover, much
lower adsorption energy of H–Co0.85Se|P relative to Co0.85Se|P
suggests that synergistic effect of Se vacancies and P substi-
tution can bring about the further advancement of hydrogen
evolution performance, which is cooperatively verified by DOS
calculations. There is substantial positive movement on p-states
for P atom of H–Co0.85Se|P compared with that of Co0.85Se|P,
demonstrating that strong interplay between Se vacancies and
adjacent P atoms may regulate the electronic structure of defec-
tive cobalt phosphoselenides, thus leading to the optimization
of HER activities.
It is worth mentioning that the integration of chalcogen
and phosphorus atoms can also bring about the innovation of
new class of electrocatalysts.[210,211] For instance, ternary CoPS
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Figure 16.  a) Schematic illustration for the synthesis of H–Co0.85Se|P. b,c) TEM and HRTEM images of H–Co0.85Se|P. d) Simulated scanning TEM image
of Co0.85Se. Reproduced with permission.[209] Copyright 2017, John Wiley and Sons. e) J–V curves after iR correction. f) Schematic representations for
hydrogen (H*) adsorption. Reproduced with permission.[210] Copyright 2015, Nature Publishing Group.

array on carbon fibers by thermal treatment of cobalt carbonate
hydroxide (precursor) in thiophosphate atmosphere was syn-
thesized for HER.[210] Raman spectra revealed the monophase
of cobalt phosphosulfide rather than mixture of phosphide
and sulfide, which was further confirmed by oxidized Co3+
state measured in XPS. What’s more, X-ray diffraction pat-
terns demonstrated the pure pyrite phase of samples due to the
well-matched peaks with that of simulated cubic CoPS. After
confirming the unique single phase of ternary phosphosulfide,
CoPS nanoplate array on carbon fibers exhibited the highest
HER activity and only overpotential of 48 mV was required to
reach current density of 10 mA cm−2, due to the inherent prom-
inent performance of CoPS and fast charge and mass transport
of the architectural array configuration with extensive active
area. Adsorption energy calculations stated that CoPS possessed
higher intrinsic HER activity compared to pyrite CoS2. More
importantly, hydrogen adsorption at neighboring phosphorus
site rendered the redox cycle between Co3+ and Co2+ during
sequential chemisorption at Co site, thus largely decreasing
the adsorption energy of hydrogen (ΔGH*). Therefore, it is
suggested that this monophase CoPS manifested superb HER
capacity owing to its distinctive electronic structure and coor-
dination surroundings.[210] Above all, nonmetal anion (N, P, S)
introduction can significantly contribute to improvement of
inherent conductivity, exposure of active sites, and decrement of
adsorption energy barriers, engendering the dramatic enhance-
ment of electrocatalysis capacity. It is generally accepted that
negatively charged N, P, and S atoms can function as adsorbed
sites of proton and greatly facilitate the sequential hydrogen
generation accordingly. Although these nonmetal elements
involving nitrides, phosphides, or sulfides also display high
activities toward water oxidation, they are prone to be oxidized
under high potential and converted into monophase metal
oxides/(oxy)hydroxides or core–shell configuration, which may

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act as the active species of OER. Therefore, the underlying OER
mechanisms are controversial and should be further subjected
to intensive investigation.
6.1.5. Phosphate-Based Engineering
It is well known that phosphate group assists the proton
transfer, thus greatly accelerating the proton coupling electron
transfer kinetics.[212] Hence, it is widely reported that metal
phosphate manifests outstanding OER activity in neutral and
alkaline media.[212,213] In 2008, Kanan and Nocera reported an
electrodeposited Co–Pi OER electrocatalyst in neutral media
for the first time, arousing the upsurge of developing robust
phosphate electrocatalysts.[212] Owing to the high surface area
and rapid charge transfer of 3D nanoarray electrodes, tremen-
dous progress of phosphate electrocatalysts has been made in
pace with the exquisite fabrication of architectural arrays.[16,213]
For instance, cobalt phosphate nanowire array on Ti mesh was
produced for efficient oxygen evolution in neutral solution,[213]
delivering current density of 10 mA cm−2 at a low overpotential
of 450 mV in 0.1 m phosphate buffer. Aside from high activity,
it also exhibited excellent electrocatalysis durability, due to the
solid attachment between catalysts and current collector. In
our group, a new type of Fe2PO5 polyhedron on nickel foam
has been produced for robust water oxidation in neutral and
basic media.[16] Nitrogen atoms and oxygen defects were simul-
taneously introduced into Fe2PO5 octahedrons (denoted as
N–Fe2PO5−x-OTs) during sequential ammoniation procedure,
contributing to the formation of unique lacunaris structure.
Electrochemical measurements revealed that N–Fe2PO5−x-OT
exhibits the highest OER capacity, achieving current density
of 10 mA cm−2 at fairly low overpotentials of 235 and 315 mV
in basic and neutral media, respectively. More importantly,
DFT calculations presented that (110) facets of Fe2PO5 mani-
fested much lower overpotentials compared to (010) planes,
suggesting the intrinsic high activity of (110) crystal planes.[16]
Furthermore, lowest overpotential of N–Fe2PO5−x implied that
the dual introduction of oxygen vacancies and nitrogen element
could also give rise to the significant enhancement of electro-
catalytic activity, which is collaboratively proved by accelerated
electron transfer on account of DOS calculations.
6.1.6. Metal Borate Engineering
Borate anion can also act as a feasible proton carrier and hasten
proton coupling electron transfer process, which is analogous
to the phosphate group.[214] It is noted that metal borate array
is regarded as a member of appropriate candidate for electro-
chemical water oxidation.[215,216] For instance, cobalt borate
(Co–Bi) array has been prepared by electrochemical alteration
of sulfide precursor.[215] The Co–Bi/CC exhibits excellent OER
performance in 0.1 m borate buffer (pH 9.2), generating current
density of 10 mA cm−2 at a low overpotential of 411 mV. Bime-
tallic Ni–Co–Bi nanoarray was prepared for the optimization of
electrocatalytic activity.[216] Only overpotential of 388 mV is able
to drive 10 mA cm−2 for Ni–Co–Bi, outperforming cobalt borate
without Ni substitution (η10  = 422 mV). Gibbs free energy
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calculations revealed that nickel introduction rendered the ΔG
variation decrement of the third step during the OER process,
where *O intermediates were combined with H2O molecules
and oxidized to *OOH sequentially, suggesting the faster water
dissociation kinetics induced by Ni substitution. Furthermore,
water oxidation can be largely activated by means of exterior
amorphous borate thin layer construction.[217] For instance,
NiFe LDH nanosheet array with NiFe borate shell exhibited
much higher OER activity relative to NiFe LDH and delivered
current density of 10 mA cm−2 at a low overpotential of 444 mV
in 0.1 m K–Bi buffer, due to the unique core–shell structure of
NiFe-LDH@NiFe–Bi composites.[217] It is instructive to note
that the phosphate or borate buffer largely retards the reaction
kinetics of electrocatalysts due to its poor mass diffusion ability.
Nevertheless, the much lower corrosiveness of (near) neutral
buffer relative to basic or acidic media is immensely beneficial
for the continuous operation of practical devices. To improve
the electrolysis efficiency of neutral electrolyzers, researchers
should dedicate themselves to rational design of electrocatalysts
or exploitation of feasible electrolytes.
6.2. Heterostructure Engineering
6.2.1. Metal-Based Heterostructures
It has been extensively reported that metal-based heterostruc-
tures can largely facilitate the adsorption of intermediates due
to the electronic interaction of interfaces in heterostructures
and synergistic effect of diverse components.[218,219] Notably,
the superb electric conductivity of metal is able to bring about
the acceleration of electron transfer.[219,220] Thus, electrocatalytic
activity can be greatly enhanced by means of metal-based heter-
ostructure construction. Due to the transcendent HER activity
of platinum metal, Pt has been utilized for fabricating com-
positional electrocatalysts.[221] For instance, platinum particles
with sizes of several nanometers implanted in CoS2 nanosheet
host as Pt-decorated CoS2 nanoarray on CC exhibited the
best HER ability among all samples, corresponding to merely
overpotential of 24 mV to deliver 10 mA cm−2 (Figure  17).[221]
Besides, it also manifested excellent OER activity, achieving
the same current density at a low overpotential of 300 mV.
Charge density calculations of interface showed that electrons
tend to accumulate on the surface of platinum, giving rise to
the generation of electron-deficient CoS2 and electron-rich Pt in
region of interface, which was further proved by d band center
downshift of platinum in Pt–CoS2 heterostructures compared
to single Pt (Figure 17).[222] Consequently, hydrogen adsorption
was optimized by virtue of electron-rich Pt. Meanwhile, elec-
tron-deficient CoS2 facilitated the formation of oxide species
on surface, which are responsible for the expedition of water
oxidization kinetics. Notwithstanding the superior activities of
Pt-based heterostructures, the valuableness and low reserves of
platinum largely hinder its practical application. Hence, a lot
of efforts have been made to explore other non–noble metal
alternatives for constructing pragmatic compositional electro-
catalysts.[218–222] For example, nonprecious copper nanodot–
embedded Ni3S2 nanotube arrays achieved current density of
10 mA cm−2 at a low overpotential of 128 mV, preponderating
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Figure 17.  a) TEM image, elemental mappings, and HRTEM image of Cu nanodot–decorated Ni3S2 nanotubes. b,c) Schematic illustration of water
adsorption, water activation, and hydrogen generation processes. Reproduced with permission.[222] Copyright 2018, American Chemical Society.
d) Differential charge density of Pt/CoS2 system. e) Projected density of states onto Pt d orbitals of Pt and Pt/CoS2. Reproduced with permission.[221]
Copyright 2018, Wiley-VCH.

over Cu nanodots and Ni3S2 nanotubes.[222] In Figure 16, Cu
nanodots with the average diameter of ≈10 nm were homoge-
neously dispersed on Ni3S2 nanotubes, which was cooperatively
verified by selected area electron diffraction (SAED) patterns
and element mappings. Charge density distribution calculations
demonstrated the evident increment in positive charge of Cu
after merging copper nanodots with Ni3S2, implying that H2O
molecules are prone to adsorb on the Cu surface of Cu/Ni3S2
heterostructure owing to the electrostatic attraction between
Cu and negatively charged oxygen atoms of H2O. Adsorption
energy calculations demonstrated that this heterostructure also
weakened the adsorption of hydrogen on Ni3S2. Collectively, the
combination of Cu and Ni3S2 contributed to the facilitation of
water adsorption as well as optimization of hydrogen adsorp-
tion, engendering the great promotion of HER performance.
Beyond single metal, MoNi4/MoO2 heterostructures on nickel
foam (denoted as MoNi4/MoO2@Ni) manifested the extraor-
dinary activity toward HER in basic media, delivering current
densities of 10 and 200 mA cm−2 at extremely low overpoten-
tials of 15 and 44 mV, respectively, as well as an exceedingly
low Tafel slope of 30 mV per decade, even outperforming
noble metal Pt electrocatalyst (32 mV per decade) due to the
synergism between MoNi4 and MoO2.[223] To understand the
mechanism in detail, theory calculations indicated that MoNi4
possessed the minimal energy barrier (0.39 eV) for the Volmer
step (H2O adsorption) among all samples, which is indeed less
than that of Pt (0.44 eV), indicating its exceedingly favorable
kinetics of the Volmer step. It should be mentioned that NiMo-
based catalysts can not only manifest superior activity toward
HER, but also act as robust OER electrocatalysts. However, the

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low conductivity of NiMo-based oxides limits the electrocata-
lytic application. To address this point, Ni4Mo nanoalloys were
homogeneously dispersed on the surface of NiMoOx nanowire
array on Ni foam by using NiMoO4 array as the precursor
through hydrogenation process in our group. To accelerate con-
tinuous electron transfer among Ni4Mo nanoalloys, NiMoOx
nanowires, and Ni foam, NC-encapsulated Ni4Mo/NiMoOx/Ni
array as the integrated array of NC/Ni4Mo/NiMoOx/Ni exhib-
ited superb activities toward water splitting.[224]
6.2.2. Mott–Schottky Electrocatalysts
Although various semiconducting metal oxides as promising
electrocatalysts have attracted considerable attention owing
to their low cost, abundance, and low toxicity,[12–15] the elec-
trocatalytic performance of these semiconductors was limited
owing to low conductivity. To address this drawback, the inte-
gration of metal and semiconductor as Mott–Schottky hybrids
was performed to promote HER and OER activities, endowing
the charge transport and reapportion impelled by the differen-
tiation of Femi level between metals and semiconductors.[225]
Consequently, HER can be improved due to dynamically
favorable metal sites with enriched electrons, while oxidized
semiconductor can act as highly active sites for OER.[225,226]
Inspired by the unique advantages of Mott–Schottky hetero-
junctions, CuO, Co3O4, and CuCo oxide nanowire arrays on
Ni foam have been treated through hydrogenation approach,
resulting in the formation of nanoalloys on the surface of dif-
ferent oxide arrays (Cu/CuOx, Co/CoOx, and CuCo/CuCoOx) as
Mott–Schottky electrocatalysts. To build the highway of electron
transfer among nanoalloys, oxides, and Ni foam, Mott–Schottky
catalysts have been encapsulated by NC layer as the integrated
arrays.[227] Impressively, NC/CuCo/CuCoOx arrays showed the
highest electrocatalytic performance, acquiring current density
of 10 mA cm−2 at small overpotentials of 112 and 190 mV for
HER and OER, respectively. Moreover, it was employed as both
cathode and anode to assemble an overall water splitting system
and only applied voltage of 1.53 V is able to drive 10 mA cm−2.
The outstanding activity of NC/CuCo/CuCoOx array can be
assigned to unimpeded charge transport induced by distinc-
tive Mott–Schottky configuration, the high conductivity of
carbon layer, and hierarchical array with high surface area. In
addition, nickel nanoparticles were embedded in amorphous
NiO nanosheet array, suggesting the successful construction
of Mott–Schottky heterostructure for overall water splitting.[226]
Intriguingly, Ni/NiO heterojunctions delivered current density
of 10 mA cm−2 at a low overpotential of 35 mV for HER under
light illumination, evidently outperforming the activity under
dark situation. Besides, OER activity of Ni/NiO was also greatly
improved after exerting light irradiation and the enlargement
of oxidation peak area signifies that illumination can assist
the oxidation of Ni2+ to Ni3+/4+. The mechanism of significant
augment for HER and OER activity was explicitly illustrated.
As a semiconductor, NiO generated electron–hole pairs upon
irradiation. Sequentially, the photogenerated electrons were
transferred to active nickel metal, leading to the acceleration of
HER kinetics. However, photogenerated holes inclined to facili-
tate the formation of Ni3+/4+ with high valence state, which is
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recognized as highly active center for OER.[226] Although the
fabrication of metal-based heterostructures is of great signifi-
cance in charge migration manipulation and water dissociation
kinetics optimization, there is a lack of definite elaboration on
the linkage of interfaces. In other words, it is still ambiguous
that metal atoms are coordinated with host compound in the
form of chemical bond or they are simply combined by means
of molecular force such as van der Waals force. Thus, the fine
structure of metal-based hybrids should be systematically inves-
tigated and it is conducive to comprehend the interaction of
interfaces at atomic scale.
6.2.3. Carbon-Based Heterostructures
Owing to the exceptional electric conductivity of carbon, the
electron migration on the interfaces can be significantly stim-
ulated by the encapsulation of carbon layer for the integrated
electrocatalysts.[227,228] Notably, it can hinder the aggregation of
nanocrystal and structure collapse resulting from intense gas
emission and corrosion by electrolyte during electrochemical
reaction, contributing to the sufficient availability of active
sites as well as considerable amelioration of electrolysis sta-
bility.[124,229] Therefore, the fabrication of carbon-encapsulated
heterostructures as typical carbon-based heterostructure arrays
is considered as a potent strategy for propelling water splitting
reaction.[227] For example, carbon shell–coated Ni–Co nanowire
array on carbon fiber was produced for water oxidation.[229] The
mesoporous nanowires with rough surface are comprised of
accumulated nanoparticles, covered by amorphous carbon thin
layer of several nanometers. The enhanced activity and dura-
bility are accredited to the mesoporous nanowire with high
surface area and conductive carbon layer, expediting the elec-
tron transfer on the interface and preventing the caving of the
arrays. In our group, NC layer was implanted on the surface of
the integrated NiCu–NiCuN array that is composed of nickel–
copper nanoalloys and nickel–copper nitrides, presenting
outstanding electrocatalytic performance.[228] The prominent
performance of NC–NiCu–NiCuN heterostructure array can
be assigned to abundant active sites and “highway” of electron
transport built by ultrathin NC layer, facilitating the fast elec-
tron transfer throughout the whole system.
Apart from carbon thin layer coverage, carbon-encapsulated
heterostructures can also be constructed by embedding active
materials into carbon carriers.[230,231] For instance, a series of
graphitic carbon nanosheet (CNS) nanoarrays with metal (Mo,
Wo, Ta, Nb) carbide implantation have been fabricated by
means of a general salt-templating tactic, giving rise to the con-
struction of carbide nanoparticle–anchored CNS heterostruc-
tures, thus displaying excellent HER performance owing to
the solid interaction between substrate and array, as well as the
unique configuration of carbon-encapsulated heterostructures
with intrinsic high electric conductivity and no agglomerate
carbide nanocrystal.[230]
Embedding catalysts into CNTs with great conductivity is also
deemed as an effective strategy for the promotion of electrocata-
lytic activities due to the strong interplay between nanoparti-
cles and CNTs, leading to the optimization of local electronic
structure and enrichment of active sites.[232,233] For example,
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cobalt-embedded NC nanotube (NCNT) array was fabricated by
the pyrolysis of ZIF thin film on melamine sponge.[232] Such
unique configuration can substantially promote the accessi-
bility of active sites, which is commonly hampered for aggre-
gated NCNTs. Moreover, Co species were anchored on the apex
of NCNTs, providing more active sites for electrocatalysis. LSV
measurements revealed that MSZIF-900 possessed the highest
activities relative to other samples, reaching current density of
10 mA cm−2 at the overpotentials of 233 mV and 337 mV for
HER and OER, respectively. DFT calculations demonstrated that
the optimization of OER kinetics was actualized by embedding
Co atom into NC matrix. Therefore, the activity improvement
can be assigned to the distinctive hierarchical heterostructures.
Similarly, NiCo alloy–incorporated NCNT (NiCo@NCNT)
heterostructure on Ni foam has been synthesized as an efficient
oxygen electrocatalyst.[233] The better OER activity of NiCo@
NCNTs relative to pure NCNTs was proposed as a result of
apical NiCo alloys in NCNTs, contributing to the generation of
supplemental active sites with electrolyte accessibility.
6.2.4. Chalcogenide-Based Heterostructures
Construction of heterogeneous chalcogenides has been proved
to play a pivotal role in kinetics acceleration, electronic struc-
ture optimization, and conductivity amelioration, engendering
the enormous improvement of electrocatalytic activity.[234–237]
Due to the dynamical favorableness of MoS2 with active edge
sites,[23] tremendous progress has been made by building
Mo-based chalcogenide heterostructures.[23,234–237] In our
group, oxygenated CoS2–MoS2 (O–CoMoS) perpendicularly
aligned nanosheet heteroarray was produced by sulfidation of
polyoxometalate precursors.[234] Notably, the appreciable electron
paramagnetic resonance signal of O–CoMoS was in sharp con-
trast with that of MoS2, implying the emergence of massive sulfur
vacancies induced by cobalt and molybdenum amalgamation.
O–CoMoS heterostructure achieves current density of
10 mA cm−2 at low overpotentials of 97 and 272 mV for HER
and OER, respectively. The marvelous enhancement of elec-
trocatalysis performance was ascribed to the vacancy-enriched
O–CoMoS heterostructure with disordered crystal configura-
tion, endowing abundant active sites, large active area, and full
exploitation of active interfaces. It is worth mentioning that the
much greater electrochemical durability of O–CoMoS compared
to MoS2 manifests the positive role of oxygen incorporation in
stability improvement. Bao and coworkers reported a perpen-
dicularly aligned MoS2/MoC heteroarray on CFP for enhanced
hydrogen generation.[235] It exhibited considerably higher HER
activity than single-constituent counterparts, realizing cur-
rent density of 10 mA cm−2 at a low overpotential of 63 mV.
The first-principles calculations indicated that the outstanding
performance of MoS2/MoC heterostructures was assigned to the
dynamically desirable Mo–S–C sites with near-optimal hydrogen
adsorption energy.
Owing to the superior conductivity of cobalt sulfide, it is very
promising to boost electrocatalysis capacity by building cobalt-
involved chalcogenide heterostructures.[236] For instance, Co9S8-
grafted Ni3Se2 nanoarray was supported on exfoliated graphene
(denoted as EG/Ni3Se2/Co9S8).[236] Small Co9S8 nanosheets were
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densely aligned on surface of Ni3Se2 with sizes of hundreds
of nanometers and the intimate contact between Ni3Se2 and
Co9S8, signifying the construction of architectural nanoarray
(Figure 18). To understand the mechanism of the considerable
augment of HER performance by DFT calculations, the dynam-
ically favorable property of Ni3Se2/Co9S8 heterostructures was
elucidated due to the lower hydrogen adsorption energy rela-
tive to Ni3Se2 or Co9S8. In addition, the less electron accept-
ance of sulfur and nickel atoms at interface of heterostructures
indicated the intense electronic interplay between Ni3Se2 and
Co9S8, collaboratively verified by the appearance of NiS bonds
in EXAFS spectrum of Ni3Se2/Co9S8. As a result, the superb
activity of EG/Ni3Se2/Co9S8 was attributed to hierarchical con-
figuration and strong electronic interplay of interface, leading
to the dramatic expedition of electrocatalysis kinetics.
6.2.5. (Hydr)oxide-Based Heterostructures
Among different electrocatalysts, (hydr)oxide is of great signifi-
cance to promote water oxidation due to its favorable adsorption
of oxygenated intermediates.[238] To optimize the electrocatalytic
activity, (hydr)oxide-based heterostructures are widely utilized
for water splitting.[239–241] For instance, Ni–Fe–OH@Ni3S2
arrays presented large current density of 1000 mA cm−2 in
KOH solution owing to electron transfer from Ni2+ to Ni3+.[241]
To construct hierarchical array, a uniform thin layer of vertically
aligned NiCo2O4 nanoflakes is in situ grown onto Ni foam by
hydrothermal and annealing approaches before the topmost
NiFe nanosheets are electrodeposited, resulting in the syn-
thesis of NiFe/NiCo2O4/Ni electrodes. Notably, NiFe/NiCo2O4/
NF arrays exhibited a low onset overpotential of 240 mV and
only overpotential of 340 mV was required to realize exceed-
ingly high current density of 1000 mA cm−2, much superior to
counterparts with single component. The superb performance
of NiFe/NiCo2O4 heterostructure was accredited to substantial
augment of surface area and active sites evoked by the dis-
tinctive 3D multilayer architecture, as well as the synergism
between NiCo2O4 and NiFe LDH. Similarly, FeOOH-interca-
lated CuCoOx (CuCoOx/FeOOH) nanowire array on Ni foam
presented the highest OER performance, achieving current
density of 309 mA cm−2 at a low potential of 1.55 V vs reversible
hydrogen electrode due to large surface area for electrocatalytic
sites, abundant pores for fast electrolyte access, efficient charge
transfer, and strong coupling between CuCoOx and FeOOH
components.[242]
It is instructive to note that hydroxides can also function as
promoters that facilitate the water adsorption and sequential
dissociation, thus engendering the significant expedition of
HER kinetics in alkaline media.[243] Consequently, hydroxide-
based heterostructures can also make a great contribution to
optimization of HER activity.[241–243] For example, Ni(OH)2
nanoparticle–anchored ultrathin MoS2 nanosheet array
grown on CC with the intimate attachment between different
constituents in this heterostructure has been designed for effi-
cient hydrogen evolution.[243] Ni(OH)2/MoS2 heterostructures
exhibited much higher HER activity than pristine MoS2, deliv-
ering current density of 10 mA cm−2 at a low overpotential of
80 mV. Adsorption energy calculations indicated that the rather
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Figure 18.  a) Polarization curves of EG, EG/Ni3Se2, EG/Co9S8, EG/Ni3Se2/Co9S8, and Pt/C for the HER. b) DFT-calculated free energy diagrams of
the HER for Co9S8, Ni3Se2, and Ni3Se2/Co9S8 and c) population distribution on Co9S8, Ni3Se2, and Ni3Se2/Co9S8 hybrids. Reproduced with permis-
sion.[236] Copyright 2018, American Chemical Society. d) Electronic energy changes for the formation of S defects and CHx substitutions on S edge of
MoS2. Reproduced with permission.[235] Copyright 2017, American Chemical Society. e,f) The mechanisms of the dissociation of H2O, OH, and OOH
intermediates on MoS2/Ni3S2 heterostructures. Reproduced with permission.[237] Copyright 2016, Wiley-VCH.

high energy barrier for water dissociation largely restricted the
generation of H*, resulting in the sluggish kinetics of MoS2.
However, cleavage of HOH bond was largely accelerated on
highly active Ni sites and much lower H2O adsorption energy
of Ni(OH)2/MoS2 relative to that of Ni(OH)2 was ascribed to
the strong synergistic effect at interfaces, greatly stimulating
the sequential hydrogen release on S sites of MoS2. Notwith-
standing the superb performance of (hydr)oxide-based hetero-
structures, the intrinsic mechanism of OER improvement has
been rarely investigated and it should be further expounded by
virtue of DFT calculations.
6.2.6. Other Heterostructures
In particular, the conductive polymers such as polyaniline
(PANI) owing to high conductivity and adhesion, and robust
stability were also exploited for building heterostructures with
conspicuous activities.[244,245] Among various inorganic elec-
trocatalysts, transition metal hydroxide–based nanoarrays have
been widely investigated as OER catalysts.[55–65] However, there
are few reports on transition metal hydroxide–based nanoarray
as electrocatalyst for HER. Interestingly, the integration of
PANI and Co(OH)2 nanosheets on Ni foam presented a low

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onset potential (50 mV) and a low Tafel slope of 91.6 mV per
decade as well as outstanding durability owing to the enhanced
electronic conductivity by the introduction of PANI. To deter-
mine the origin of superior electrocatalytic activity, Gibbs free
energies (ΔGH*) of PANI, Co(OH)2, and the Co(OH)2@PANI
hybrid were calculated by the DFT technique, indicating the
lowest ΔGH* value of Co(OH)2@PANI in comparison with
PANI and Co(OH)2 and facilitating the H adsorption and the
optimization of HER.[244] Beyond hydroxide-based arrays, the
hybrid arrays of CoP nanowire nanoarray by coupling of PANI
nanoparticles achieved superior HER activity.[245] The authors
presumed that proton is prone to coordinate with one water
molecule in aqueous solution, resulting in the formation of
hydronium cation (H13O6+) and sluggish reduction of proton
into hydrogen. However, with the assistance of protonated
amine group in PANI, hydrogen ions can be easily detached
from H13O6+ and captured by PANI. Moreover, DFT calcula-
tions demonstrated that PANI/CoP hybrid engendered the
evident decrement on Gibbs free energy variation (ΔG) of the
process where H+ is migrated to active CoP, contributing to
the expedition of sequential hydrogen evolution. The near-zero
value of hydrogen adsorption energy further substantiates the
kinetics optimization promoted by this unique heterostructure.
6.3. Defect Engineering
Defect engineering is universally acknowledged as a signifi-
cant and effective strategy to promote the sluggish reaction
kinetics, which greatly promotes the exposure of active sites,
optimization of intrinsic kinetics, enlargement of active area,
and improvement of electric conductivity, thus bringing out
the remarkable enrichment of water splitting capacity.[246,247]
In this typical strategy, oxygen vacancies are the most popular
anion vacancies in transition metal oxides owing to low forma-
tion energy.[247] For example, metal oxides/(oxy)hydroxides with
massive oxygen vacancies presented much superior activities
compared to untreated samples.[248–252] Vacancy-incorporated
CoOOH (Vo-CoOOH) nanotube array has been designed
toward efficient OER.[248] With the introduction of oxygen
vacancies (Vo), Vo-CoOOH nanotubes were densely covered
by a great deal of nanosheets and nanosized pores were gen-
erated at the same time, indicating much higher surface area
of Vo-CoOOH relative to original CoOOH. In alkaline media,
the overpotential at current density of 10 mA cm−2 was low-
ered by 40 mV after deficiency formation, suggesting that Vo
plays a positive role in steering OER activities. Intriguingly, a
five-step OER mechanism was proposed, where two adsorbed
sites were involved. Specifically, one H2O molecule was prefer-
ably adsorbed on Co site near Vo due to facilitated adsorption
induced by vacancy introduction, and then hydrogen atom of
adsorbed H2O was transferred to adjacent absorbed *O sites.
In this way, H2O dissociation can be divided into two steps and
the rate-limiting step was converted to the step where *OH was
oxidized to *O, leading to substantial reduction of overpoten-
tial. In addition, DOS calculations were utilized for analyzing
the underlying mechanism of *O adsorption manipulated by
vacancies. The unpaired electrons of Vo-COOH render the for-
mation of impurity d state. Consequently, filling of antibonding
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state was reduced, giving rise to the intensification of *O
adsorption. Generally, doping strategy is regarded as a versa-
tile way to optimize the electrocatalytic activity by modulating
the conductivity and electronic structure of architectural arrays.
Motivated by this point, lower valence-state Zn-doped CoOOH
(Zn–CoOOH) nanotube array by experimental results and
DFT calculations induced lattice distortions, facilitated proton
transfer and dissociation, and excited the inert OER reaction,
presenting an efficient OER with a large current density and
a small Tafel slope of 44 mV per decade.[249] After Zn doping,
the existence of Vo along with Jahn–Teller effect improved the
lift degeneracy of the t2g and eg orbitals, conducting the dz2
orbital partially occupied, thus facilitating the adsorption of
water to yield a lower theoretical overpotential.[249] Meanwhile,
the formed hydrogen bonds (O┈HOad) in Zn–CoOOH array
can trigger the dual activity center to facilitate proton transfer
and dissociation, leading to a fast kinetics OER pathway. Engi-
neering oxygen vacancy on NiO nanorod arrays simultane-
ously can enhance electronic conduction and HER reaction
kinetics, delivering current density of 10 mA cm−2 at a low
overpotential of 110 mV.[250] Beyond anion vacancies, there is
another promising way to regulate the activities of electrocata-
lysts by use of cation vacancies owing to various electron and
orbital distributions.[247] For instance, A-site cation–deficient
La1−xFeO3−δ perovskites presented excellent OER activities
owing to the formation of oxygen vacancies (O22−/O− species)
and a small number of Fe4+ species with an optimal eg orbital
filling (t2g3eg1).[251] However, few reports have been focused on
cation-deficient nanoarray architectures. Interestingly, there is
enough space to explore the construction of defect-rich archi-
tectural arrays with high electrocatalytic activities. Based on the
above-mentioned analysis, the anion and cation vacancies with
the unsaturated sites could enhance the electrical conductivity
and charge transfer, and optimize the adsorption of water as
well as improve the electrocatalytic performance. Above all,
defect engineering plays a valuable role in charge transport and
inherent kinetics manipulation, contributing to the enormous
improvement of electrocatalytic activities. Apart from (oxygen,
sulfur, selenium, etc.) vacancies, the other defects, such as lat-
tice dislocations and expansion and distortion, stepped sur-
faces, and boundaries, may also be favorable to enhance the
electrocatalytic performance. However, it is a big challenge to
explore a general strategy for the fabrication of defects confined
in architectural arrays with precise control of various defects.
What’s more, the advanced characterization techniques are
required to identify various defects and gain more information
about defects as well as understand the relationship between
defect structure and performance.
7. Mechanism Decipherment
Generally, catalytic reaction takes place on the surface of elec-
trocatalysts, indicating that the geometric structure can signifi-
cantly influence the electrocatalytic performance of catalysts.
As a result, it is imperative to track the changes of the surface
in architectural arrays during electrochemical reaction process,
understanding the in-depth mechanisms and functionalities
of promising electrocatalysts. Notably, operando analysis can
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www.advancedsciencenews.com
provide profound insights into the underlying reaction mecha-
nisms, shedding light on the dynamic variation of electronic
configuration and coordination surroundings during water dis-
sociation process.[252,253] For example, hierarchical binary Ni–
Co oxide nanosheet array on FTO has been produced toward
OER.[252] In situ EXAFS spectra of Ni K-edge reveal the for-
mation of NiOOH and distortion of octahedral coordination
during water oxidation process, while no apparent change of
Co K-edge plots was recognized regardless of electrochemical
reaction. Fourier transform spectra indicated the tetrahedral
coordination of nickel with oxygen due to single peak at 2.5 Å
derived from adjacent metal around Ni. However, there are two
peaks of Co K-edge that are, respectively, located at 2.5 Å and
3.0 Å, implying the octahedral coordination of Co and O. More
importantly, operando EXAFS spectra suggested the partial
oxidation of nickel cations and no evident alteration of coor-
dination structure of cobalt during OER. Based on the above
discussion, it is comprehensively concluded that NiOOH acted
as the real active sites in this Ni–Co oxide electrocatalyst. For
the advanced technology, X-ray absorption spectroscopy is a
promising way to determine the geometric or electronic struc-
ture of catalysts. For instance, time-resolved X-ray absorption
spectroscopy has been employed to capture the dynamic local
electronic and geometric structures of Ba0.5Sr0.5Co0.8Fe0.2O3
nanocatalysts. Notably, flexible perovskite structures with a
large oxygen vacancy content favored the operando forma-
tion of a highly OER-active oxy(hydroxide) surface layer.[253] To
extensively investigate the details, it is necessary to adopt the
advanced measurement and characterization technologies to
grasp these changes and grant clear knowledge to researchers
about the identification of various changes in reaction process.
X-ray photoelectron spectroscopy is a surface-sensitive spectro-
scopic technique, evaluating the chemical and electronic states
of the elements, especially detecting the extra new peaks, or
the slightly shifting peaks within the catalysts. Raman spec-
troscopy is also a useful tool to evaluate defects in materials.
To capture the origin of robust performance of Fe/V codoped
Ni(OH)2 catalysts, in situ electrochemical Raman spectroscopy
and in situ X-ray absorption spectroscopy have been adopted,
capturing the clear changes in local atomic environments and
electronic structures of Ni3Fe0.5V0.5.[194] From the analysis of
electrochemical Raman spectra, the enhanced performance is
ascribed to the formation of NiIII–OOH phase in Fe/V codoped
Ni(OH)2.[194] With regard to defect-rich catalysts, electron spin
resonance is a promising technique to track the changes of the
surface in defect-rich arrays. Beyond these measurement and
characterization technologies, theoretical calculations could
be conducted to have in-depth understanding on the enhance-
ment of electrocatalytic activity of the architectural arrays.
With recent advances in in situ techniques, it is possible to
conduct simultaneously property measurement and structural
imaging in the electron microscope, correlating the measured
physical, chemical, and mechanical properties with local struc-
tures and structural evolution of materials. Especially, in situ
electron microscope also provide a platform for visualizing
and manipulating individual nanomaterials and characterizing
their properties. Therefore, it is of great significance to use
operando spectra for identifying the genuine active centers of
electrocatalysts.
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8. Conclusion and Future Perspectives
As an indispensible member of energy conversion systems,
electrocatalytic water splitting is acknowledged as an ideal
methodology for producing carbon-free and high-energy
hydrogen fuels under circumstance of no collateral contami-
nation. To accomplish the practical application of hydrogen
manufacturing, it is very important to develop efficient and
stable electrocatalysts. In recent years, nanoarray architectures
exhibited marvelous electrocatalytic activity and durability
owing to their distinctive hierarchical configuration with high
surface area, a great deal of active sites, facile electron migra-
tion and mass transport, intimate interface contact, and fast gas
bubble release.
Herein, we comprehensively elaborate the progress of
architectural nanoarray starting with the introduction of fun-
damental principles of water splitting, catalyst categories, and
synthetic approaches of different electrocatalysts. Then we
place great emphasis on activity regulation strategies of various
nanoarrays. Specifically, we first systemically elucidate the per-
formance optimization triggered by compositional tuning, i.e.,
foreign element introduction. With regard to metal element
incorporation, the synergism between varied metal cations
usually promotes the electronic framework modulation and
moderation of intermediates’ adsorption, giving rise to the
great acceleration of reaction kinetics. Similarly, promotion of
electrocatalytic activity can also be realized via introducing non-
metal elements (N, P, S, B, etc.), which contributes to the tre-
mendous amelioration of electric conductivity and unhindered
charge transport. More importantly, negatively charged N, S, or
P atoms can act as ideal active centers for proton adsorption,
bringing about the dynamical optimization of HER. As for
OER, the unique core–shell structure derived from surface elec-
trochemical oxidation may account for the fast electron migra-
tion of interior region and favorable water dissociation of sur-
face. It should be mentioned that porous structure is inclined
to be constructed induced by nonmetal element substitution,
engendering the expansion of surface area and exposure of
active sites. Then, we thoroughly expound the activity regula-
tion of architectural array in the manner of heterostructure fab-
rication. Strikingly, the strong electronic interplay at interfaces
of heteroarray plays a crucial role in redistributing electron
density, leading to the facilitation of intermediates’ adsorption
and expedition of electron transfer at interfaces. The syner-
gistic effect between varied constituents is also conducive to
performance improvement of hybrid electrocatalysts. Notably,
3D hierarchical configuration can be developed along with
the construction of heterostructures. It possesses high surface
area and a great number of active sites, which is immensely
beneficial for electrocatalysis capacity enhancement. Due to
the extensive application of defect engineering in energy con-
version systems, we also interpret the positive effect of defect
engineering in steering water dissociation activity. Specifically,
intentional incorporation of various defects can stimulate the
optimization of inherent kinetics, enrichment of active sites,
and augment of active area, thus making great contribution
to expedition of water splitting reaction. Last but not the least,
we briefly introduce the operando characterization technolo-
gies for the mechanism elaboration. It is worth mentioning
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
that in situ spectroscopy can be a paramount technique for the
decipherment of genuine active sites, providing deep insights
into the electrocatalysis reaction process at atomic level. Above
all, we not only perceive the origin of activity optimization by
analyzing experimental results, but also profoundly dissect the
inherent mechanism by virtue of theory calculation as well as
sophisticated spectroscopy.
Despite extensive progress on nanoarray architectures, it is
still a big challenge to enhance the electrocatalytic performance.
Several steps could be further taken toward rational design of
nanoarray architectures for efficient and stable electrocatalytic
water splitting. First, morphology engineering is a promising
direction to manipulate the composition, morphology, size,
interface, and nanostructure by effective and advanced syn-
thesis approaches, improving the specific surface area and cata-
lytic active sites, and enhancing electrochemical performance.
With regard to various nanoarrays in a controllable manner,
it is difficult but urgently required to accurately identify
nanoarray architectures on conductive substrates (e.g., metal
mesh, metal foam, carbon paper, carbon cloth, etc.). Second,
electronic structure or electrical conductivity is effectively regu-
lated by the introduction of dopants or defects, understanding
the role of the dopants or defects by controlling the concentra-
tion of the dopants or defects. Especially, the main purposes
of electronic structure manipulation are to increase the elec-
trical conductivity, catalytic active sites, and intrinsic activity of
each active site, facilitate charge transfer, and promote catalytic
activity. Third, interface or heterostructure engineering is an
effective approach to produce novel nanoarray architectures
with diverse scaffolds. It is very important to apply innova-
tive approach for rational design and synthesis of nanoarray
architectures, maximizing the exposure of active sites and
intrinsic activity, regulating the electrical behavior and electron
transfer throughout the whole system, and the synergistic effect
between the components, among others.
Although extraordinary achievement has been made for
architectural nanoarray via exquisite regulation of macroscopic
morphology, crystal structure, electronic configuration, electric
conductivity, and active site availability, it is still a big challenge
to develop earth-abundant and efficient electrocatalysts suitable
for large-scale manufacturing. Therefore, tremendous efforts
should be made to further enhance the activity and stability
of HER and OER electrocatalysts. To accomplish the goal of
hydrogen fuel application, we present several perspectives for
research tasks in the future: i) More attention could be paid
to the performance and durability at high current for meeting
the actual demand of large-scale application. Due to the indis-
pensability of superior stability in practical manufacturing, the
origin of activity degradation (such as electrolyte corrosion,
catalyst secession, etc.) should be systematically investigated.
ii) The subtle contrivance of satisfactory electrocatalysts can
only be effectuated on the premise of explicit comprehen-
sion of the underlying reaction mechanism. It is essential to
exert theoretical calculation to simulate the reaction pathway
of HER and OER. The operando characterizations are also of
great significance for elucidation of mechanism, revealing the
real active centers and valence-state transformation during
electrochemical reaction process. iii) Notwithstanding the
thrilling accomplishment of electrocatalyst development, few
Adv. Funct. Mater. 2019, 29, 1808367 1808367  (35 of 39)
www.afm-journal.de
researchers devote themselves to activity and stability evalu-
ation in industrial alkaline electrolyzer, where hydrogen fuels
are usually generated in concentrated potassium hydroxide
solution with high temperature. Such harsh conditions will
largely restrain the normal operation of electrochemical reac-
tion and it may result in the unserviceability of catalysts. There-
fore, water splitting performance of electrocatalysts should also
be comprehensively appraised in view of practical utilization.
iv) Nanoarray architectures are generally fabricated on hierar-
chical substrates such as metal foam, carbon fiber cloth, and so
forth. Notably, the activities of integrated electrodes are greatly
influenced by the thickness, density, and roughness of conduc-
tive supports, leading to ambiguous judgment for the intrinsic
activities of electrocatalysts. To accurately evaluate the electro-
catalysis capacity of architectural arrays, the unified standard of
various collectors should be established.
Above all, the exploration of practicable nanoarray
architectural electrocatalysts has emerged as a hot research topic
in electrochemical water splitting systems. With the concerted
efforts made by the scientists all over the world, we believe that
there will be proper development on nanoarray architectures as
promising electrocatalysts, promoting substantial contribution to
the advancement of the industrial utilization of hydrogen fuels.
Acknowledgements
This work was supported by National Science Foundation of China
(No. 51672034), the Fundamental Research Funds for the Central
Universities (Grant No. DUT18RC(3)013), the Swedish Research Council
(2017-00935), the Swedish Energy Agency, and the K&A Wallenberg
Foundation.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
earth-abundant electrocatalysts, electrocatalytic water splitting,
electrochemical energy, modulated strategies, nanoarray architectures
Received: November 25, 2018
Revised: December 27, 2018
Published online: January 21, 2019
[1] N. T. Suen, S. F. Hung, Q. Quan, N. Zhang, Y. J. Xu, H. M. Chen,
Chem. Soc. Rev. 2017, 46, 337.
[2] a) Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff,
J. K. Norskov, T. F. Jaramillo, Science 2017, 355, eaad4998;
b) J. D. Benck, T. R. Hellstern, J. Kibsgaard, P. Chakthranont,
T. F. Jaramillo, ACS Catal. 2014, 4, 3957.
[3] a) C. Tang, H. Wang, Q. Zhang, Acc. Chem. Res. 2018, 51, 881;
b) M. C. Luo, S. J. Guo, Nat. Rev. Mater. 2017, 2, 17059.
[4] L. Schlapbach, A. Züttel, Nature 2001, 414, 353.
[5] J. Luo, J.-H. Im, M. T. Mayer, M. Schreier, M. K. Nazeeruddin,
N.-G. Park, S. D. Tilley, H. J. Fan, M. Grätzel, Science 2014, 345,
1593.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[6] Y. Shi, B. Zhang, Chem. Soc. Rev. 2016, 45, 1529.
[7] X. Zou, Y. Zhang, Chem. Soc. Rev. 2015, 44, 5148.
[8] a) Z. Huang, J. Wang, Y. Peng, C. Jung, A. Fisher, X. Wang,
Adv. Energy Mater. 2017, 7, 1700544; b) X. Zhang, J. Li, Y. Yang,
S. Zhang, H. Zhu, X. Zhu, H. Xing, Y. Zhang, B. Huang, S. J. Guo,
E. Wang, Adv. Mater. 2018, 30, 1803551.
[9] a) K. Wang, B. Huang, F. Lin, F. Lv, M. Luo, P. Zhou, Q. Liu,
W. Zhang, C. Yang, Y. Tang, Y. Yang, W. Wang, H. Wang, S. Guo,
Adv. Energy Mater. 2018, 8, 1801891; b) J. Zhao, F. Rong, Y. Yao,
W. Fan, M. Li, Q. Yang, J. Energy Chem. 2018, 27, 1261.
[10] a) J. Zhang, J. Liu, L. Xi, Y. Yu, N. Chen, S. Sun, W. Wang,
K. M. Lange, B. Zhang, J. Am. Chem. Soc. 2018, 140, 3876;
b) M. Kiani, J. Zhang, Y. Luo, C. Jiang, J. Fan, G. Wang, J. Chen,
R. Wang, J. Energy Chem. 2018, 27, 1124; c) Z. Liu, Y. Gao, J. Wang,
Y. Yao, X. Chen, J. Energy Chem. 2018, 27, 1402.
[11] C. Tan, Z. Luo, A. Chaturvedi, Y. Cai, Y. Du, Y. Gong, Y. Huang,
Z. Lai, X. Zhang, L. Zheng, X. Qi, M. H. Goh, J. Wang, S. Han,
X. J. Wu, L. Gu, C. Kloc, H. Zhang, Adv. Mater. 2018, 30, 1705509.
[12] a) L. Yan, L. Cao, P. Dai, X. Gu, D. Liu, L. Li, Y. Wang, X. Zhao,
Adv. Funct. Mater. 2017, 27, 1703455; b) Y. Tang, Y. Yang, W. Wang,
H. Wang, S. J. Guo, Adv. Energy Mater. 2018, 8, 1801891; c) H. Zhu,
G. Gao, M. Du, J. Zhou, K. Wang, W. Wu, X. Chen, Y. Li, P. Ma,
W. Dong, F. Duan, M. Chen, G. Wu, J. Wu, H. Yang, S. J. Guo, Adv.
Mater. 2018, 30, 1707301.
[13] X. Wang, L. Yu, B. Y. Guan, S. Song, X. W. D. Lou, Adv. Mater.
2018, 30, 1801211.
[14] a) Y. Gu, S. Chen, J. Ren, Y. A. Jia, C. Chen, S. Komarneni, D. Yang,
X. Yao, ACS Nano 2018, 12, 245; b) H. Xu, L. Ma, Z. Jin, J. Energy
Chem. 2018, 27, 146; c) S. Li, W. Wang, H. Duan, Y. Guo, J. Energy
Chem. 2018, 27, 1555.
[15] a) G.-F. Chen, T. Y. Ma, Z.-Q. Liu, N. Li, Y.-Z. Su, K. Davey,
S.-Z. Qiao, Adv. Funct. Mater. 2016, 26, 3314; b) Y. Yang, M. Luo,
Y. Xing, S. Wang, W. Zhang, F. Lv, Y. Li, Y. Zhang, W. Wang,
S. J. Guo, Adv. Mater. 2018, 30, 1706085; c) J. Yin, Y. Li, F. Lv,
M. Lu, K. Sun, W. Wang, L. Wang, F. Cheng, Y. Li, P. Xi, S. J. Guo,
Adv. Mater. 2017, 29, 1704681.
[16] a) Y. Wu, Y. Meng, J. Hou, S. Cao, Z. Gao, Z. Wu, L. Sun, Adv.
Funct. Mater. 2018, 28, 1801397; b) F. Li, J. Li, Q. Feng, J. Yan,
Y. Tang, H. Wang, J. Energy Chem. 2018, 27, 419.
[17] a) M. Fang, G. Dong, R. Wei, J. C. Ho, Adv. Energy Mater. 2017, 7,
1700559; b) J. Mei, T. Liao, Z. Sun, J. Energy Chem. 2018, 27, 117;
c) L. Zhang, W. Shi, B. Zhang, J. Energy Chem. 2017, 26, 1117.
[18] M. S. Faber, S. Jin, Energy Environ. Sci. 2014, 7, 3519.
[19] H. Zhao, Y.-P. Zhu, Z.-Y. Yuan, Eur. J. Inorg. Chem. 2016, 2016,
1916.
[20] a) N. K. Chaudhari, H. Jin, B. Kim, K. Lee, Nanoscale 2017, 9,
12231; b) B. Zhang, J. Zhang, J. Energy Chem. 2017, 26, 1050.
[21] a) J. Liu, D. Zhu, Y. Zheng, A. Vasileff, S.-Z. Qiao, ACS Catal. 2018,
8, 6707; b) X. Sun, J. Huo, Y. Yang, L. Xu, S. Wang, J. Energy Chem.
2017, 26, 1136.
[22] Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, Chem. Soc. Rev. 2015, 44,
2060.
[23] Y. Li, H. Wang, L. Xie, Y. Liang, G. Hong, H. Dai, J. Am. Chem. Soc.
2011, 133, 7296.
[24] a) N. Mahmood, Y. Yao, J. W. Zhang, L. Pan, X. Zhang, J. J. Zou,
Adv. Sci. 2018, 5, 1700464; b) L. Zhou, M. Shao, M. Wei, X. Duan,
J. Energy Chem. 2017, 26, 1094; c) Z. Zhou, N. Mahmood,
Y. Zhang, L. Pan, J. Zou, J. Energy Chem. 2017, 26, 1223.
[25] G. Zhao, K. Rui, S. X. Dou, W. Sun, Adv. Funct. Mater. 2018, 28,
1803291.
[26] J. Staszak-Jirkovsky, C. D. Malliakas, P. P. Lopes, N. Danilovic,
S. S. Kota, K. C. Chang, B. Genorio, D. Strmcnik, V. R. Stamenkovic,
M. G. Kanatzidis, N. M. Markovic, Nat. Mater. 2016, 15, 197.
[27] K. Xu, H. Ding, M. Zhang, M. Chen, Z. Hao, L. Zhang, C. Wu,
Y. Xie, Adv. Mater. 2017, 29, 1606980.
Adv. Funct. Mater. 2019, 29, 1808367 1808367  (36 of 39)
www.afm-journal.de
[28] J. S. Kim, B. Kim, H. Kim, K. Kang, Adv. Energy Mater. 2018, 8,
1702774.
[29] J. Rossmeisl, A. Logadottir, J. K. Nørskov, Chem. Phys. 2005, 319,
178.
[30] Á. Valdés, Z. W. Qu, G. J. Kroes, J. Rossmeisl, J. K. Nørskov, J. Phys.
Chem. C 2008, 112, 9872.
[31] Z. Xu, J. Rossmeisl, J. R. Kitchin, J. Phys. Chem. C 2015, 119, 4827.
[32] I. C. Man, H.-Y. Su, F. Calle-Vallejo, H. A. Hansen, J. I. Martínez,
N. G. Inoglu, J. Kitchin, T. F. Jaramillo, J. K. Nørskov, J. Rossmeisl,
ChemCatChem 2011, 3, 1159.
[33] C. C. McCrory, S. Jung, I. M. Ferrer, S. M. Chatman, J. C. Peters,
T. F. Jaramillo, J. Am. Chem. Soc. 2015, 137, 4347.
[34] B. You, X. Liu, X. Liu, Y. Sun, ACS Catal. 2017, 7, 4564.
[35] I. A. Raj, K. Vasu, J. Appl. Electrochem. 1990, 20, 32.
[36] E. Navarro-Flores, Z. Chong, S. Omanovic, J. Mater. Chem. A 2005,
226, 179.
[37] Y. Jin, X. Yue, C. Shu, S. Huang, P. K. Shen, J. Mater. Chem. A
2017, 5, 2508.
[38] M. Fang, W. Gao, G. Dong, Z. Xia, S. Yip, Y. Qin, Y. Qu, J. C. Ho,
Nano Energy 2016, 27, 247.
[39] Y. Wang, G. Zhang, W. Xu, P. Wan, Z. Lu, Y. Li, X. Sun,
ChemElectroChem 2014, 1, 1138.
[40] S. Zhao, J. Huang, Y. Liu, J. Shen, H. Wang, X. Yang, Y. Zhu, C. Li,
J. Mater. Chem. A 2017, 5, 4207.
[41] J. Lu, T. Xiong, W. Zhou, L. Yang, Z. Tang, S. Chen, ACS Appl.
Mater. Interfaces 2016, 8, 5065.
[42] I. A. Raj, Int. J. Hydrogen Energy 1992, 17, 413.
[43] L. Han, S. Dong, E. Wang, Adv. Mater. 2016, 28, 9266.
[44] J. Wang, W. Cui, Q. Liu, Z. Xing, A. M. Asiri, X. Sun, Adv. Mater.
2016, 28, 215.
[45] Y. Yu, J. Zhang, M. Zhong, S. Guo, Electrocatalysis 2018, 9, 653.
[46] Y. P. Zhu, T. Y. Ma, M. Jaroniec, S. Z. Qiao, Angew. Chem., Int. Ed.
2017, 56, 1324.
[47] J. Liang, Y.-Z. Wang, C.-C. Wang, S.-Y. Lu, J. Mater. Chem. A 2016,
4, 9797.
[48] C. C. Hou, W. F. Fu, Y. Chen, ChemSusChem 2016, 9, 2069.
[49] C. Shu, S. Kang, Y. Jin, X. Yue, P. K. Shen, J. Mater. Chem. A 2017,
5, 9655.
[50] Y. Jin, H. Wang, J. Li, X. Yue, Y. Han, P. K. Shen, Y. Cui, Adv. Mater.
2016, 28, 3785.
[51] C. C. McCrory, S. Jung, J. C. Peters, T. F. Jaramillo, J. Am. Chem.
Soc. 2013, 135, 16977.
[52] C. Dong, T. Kou, H. Gao, Z. Peng, Z. Zhang, Adv. Energy Mater.
2018, 8, 1701347.
[53] Z. Lu, H. Wang, D. Kong, K. Yan, P. C. Hsu, G. Zheng, H. Yao,
Z. Liang, X. Sun, Y. Cui, Nat. Commun. 2014, 5, 4345.
[54] A. Grimaud, O. Diaz-Morales, B. Han, W. T. Hong, Y. L. Lee,
L. Giordano, K. A. Stoerzinger, M. T. M. Koper, Y. Shao-Horn, Nat.
Chem. 2017, 9, 457.
[55] G. Fan, F. Li, D. G. Evans, X. Duan, Chem. Soc. Rev. 2014, 43, 7040.
[56] X. Lu, C. Zhao, Nat. Commun. 2015, 6, 6616.
[57] Z. Zhao, H. Wu, H. He, X. Xu, Y. Jin, Adv. Funct. Mater. 2014, 24,
4698.
[58] J. Jiang, A. Zhang, L. Li, L. Ai, J. Power Sources 2015, 278, 445.
[59] A.-L. Wang, H. Xu, G.-R. Li, ACS Energy Lett. 2016, 1, 445.
[60] J. Feng, S. Ye, H. Xu, Y. Tong, G. Li, Adv. Mater. 2016, 28, 4698.
[61] L. Yu, H. Zhou, J. Sun, F. Qin, F. Yu, J. Bao, Y. Yu, S. Chen, Z. Ren,
Energy Environ. Sci. 2017, 10, 1820.
[62] S. Jin, ACS Energy Lett. 2017, 2, 1937.
[63] Z. Chen, C. X. Kronawitter, Y.-W. Yeh, X. Yang, P. Zhao, N. Yao,
B. E. Koel, J. Mater. Chem. A 2017, 5, 842.
[64] L. Trotochaud, S. L. Young, J. K. Ranney, S. W. Boettcher, J. Am.
Chem. Soc. 2014, 136, 6744.
[65] J. X. Feng, H. Xu, Y. T. Dong, S. H. Ye, Y. X. Tong, G. R. Li, Angew.
Chem., Int. Ed. 2016, 55, 3694.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[66] P. Liu, J. A. Rodriguez, J. Am. Chem. Soc. 2005, 127, 14871.
[67] Y. Tan, H. Wang, P. Liu, C. Cheng, F. Zhu, A. Hirata, M. Chen,
Adv. Mater. 2016, 28, 2951.
[68] J. Tian, Q. Liu, A. M. Asiri, X. Sun, J. Am. Chem. Soc. 2014, 136, 7587.
[69] J. Tian, Q. Liu, N. Cheng, A. M. Asiri, X. Sun, Angew. Chem., Int.
Ed. 2014, 53, 9577.
[70] Y. Tan, H. Wang, P. Liu, Y. Shen, C. Cheng, A. Hirata, T. Fujita,
Z. Tang, M. Chen, Energy Environ. Sci. 2016, 9, 2257.
[71] X.-D. Wang, Y.-F. Xu, H.-S. Rao, W.-J. Xu, H.-Y. Chen, W.-X. Zhang,
D.-B. Kuang, C.-Y. Su, Energy Environ. Sci. 2016, 9, 1468.
[72] M. Qian, S. Cui, D. Jiang, L. Zhang, P. Du, Adv. Mater. 2017, 29,
1704075.
[73] H. Kim, J. Park, I. Park, K. Jin, S. E. Jerng, S. H. Kim, K. T. Nam,
K. Kang, Nat. Commun. 2015, 6, 8253.
[74] K. Jin, J. Park, J. Lee, K. D. Yang, G. K. Pradhan, U. Sim, D. Jeong,
H. L. Jang, S. Park, D. Kim, N. E. Sung, S. H. Kim, S. Han,
K. T. Nam, J. Am. Chem. Soc. 2014, 136, 7435.
[75] J. Huang, Y. Sun, Y. Zhang, G. Zou, C. Yan, S. Cong, T. Lei, X. Dai,
J. Guo, R. Lu, Y. Li, J. Xiong, Adv. Mater. 2018, 30, 1705045.
[76] L. Yang, Z. Guo, J. Huang, Y. Xi, R. Gao, G. Su, W. Wang, L. Cao,
B. Dong, Adv. Mater. 2017, 29, 1704574.
[77] J. Xing, H. Li, M. Ming-Cheng Cheng, S. M. Geyer, K. Y. S. Ng,
J. Mater. Chem. A 2016, 4, 13866.
[78] J. Kibsgaard, Z. Chen, B. N. Reinecke, T. F. Jaramillo, Nat. Mater.
2012, 11, 963.
[79] K. Liang, Y. Yan, L. Guo, K. Marcus, Z. Li, L. Zhou, Y. Li, R. Ye,
N. Orlovskaya, Y.-H. Sohn, Y. Yang, ACS Energy Lett. 2017, 2, 1315.
[80] W. Jaegermann, H. Tributsch, Prog. Surf. Sci. 1988, 29, 1.
[81] M. S. Faber, M. A. Lukowski, Q. Ding, N. S. Kaiser, S. Jin, J. Phys.
Chem. C 2014, 118, 21347.
[82] M. S. Faber, R. Dziedzic, M. A. Lukowski, N. S. Kaiser, Q. Ding,
S. Jin, J. Am. Chem. Soc. 2014, 136, 10053.
[83] L. L. Feng, G. Yu, Y. Wu, G. D. Li, H. Li, Y. Sun, T. Asefa, W. Chen,
X. Zou, J. Am. Chem. Soc. 2015, 137, 14023.
[84] C. Tang, N. Cheng, Z. Pu, W. Xing, X. Sun, Angew. Chem., Int. Ed.
2015, 54, 9351.
[85] R. Xu, R. Wu, Y. Shi, J. Zhang, B. Zhang, Nano Energy 2016, 24, 103.
[86] W. Li, X. Gao, D. Xiong, F. Wei, W.-G. Song, J. Xu, L. Liu, Adv.
Energy Mater. 2017, 7, 1602579.
[87] B. Liu, Y. F. Zhao, H. Q. Peng, Z. Y. Zhang, C. K. Sit, M. F. Yuen,
T. R. Zhang, C. S. Lee, W. J. Zhang, Adv. Mater. 2017, 29, 1606521.
[88] Y. Wu, G.-D. Li, Y. Liu, L. Yang, X. Lian, T. Asefa, X. Zou, Adv. Funct.
Mater. 2016, 26, 4839.
[89] a) J. Li, W. Xu, J. Luo, D. Zhou, D. Zhang, L. Wei, P. Xu, D. Yuan,
Nano-Micro Lett. 2018, 10, 6; b) Q. Cheng, D. Wang, H. Zhou,
J. Energy Chem. 2018, 27, 913; c) T. Li, Q. Zhang, J. Energy Chem.
2018, 27, 373.
[90] J. Miao, F.-X. Xiao, H. B. Yang, S. Y. Khoo, J. Chen, Z. Fan,
Y.-Y. Hsu, H. M. Chen, H. Zhang, B. Liu, Sci. Adv. 2015, 1,
e1500259;
[91] F. Wang, Y. Li, T. A. Shifa, K. Liu, F. Wang, Z. Wang, P. Xu,
Q. Wang, J. He, Angew. Chem., Int. Ed. 2016, 55, 6919.
[92] M.-S. Balogun, Y. Huang, W. Qiu, H. Yang, H. Ji, Y. Tong, Mater.
Today 2017, 20, 425.
[93] P. Chen, K. Xu, Z. Fang, Y. Tong, J. Wu, X. Lu, X. Peng, H. Ding,
C. Wu, Y. Xie, Angew. Chem., Int. Ed. 2015, 54, 14710.
[94] Y. Zhang, B. Ouyang, J. Xu, G. Jia, S. Chen, R. S. Rawat, H. J. Fan,
Angew. Chem., Int. Ed. 2016, 55, 8670.
[95] T. Liu, M. Li, C. Jiao, M. Hassan, X. Bo, M. Zhou, H.-L. Wang,
J. Mater. Chem. A 2017, 5, 9377.
[96] Z. Chen, Y. Song, J. Cai, X. Zheng, D. Han, Y. Wu, Y. Zang, S. Niu,
Y. Liu, J. Zhu, X. Liu, G. Wang, Angew. Chem., Int. Ed. 2018, 57,
5076.
[97] Y. Ma, Z. He, Z. Wu, B. Zhang, Y. Zhang, S. Ding, C. Xiao, J. Mater.
Chem. A 2017, 5, 24850.
Adv. Funct. Mater. 2019, 29, 1808367 1808367  (37 of 39)
www.afm-journal.de
[98] B. Zhang, C. Xiao, S. Xie, J. Liang, X. Chen, Y. Tang, Chem. Mater.
2016, 28, 6934.
[99] J. Jia, M. Zhai, J. Lv, B. Zhao, H. Du, J. Zhu, ACS Appl. Mater.
Interfaces 2018, 10, 30400.
[100] Q. Gao, W. Zhang, Z. Shi, L. Yang, Y. Tang, Adv. Mater. 2019, 31,
e1802880.
[101] H. Ang, H. Wang, B. Li, Y. Zong, X. Wang, Q. Yan, Small 2016, 12,
2859.
[102] F. Li, X. Zhao, J. Mahmood, M. S. Okyay, S.-M. Jung, I. Ahmad,
S.-J. Kim, G.-F. Han, N. Park, J.-B. Baek, ACS Nano 2017, 11, 7527.
[103] a) K. Xiong, L. Li, L. Zhang, W. Ding, L. Peng, Y. Wang, S. Chen,
S. Tan, Z. Wei, J. Mater. Chem. A 2015, 3, 1863; b) X. Li, Q. Xiao,
H. Zhang, H. Xu, Y. Zhang, J. Energy Chem. 2018, 27, 940.
[104] X. Fan, H. Zhou, X. Guo, ACS Nano 2015, 9, 5125.
[105] N. Han, K. R. Yang, Z. Lu, Y. Li, W. Xu, T. Gao, Z. Cai, Y. Zhang,
V. S. Batista, W. Liu, X. Sun, Nat. Commun. 2018, 9, 924.
[106] X. Fan, Y. Liu, Z. Peng, Z. Zhang, H. Zhou, X. Zhang,
B. I. Yakobson, W. A. Goddard, X. Guo, R. H. Hauge, J. M. Tour,
ACS Nano 2017, 11, 384.
[107] a) Z.-Y. Wu, B.-C. Hu, P. Wu, H.-W. Liang, Z.-L. Yu, Y. Lin,
Y.-R. Zheng, Z. Li, S.-H. Yu, NPG Asia Mater. 2016, 8, e288;
b) L. Gao, M. Xiao, Z. Jin, C. Liu, J. Zhu, J. Ge, W. Xing, J. Energy
Chem. 2018, 27, 1668.
[108] X. Fan, Z. Peng, R. Ye, H. Zhou, X. Guo, ACS Nano 2015,
9, 7407.
[109] Z. Wei, W. Zhu, Y. Li, Y. Ma, J. Wang, N. Hu, Y. Suo, J. Wang, Inorg.
Chem. 2018, 57, 8422.
[110] L. Wang, Y. Wu, R. Cao, L. Ren, M. Chen, X. Feng, J. Zhou,
B. Wang, ACS Appl. Mater. Interfaces 2016, 8, 16736.
[111] W. Luo, J. Hu, H. Diao, B. Schwarz, C. Streb, Y. F. Song, Angew.
Chem., Int. Ed. 2017, 56, 4941.
[112] Y. Guo, T. Wang, J. Chen, J. Zheng, X. Li, K. K. Ostrikov, Adv. Energy
Mater. 2018, 8, 1800085.
[113] G. Chen, J. Zhang, F. Wang, L. Wang, Z. Liao, E. Zschech,
K. Mullen, X. Feng, Chem. Eur. J. 2018, 24, 18413.
[114] J. Q. Shen, P. Q. Liao, D. D. Zhou, C. T. He, J. X. Wu, W. X. Zhang,
J. P. Zhang, X. M. Chen, J. Am. Chem. Soc. 2017, 139, 1778.
[115] X. F. Lu, P. Q. Liao, J. W. Wang, J. X. Wu, X. W. Chen, C. T. He,
J. P. Zhang, G. R. Li, X. M. Chen, J. Am. Chem. Soc. 2016, 138,
8336.
[116] S. Zhao, Y. Wang, J. Dong, C.-T. He, H. Yin, P. An, K. Zhao,
X. Zhang, C. Gao, L. Zhang, J. Lv, J. Wang, J. Zhang, A. M. Khattak,
N. A. Khan, Z. Wei, J. Zhang, S. Liu, H. Zhao, Z. Tang, Nat. Energy
2016, 1, 16184.
[117] P.-Q. Liao, J.-Q. Shen, J.-P. Zhang, Coord. Chem. Rev. 2018, 373,
22.
[118] W. Wang, D. Liu, S. Hao, F. Qu, Y. Ma, G. Du, A. M. Asiri, Y. Yao,
X. Sun, Inorg. Chem. 2017, 56, 3131.
[119] L. Peng, J. Wang, Y. Nie, K. Xiong, Y. Wang, L. Zhang, K. Chen,
W. Ding, L. Li, Z. Wei, ACS Catal. 2017, 7, 8184.
[120] Z. Liu, J. Zhang, Y. Liu, W. Zhu, X. Zhang, Q. Wang, ChemElectro-
Chem 2018, 5, 1677.
[121] J. Duan, S. Chen, B. A. Chambers, G. G. Andersson, S. Z. Qiao,
Adv. Mater. 2015, 27, 4234.
[122] F. Li, J. Du, X. Li, J. Shen, Y. Wang, Y. Zhu, L. Sun, Adv. Energy
Mater. 2018, 8, 1702598.
[123] X. Zhu, X. Shi, A. M. Asiri, Y. Luo, X. Sun, Inorg. Chem. Front. 2018,
5, 1188.
[124] B. Liu, H. Li, B. Cao, J. Jiang, R. Gao, J. Zhang, Adv. Funct. Mater.
2018, 28, 1801527.
[125] H. Zhang, Y. Liu, H. Wu, W. Zhou, Z. Kou, S. J. Pennycook, J. Xie,
C. Guan, J. Wang, J. Mater. Chem. A 2018, 6, 20214.
[126] M. Zhang, A. Hu, Z. Liu, Y. Xu, B. Fan, Q. Tang, S. Zhang,
W. Deng, X. Chen, Electrochim. Acta 2018, 285, 254.
[127] A. Rabenau, Angew. Chem., Int. Ed. Engl. 1985, 24, 1026.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[128] K. Wang, C. Zhou, D. Xi, Z. Shi, C. He, H. Xia, G. Liu, G. Qiao,
Nano Energy 2015, 18, 1.
[129] X. Zou, Y. Wu, Y. Liu, D. Liu, W. Li, L. Gu, H. Liu, P. Wang, L. Sun,
Y. Zhang, Chem 2018, 4, 1139.
[130] Y. Hou, M. R. Lohe, J. Zhang, S. Liu, X. Zhuang, X. L. Feng, Energy
Environ. Sci. 2016, 9, 478.
[131] J. Liu, Y. Zheng, Z. Wang, Z. Lu, A. Vasileff, S. Z. Qiao, Chem.
Commun. 2018, 54, 463.
[132] B. Konkena, J. Masa, A. J. R. Botz, I. Sinev, W. Xia, J. Koßmann,
R. Drautz, M. Muhler, W. Schuhmann, ACS Catal. 2017, 7, 229.
[133] Q. Fu, T. Wu, G. Fu, T. Gao, J. Han, T. Yao, Y. Zhang, W. Zhong,
X. Wang, B. Song, ACS Energy Lett. 2018, 3, 1744.
[134] Z. Pu, Q. Liu, A. M. Asiri, X. Sun, ACS Appl. Mater. Interfaces 2014,
6, 21874.
[135] M. Ma, G. Zhu, F. Xie, F. Qu, Z. Liu, G. Du, A. M. Asiri, Y. Yao,
X. Sun, ChemSusChem 2017, 10, 3188.
[136] W. Zhou, X.-J. Wu, X. Cao, X. Huang, C. Tan, J. Tian, H. Liu,
J. Wang, H. Zhang, Energy Environ. Sci. 2013, 6, 2921.
[137] D. Kong, Y. Wang, Y. V. Lim, S. Huang, J. Zhang, B. Liu, T. Chen,
H. Y. Yang, Nano Energy 2018, 49, 460.
[138] H. Xu, J.-X. Feng, Y.-X. Tong, G.-R. Li, ACS Catal. 2017, 7, 986.
[139] G. Zhang, G. Wang, H. Liu, J. Qu, J. Li, Nano Energy 2018, 43, 359.
[140] X. Wang, W. Li, D. Xiong, D. Y. Petrovykh, L. Liu, Adv. Funct. Mater.
2016, 26, 4067.
[141] S. H. Ye, Z. X. Shi, J. X. Feng, Y. X. Tong, G. R. Li, Angew. Chem.,
Int. Ed. 2018, 57, 2672.
[142] J. Yu, Q. Li, Y. Li, C.-Y. Xu, L. Zhen, V. P. Dravid, J. Wu, Adv. Funct.
Mater. 2016, 26, 7644.
[143] P. Zhang, M. Wang, Y. Yang, T. Yao, L. Sun, Angew. Chem., Int. Ed.
2014, 53, 13803.
[144] P. Zhang, M. Wang, H. Chen, Y. Liang, J. Sun, L. Sun, Adv. Energy
Mater. 2016, 6, 1502319.
[145] Y. Liu, J. Goebl, Y. Yin, Chem. Soc. Rev. 2013, 42, 2610.
[146] G. Cao, D. Liu, Adv. Colloid Interface Sci. 2008, 136, 45.
[147] Q. Xu, G. Meng, F. Han, Prog. Mater. Sci. 2018, 95, 243.
[148] L. Zhang, L. Liu, H. Wang, H. Shen, Q. Cheng, C. Yan, S. Park,
Nanomaterials 2017, 7, 103.
[149] H.-M. Zhang, Y.-G. Guo, L.-J. Wan, C.-L. Bai, Chem. Commun.
2003, 3022.
[150] Z. Zhao, H. Wu, H. He, X. Xu, Y. Jin, Adv. Funct. Mater. 2014, 24,
4698.
[151] A. L. Wang, Y. T. Dong, M. Li, C. Liang, G. R. Li, ACS Appl. Mater.
Interfaces 2017, 9, 34954.
[152] J. Nai, Y. Tian, X. Guan, L. Guo, J. Am. Chem. Soc. 2013, 135, 16082.
[153] M. Wu, Y. Huang, X. Cheng, X. Geng, Q. Tang, Y. You, Y. Yu,
R. Zhou, J. Xu, Adv. Mater. Interfaces 2017, 4, 1700948.
[154] S. Li, Y. Wang, S. Peng, L. Zhang, A. M. Al-Enizi, H. Zhang, X. Sun,
G. Zheng, Adv. Energy Mater. 2016, 6, 1501661.
[155] J. Hou, Y. Sun, S. Cao, Y. Wu, H. Chen, L. Sun, ACS Appl. Mater.
Interfaces 2017, 9, 24600.
[156] J. Wang, H. X. Zhong, Z. L. Wang, F. L. Meng, X. B. Zhang, ACS
Nano 2016, 10, 2342.
[157] T. Sun, L. Xu, Y. Yan, A. A. Zakhidov, R. H. Baughman, J. Chen,
ACS Catal. 2016, 6, 1446.
[158] S. Zhuo, Y. Shi, L. Liu, R. Li, L. Shi, D. H. Anjum, Y. Han, P. Wang,
Nat. Commun. 2018, 9, 3132.
[159] Organic Nanostructures (Eds: J. L. Atwood, J. W. Steed), Wiley-VCH,
Weinheim, Germany 2008.
[160] G. Cai, W. Zhang, L. Jiao, S.-H. Yu, H.-L. Jiang, Chem 2017, 2, 791.
[161] C. Guan, X. Liu, W. Ren, X. Li, C. Cheng, J. Wang, Adv. Energy
Mater. 2017, 7, 1602391.
[162] J. Zhou, Y. Dou, A. Zhou, R.-M. Guo, M.-J. Zhao, J.-R. Li, Adv.
Energy Mater. 2017, 7, 1602643.
[163] H. Zhang, T. Wang, A. Sumboja, W. Zang, J. Xie, D. Gao, S. J. Pennycook,
Z. Liu, C. Guan, J. Wang, Adv. Funct. Mater. 2018, 28, 1804846.
Adv. Funct. Mater. 2019, 29, 1808367 1808367  (38 of 39)
www.afm-journal.de
[164] X. F. Lu, L. F. Gu, J. W. Wang, J. X. Wu, P. Q. Liao, G. R. Li, Adv.
Mater. 2017, 29, 1604437.
[165] I. S. Amiinu, X. Liu, Z. Pu, W. Li, Q. Li, J. Zhang, H. Tang,
H. Zhang, S. Mu, Adv. Funct. Mater. 2018, 28, 1704638.
[166] Z. Zhang, W. Li, M. F. Yuen, T.-W. Ng, Y. Tang, C.-S. Lee, X. Chen,
W. Zhang, Nano Energy 2015, 18, 196.
[167] P. Guo, J. Wu, X.-B. Li, J. Luo, W.-M. Lau, H. Liu, X.-L. Sun,
L.-M. Liu, Nano Energy 2018, 47, 96.
[168] J. Li, X. Gao, X. Jiang, X.-B. Li, Z. Liu, J. Zhang, C.-H. Tung,
L.-Z. Wu, ACS Catal. 2017, 7, 5209.
[169] S. Sarawutanukul, N. Phattharasupakun, J. Wutthiprom,
M. Sawangphruk, Sustainable Energy Fuels 2018, 2, 1305.
[170] Z. Zhao, D. E. Schipper, A. P. Leitner, H. Thirumalai, J.-H. Chen,
L. Xie, F. Qin, M. K. Alam, L. C. Grabow, S. Chen, D. Wang, Z. Ren,
Z. Wang, K. H. Whitmire, J. Bao, Nano Energy 2017, 39, 444.
[171] B. Zheng, Y. Chen, F. Qi, X. Wang, W. Zhang, Y. Li, X. Li, 2D Mater.
2017, 4, 025092.
[172] L. He, D. Zhou, Y. Lin, R. Ge, X. Hou, X. Sun, C. Zheng, ACS Catal.
2018, 8, 3859.
[173] K. Xu, H. Cheng, H. Lv, J. Wang, L. Liu, S. Liu, X. Wu, W. Chu,
C. Wu, Y. Xie, Adv. Mater. 2018, 30, 1703322.
[174] S. Ekeroth, E. P. Munger, R. Boyd, J. Ekspong, T. Wagberg,
L. Edman, N. Brenning, U. Helmersson, Nano Lett. 2018, 18, 3132.
[175] Y. Qu, H. Medina, S. W. Wang, Y. C. Wang, C. W. Chen, T. Y. Su,
A. Manikandan, K. Wang, Y. C. Shih, J. W. Chang, H. C. Kuo,
C. Y. Lee, S. Y. Lu, G. Shen, Z. M. Wang, Y. L. Chueh, Adv. Mater.
2016, 28, 9831.
[176] B. Liu, B. He, H. Q. Peng, Y. Zhao, J. Cheng, J. Xia, J. Shen,
T. W. Ng, X. Meng, C. S. Lee, W. Zhang, Adv. Sci. 2018, 5, 1800406.
[177] D. Friebel, M. W. Louie, M. Bajdich, K. E. Sanwald, Y. Cai,
A. M. Wise, M. J. Cheng, D. Sokaras, T. C. Weng, R. Alonso-Mori,
R. C. Davis, J. R. Bargar, J. K. Norskov, A. Nilsson, A. T. Bell, J. Am.
Chem. Soc. 2015, 137, 1305.
[178] B. Zhang, X. Zheng, O. Voznyy, R. Comin, M. Bajdich, M. García-
Melchor, L. Han, J. Xu, M. Liu, L. Zheng, Science 2016, 352, 333.
[179] Y. Pi, Q. Shao, P. Wang, F. Lv, S. Guo, J. Guo, X. Huang, Angew.
Chem., Int. Ed. 2017, 56, 4502.
[180] R. Zhang, X. Wang, S. Yu, T. Wen, X. Zhu, F. Yang, X. Sun, X. Wang,
W. Hu, Adv. Mater. 2017, 29, 1605502.
[181] L. Yang, L. Xie, X. Ren, Z. Wang, Z. Liu, G. Du, A. M. Asiri, Y. Yao,
X. Sun, Chem. Commun. 2018, 54, 78.
[182] Y. Li, H. Zhang, M. Jiang, Y. Kuang, X. Sun, X. Duan, Nano Res.
2016, 9, 2251.
[183] J. Zheng, X. Chen, X. Zhong, S. Li, T. Liu, G. Zhuang, X. Li,
S. Deng, D. Mei, J.-G. Wang, Adv. Funct. Mater. 2017, 27, 1704169.
[184] M. Huynh, D. K. Bediako, D. G. Nocera, J. Am. Chem. Soc. 2014,
136, 6002.
[185] Z. Ye, T. Li, G. Ma, Y. Dong, X. Zhou, Adv. Funct. Mater. 2017, 27,
1704083.
[186] T. Tang, W. J. Jiang, S. Niu, N. Liu, H. Luo, Y. Y. Chen, S. F. Jin,
F. Gao, L. J. Wan, J. S. Hu, J. Am. Chem. Soc. 2017, 139, 8320.
[187] L. Hui, Y. Xue, D. Jia, H. Yu, C. Zhang, Y. Li, Adv. Energy Mater.
2018, 8, 1800175.
[188] C. Tang, L. Gan, R. Zhang, W. Lu, X. Jiang, A. M. Asiri, X. Sun,
J. Wang, L. Chen, Nano Lett. 2016, 16, 6617.
[189] Y. Li, H. Zhang, M. Jiang, Q. Zhang, P. He, X. Sun, Adv. Funct.
Mater. 2017, 27, 1702513.
[190] T. Liu, D. Liu, F. Qu, D. Wang, L. Zhang, R. Ge, S. Hao, Y. Ma,
G. Du, A. M. Asiri, L. Chen, X. Sun, Adv. Energy Mater. 2017, 7,
1700020.
[191] X. Liu, W. Xi, C. Li, X. Li, J. Shi, Y. Shen, J. He, L. Zhang, L. Xie,
X. Sun, P. Wang, J. Luo, L.-M. Liu, Y. Ding, Nano Energy 2018, 44,
371.
[192] Y. Yang, L. Dang, M. J. Shearer, H. Sheng, W. Li, J. Chen, P. Xiao,
Y. Zhang, R. J. Hamers, S. Jin, Adv. Energy Mater. 2018, 8, 1703189.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[193] X. Bo, Y. Li, R. K. Hocking, C. Zhao, ACS Appl. Mater. Interfaces
2017, 9, 41239.
[194] J. Jiang, F. Sun, S. Zhou, W. Hu, H. Zhang, J. Dong, Z. Jiang,
J. Zhao, J. Li, W. Yan, M. Wang, Nat. Commun. 2018, 9, 2885.
[195] Y. Sun, K. Xu, Z. Wei, H. Li, T. Zhang, X. Li, W. Cai, J. Ma, H. J. Fan,
Y. Li, Adv. Mater. 2018, 30, 1802121.
[196] K. Fan, H. Chen, Y. Ji, H. Huang, P. M. Claesson, Q. Daniel,
B. Philippe, H. Rensmo, F. Li, Y. Luo, L. Sun, Nat. Commun. 2016,
7, 11981.
[197] P. Li, X. Duan, Y. Kuang, Y. Li, G. Zhang, W. Liu, X. Sun, Adv.
Energy Mater. 2018, 8, 1703341.
[198] X. Jia, Y. Zhao, G. Chen, L. Shang, R. Shi, X. Kang,
G. I. N. Waterhouse, L.-Z. Wu, C.-H. Tung, T. Zhang, Adv. Energy
Mater. 2016, 6, 1502585.
[199] B. You, X. Liu, G. Hu, S. Gul, J. Yano, D.-e. Jiang, Y. Sun, J. Am.
Chem. Soc. 2017, 139, 12283.
[200] S. Deng, Y. Zhong, Y. Zeng, Y. Wang, Z. Yao, F. Yang, S. Lin,
X. Wang, X. Lu, X. Xia, J. Tu, Adv. Mater. 2017, 29, 1700748.
[201] H. Li, S. Chen, Y. Zhang, Q. Zhang, X. Jia, Q. Zhang, L. Gu, X. Sun,
L. Song, X. Wang, Nat. Commun. 2018, 9, 2452.
[202] X. Xu, F. Song, X. Hu, Nat. Commun. 2016, 7, 12324.
[203] C. Hu, L. Zhang, Z. J. Zhao, A. Li, X. Chang, J. Gong, Adv. Mater.
2018, 30, 1705538.
[204] J. Zhuo, M. Cabán-Acevedo, H. Liang, L. Samad, Q. Ding, Y. Fu,
M. Li, S. Jin, ACS Catal. 2015, 5, 6355.
[205] X. Wang, Y. V. Kolen’ko, X. Q. Bao, K. Kovnir, L. Liu, Angew. Chem.,
Int. Ed. 2015, 54, 8188.
[206] Y.-P. Zhu, Y.-P. Liu, T.-Z. Ren, Z.-Y. Yuan, Adv. Funct. Mater. 2015,
25, 7337.
[207] B. Zhang, Y. H. Lui, H. Ni, S. Hu, Nano Energy 2017, 38, 553.
[208] Z. Wang, H. Liu, R. Ge, X. Ren, J. Ren, D. Yang, L. Zhang, X. Sun,
ACS Catal. 2018, 8, 2236.
[209] Y. Hou, M. Qiu, T. Zhang, X. Zhuang, C. S. Kim, C. Yuan, X. Feng,
Adv. Mater. 2017, 29, 1701589.
[210] M. Caban-Acevedo, M. L. Stone, J. R. Schmidt, J. G. Thomas, Q. Ding,
H. C. Chang, M. L. Tsai, J. H. He, S. Jin, Nat. Mater. 2015, 14, 1245.
[211] T. Wu, M. L. Stone, M. J. Shearer, M. J. Stolt, I. A. Guzei,
R. J. Hamers, R. Lu, K. Deng, S. Jin, J. R. Schmidt, ACS Catal. 2018,
8, 1143.
[212] M. W. Kanan, D. G. Nocera, Science 2008, 321, 1072.
[213] L. Xie, R. Zhang, L. Cui, D. Liu, S. Hao, Y. Ma, G. Du, A. M. Asiri,
X. Sun, Angew. Chem., Int. Ed. 2017, 56, 1064.
[214] M. Dincă, Y. Surendranath, D. G. Nocera, Proc. Natl. Acad. Sci.
USA 2010, 107, 10337.
[215] R. Ge, H. Du, K. Tao, Q. Zhang, L. Chen, ACS Appl. Mater. Inter-
faces 2017, 9, 15383.
[216] M. Ma, F. Qu, X. Ji, D. Liu, S. Hao, G. Du, A. M. Asiri, Y. Yao,
L. Chen, X. Sun, Small 2017, 13, 1700394.
[217] L. Yang, L. Xie, R. Ge, R. Kong, Z. Liu, G. Du, A. M. Asiri, Y. Yao,
Y. Luo, ACS Appl. Mater. Interfaces 2017, 9, 19502.
[218] a) Q. Wang, Z. L. Zhao, S. Dong, D. He, M. J. Lawrence, S. Han,
C. Cai, S. Xiang, P. Rodriguez, B. Xiang, Z. Wang, Y. Liang, M. Gu,
Nano Energy 2018, 53, 458; b) J. Hou, C. Yang, H. Cheng, S. Jiao,
O. Takeda, H. Zhu, Energy Environ. Sci. 2014, 7, 3758; c) J. Hou,
H. Cheng, O. Takeda, H. Zhu, Energy Environ. Sci. 2015, 8, 1348;
d) J. Hou, S. Cao, Y. Wu, F. Liang, Y. Sun, Z. Lin, L. Sun, Adv.
Energy Mater. 2018, 8, 11701114.
[219] a) Y. Zhang, B. Cui, Z. Qin, H. Lin, J. Li, Nanoscale 2013, 5, 6826;
b) J. Hou, H. Cheng, O. Takeda, H. Zhu, Angew. Chem., Int. Ed.
2015, 54, 8480; c) J. Hou, Y. Wu, S. Cao, F. Liang, Z. Lin, Z. Gao,
L. Sun, Adv. Energy Mater. 2017, 7, 1700171.
[220] Y. Liu, Q. Li, R. Si, G. D. Li, W. Li, D. P. Liu, D. Wang, L. Sun,
Y. Zhang, X. Zou, Adv. Mater. 2017, 29, 1606200.
[221] X. Han, X. Wu, Y. Deng, J. Liu, J. Lu, C. Zhong, W. Hu, Adv. Energy
Mater. 2018, 8, 1800935.
Adv. Funct. Mater. 2019, 29, 1808367 1808367  (39 of 39)
www.afm-journal.de
[222] J. X. Feng, J. Q. Wu, Y. X. Tong, G. R. Li, J. Am. Chem. Soc. 2018,
140, 610.
[223] J. Zhang, T. Wang, P. Liu, Z. Liao, S. Liu, X. Zhuang, M. Chen,
E. Zschech, X. Feng, Nat. Commun. 2017, 8, 15437.
[224] J. Hou, Y. Wu, S. Cao, Y. Sun, L. Sun, Small 2017, 13, 1702018.
[225] Z.-H. Xue, H. Su, Q.-Y. Yu, B. Zhang, H.-H. Wang, X.-H. Li,
J.-S. Chen, Adv. Energy Mater. 2017, 7, 1602355.
[226] J. Hou, Y. Sun, Y. Wu, S. Cao, L. Sun, Adv. Funct. Mater. 2018, 28,
1704447.
[227] X. Han, Y. Yu, Y. Huang, D. Liu, B. Zhang, ACS Catal. 2017, 7, 6464.
[228] J. Hou, Y. Sun, Z. Li, B. Zhang, S. Cao, Y. Wu, Z. Gao, L. Sun, Adv.
Funct. Mater. 2018, 28, 1803278.
[229] a) S.-H. Bae, J.-E. Kim, H. Randriamahazaka, S.-Y. Moon, J.-Y. Park,
I.-K. Oh, Adv. Energy Mater. 2017, 7, 1601492; b) J. Shi, C. Tang,
J. Huang, W. Zhu, Q. Zhang, J. Energy Chem. 2018, 27, 167.
[230] J. Zhu, K. Sakaushi, G. Clavel, M. Shalom, M. Antonietti,
T.-P. Fellinger, J. Am. Chem. Soc. 2015, 137, 5480.
[231] Y. Feng, H. Zhang, L. Fang, Y. Mu, Y. Wang, ACS Catal. 2016, 6, 4477.
[232] G. Jia, W. Zhang, G. Fan, Z. Li, D. Fu, W. Hao, C. Yuan, Z. Zou,
Angew. Chem., Int. Ed. 2017, 56, 13781.
[233] W. Niu, S. Pakhira, K. Marcus, Z. Li, J. L. Mendoza-Cortes, Y. Yang,
Adv. Energy Mater. 2018, 8, 1800480.
[234] J. Hou, B. Zhang, Z. Li, S. Cao, Y. Sun, Y. Wu, Z. Gao, L. Sun, ACS
Catal. 2018, 8, 4612.
[235] Z. Zhao, F. Qin, S. Kasiraju, L. Xie, M. K. Alam, S. Chen, D. Wang,
Z. Ren, Z. Wang, L. C. Grabow, J. Bao, ACS Catal. 2017, 7, 7312.
[236] Z. M. Luo, J. W. Wang, J. B. Tan, Z. M. Zhang, T. B. Lu, ACS Appl.
Mater. Interfaces 2018, 10, 8231.
[237] J. Zhang, T. Wang, D. Pohl, B. Rellinghaus, R. Dong, S. Liu,
X. Zhuang, X. Feng, Angew. Chem., Int. Ed. 2016, 55, 6702.
[238] X. Zhou, X. Yang, M. N. Hedhili, H. Li, S. Min, J. Ming,
K.-W. Huang, W. Zhang, L.-J. Li, Nano Energy 2017, 32, 470.
[239] M. Kuang, Q. Wang, H. Ge, P. Han, Z. Gu, A. M. Al-Enizi,
G. Zheng, ACS Energy Lett. 2017, 2, 2498.
[240] M. Kuang, P. Han, Q. Wang, J. Li, G. Zheng, Adv. Funct. Mater.
2016, 26, 8555.
[241] X. Zou, Y. Liu, G. D. Li, Y. Wu, D. P. Liu, W. Li, H. W. Li, D. Wang,
Y. Zhang, X. Zou, Adv. Mater. 2017, 29, 1700404.
[242] H. Liang, A. N. Gandi, C. Xia, M. N. Hedhili, D. H. Anjum,
U. Schwingenschlögl, H. N. Alshareef, ACS Energy Lett. 2017, 2, 1035.
[243] L. An, L. Huang, P. Zhou, J. Yin, H. Liu, P. Xi, Adv. Funct. Mater.
2015, 25, 6814.
[244] a) J. X. Feng, L. X. Ding, S. H. Ye, X. J. He, H. Xu, Y. X. Tong, G. R. Li,
Adv. Mater. 2015, 27, 7051; b) Shehnaz, X. Song, S. Ren, Y. Yang,
Y. Guo, H. Jing, Q. Mao, C. Hao, J. Energy Chem. 2017, 26, 182.
[245] J. X. Feng, S. Y. Tong, Y. X. Tong, G. R. Li, J. Am. Chem. Soc. 2018,
140, 5118.
[246] S. Dou, X. Wang, S. Wang, Small Methods 2019, 3, 1800211.
[247] D. Yan, Y. Li, J. Huo, R. Chen, L. Dai, S. Wang, Adv. Mater. 2017,
29, 1606459.
[248] J. Wang, J. Liu, B. Zhang, H. Wan, Z. Li, X. Ji, K. Xu, C. Chen,
D. Zha, L. Miao, J. Jiang, Nano Energy 2017, 42, 98.
[249] J. Wang, J. Liu, B. Zhang, F. Cheng, Y. Ruan, X. Ji, K. Xu, C. Chen,
L. Miao, J. Jiang, Nano Energy 2018, 53, 144.
[250] T. Zhang, M.-Y. Wu, D.-Y. Yan, J. Mao, H. Liu, W.-B. Hu, X.-W. Du,
T. Ling, S.-Z. Qiao, Nano Energy 2018, 43, 103.
[251] Y. Zhu, W. Zhou, J. Yu, Y. Chen, M. Liu, Z. Shao, Chem. Mater.
2016, 28, 1691.
[252] a) H.-Y. Wang, Y.-Y. Hsu, R. Chen, T.-S. Chan, H. M. Chen, B. Liu,
Adv. Energy Mater. 2015, 5, 1500091; b) Z. Gong, Y. Yang, J. Energy
Chem. 2018, 27, 1566; c) H. Su, Y. Xu, S. Shen, J. Wang, J. Li,
L. Huang, S. Sun, J. Energy Chem. 2018, 27, 1637.
[253] E. Fabbri, M. Nachtegaal, T. Binninger, X. Cheng, B. J. Kim,
J. Durst, F. Bozza, T. Graule, R. Schaublin, L. Wiles, M. Pertoso,
N. Danilovic, K. E. Ayers, T. J. Schmidt, Nat. Mater. 2017, 16, 925.
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