DOI: 10.1002/cctc.

201701637 Reviews

Very Important Paper

Porous Materials as Highly Efficient Electrocatalysts for the

Oxygen Evolution Reaction
Jing Qi,[a] Wei Zhang,*[a] and Rui Cao*[a, b]

ChemCatChem 2018, 10, 1206 – 1220 1206 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Carbon-neutral hydrogen has potential to alleviate the energy
crisis and ease environmental problems. Water electrolysis is a
sustainable way for large-scale hydrogen production when
electricity is generated from renewable energy resources. The
key challenge in water splitting is the sluggish kinetics of the
oxygen evolution reaction (OER). Thus, it is important and nec-
essary to develop highly efficient electrocatalysts in a cost-ef-
fective way for OER. Porous materials have proven to be versa-
tile in catalysis due to their large surface area, the fast mass
1. Introduction
1.1. Electrocatalytic water oxidation
Hydrogen is the most abundant element in nature, and H2 gas
is expected to be a green and efficient energy carrier in the
future.[1] It is, however, critical and challenging to produce H2
economically and conveniently in a large scale. Currently, most
H2 is generated as a secondary energy resource from nonre-
newable fossil fuels by traditional petrochemical methods.[2]
This conversion process suffers from the low energy conver-
sion efficiency and causes severe environmental pollution.
Water electrolysis to produce H2 has been recognized as an ef-
ficient and green process when the electricity is generated
from sustainable energy resources, such as solar, tide, and
wind.[3, 4] These clean energy resources are tightly subject to
natural environment, and maintaining a constant output to
the electricity grid system is difficult. To store this sustainable
electricity, one way is to use rechargeable batteries. However,
the high cost and the difficulty in transporting batteries limits
this kind of application. In addition to the use of rechargeable
batteries, water electrolysis is an ideal strategy for the storage
and transport of “sustainable electricity” in the form of H2.[5] To
minimize the energy cost in water electrolysis, it is crucial to
develop effective catalysts to reduce the overpotentials. Com-
pared with the water oxidation on the anode, the H2 produc-
tion on the cathode is relatively easy.[6] As a sluggish half-reac-
tion of water electrolysis, the oxygen evolution reaction (OER)
is the bottleneck for water splitting.[7–9] The development of ef-
ficient and stable water oxidation electrocatalysts is of practical
importance to reduce the energy cost of water electroly-
sis.[10–12]
[a] J. Qi, Prof. W. Zhang, Prof. R. Cao
Key Laboratory of Applied Surface and Colloid Chemistry
Ministry of Education and School of Chemistry and Chemical Engineering
Shaanxi Normal University
Xi’an 710119 (P.R. China)
E-mail: zw@snnu.edu.cn
ruicao@ruc.edu.cn
[b] Prof. R. Cao
Department of Chemistry
Renmin University of China
Beijing 100872 (P.R. China)
The ORCID identification number(s) for the author(s) of this article can
be found under:
https://doi.org/10.1002/cctc.201701637.
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diffusion, and the buffer ability of volume change. Herein, we
summarize the recent progress of representative methodolo-
gies for the synthesis of porous materials toward electrocata-
lytic OER. The materials discussed in this Review include the
cheap transition-metal-based (Co, Ni, and Fe) and metal-free
porous materials. This Review sheds light on the different strat-
egies to construct catalysts with porous structures to facilitate
OER.
A variety of solid materials has been reported as OER elec-
trocatalysts in electrolytes with different pHs. Noble metal-
based materials exhibit high activity and stability for OER catal-
ysis in electrolytes with a wide range of pHs.[13] However, the
employment of these expensive elements will add extra cost
to water electrolysis. Cheap transition metal-based (Mn, Fe, Co,
Ni) materials have thus attracted continuing interest. Typically,
these materials have high activity in basic solutions but inferior
performance in neutral to acidic electrolytes.[5, 14]
When developing an effective electrocatalyst, the following
four issues need to be taken into consideration. First, the im-
provement of activity of the surface catalytic sites is important
to reduce the activation energy barrier of OER.[11] Second, the
enhancement of electronic conductivity of the materials can
assure a fast charge transfer from the surface reaction sites to
the substrate electrode.[15] Third, the enlargement of surface
areas of materials is beneficial to exposure more available reac-
tion sites to realize high current densities at low overpoten-
tials.[16] Fourth, the increase of mass diffusion within the mate-
rials is indispensable for a better migration of reaction substan-
ces and an easier release of O2 bubbles.[17] The former two as-
pects are related to the intrinsic chemical properties of the ma-
terials, and the latter two issues are subject to the
microcosmic physical structures of the materials.
The activity of the surface sites can be finely tuned by chem-
ical composition of the materials.[18] For example, NiFe-based
materials have shown excellent activity in basic solutions for
electrocatalytic OER.[19, 20] A very little amount of FeIII dopant in
NiII-based materials can dramatically enhance the OER per-
formance. The general reasons for the enhancement of activity
by doping are as follows. First, the doped elements can affect
the electronic structure of the active sites to reduce the activa-
tion energies. Second, the doped elements can participate in
the activation of intermediates by assisting the translocation of
protons during OER. Third, doping can induce unsaturated co-
ordination to increase the number of active sites. Forth,
doping can enhance the bulk conductivity of the material by
generating free charges. The surface ligand anions in a variety
of Co-based materials have impact on their OER activity and
stability.[7] The ligands in the material help in the translocation
of protons to lower the activation energy barrier of OER inter-
mediates.[1] The electronic conductivity of materials has also
drawn significant attention in recent studies, as bulk conduc-
tivity is equally essential to surface activity in electrocatalysis.[21]
General interests have mainly been focused on transition
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metal-based phosphides, chalcogenides and nitrides, which
displayed excellent OER activity.[22–25] These materials are con-
sidered as “interstitial alloys” with much better conductivities,
as compared with their metal oxide/hydroxide counterparts.[26]
However, the surface sites are in situ oxidized under OER con-
ditions to form metal oxides/hydroxides as the genuine active
sites.[15] To increase the number of surface sites and the mass
diffusion ability of materials, one general method is construct-
ing porous structures in materials, which will be introduced in
the next section.
Jing Qi is currently a fourth-year grad-
uate student under the supervision of
Prof. Rui Cao and Assoc. Prof. Wei
Zhang in the School of Chemistry and
Chemical Engineering at Shaanxi
Normal University. She finished her
Master degree and transferred to a
Ph.D. candidate in 2017. Her current
research focus is the water splitting re-
action electrocatalyzed by cheap tran-
sition metal-based solid materials. She
received her B.S. (2014) in chemistry
from Bohai University.
Wei Zhang is currently an associate
professor in the School of Chemistry
and Chemical Engineering at Shaanxi
Normal University. His current research
focuses are the catalytic reactions of
water splitting. He received his B.S.
(2007) in chemistry from Peking Uni-
versity in China and Ph.D. degree
(2012) from Nanyang Technological
University in Singapore with Professor
Rong Xu. After photocatalytic CO2 re-
duction postdoctoral work with Profes-
sor Rong Xu, he joined the faculty at Shaanxi Normal University in
2014.
Rui Cao is currently a professor in the
School of Chemistry and Chemical En-
gineering at Shaanxi Normal University.
His main research interests are in bio-
inorganic chemistry and catalytic small
molecule activations. He received his
B.S. (2003) in chemistry from Peking
University and Ph.D. (2008) from
Emory University. He was the Dreyfus
Postdoctoral Fellow from 2009 to 2011
in the Department of Chemistry at
Massachusetts Institute of Technology
under the guidance of Professor Stephen J. Lippard. In 2011, he
became the professor in the Department of Chemistry at Renmin
University of China, and transferred to Shaanxi Normal University
in 2014.
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1.2. Porous materials as electrocatalysts
As promising catalysts, porous materials have drawn extensive
attention in variety areas of chemical engineering process-
es.[27, 28] Owing to the unique physical and chemical characteris-
tics different from bulk materials, porous materials have also
been widely applied in electrocatalysis, which is a heterogene-
ous process happening on the interface.[29–31] Porous materials
have been shown to be versatile in electrocatalysis to provide
more surface sites and easier mass diffusion during electroca-
talysis. There are three general approaches to construct pores
in electrodes. The first method is constructing multi-dimen-
sional structures to generate constructional voids. There are
typically two general strategies for the preparation of materials
with constructional voids. The first is the hard-template synthe-
sis using porous materials such as silica, anodic aluminum
oxide, and etched polymer. Nanowires are synthesized in the
pores of the templates. By removing the templates, nanowires
are connected to construct the voids in the final product. The
second method is the seeded epitaxial growth on substrates at
high temperatures. Nanowire/nanorod arrays are formed by
the epitaxial growth, leaving open spaces between each wire/
rod. Our group recently reported a unique three-dimensional
(3D) Co(OH)F superstructure built by low-dimensional sub-
structures for efficient OER.[17] The building of low-dimensional
substructures (1D nanorods and 2D nanoflakes) brought about
abundant open spaces in the resulting 3D structure. Jin’s
group reported a NiCo hydroxide with a 3D structure by direct
electrodeposition method.[32] The special 3D morphology in-
creased the accessible specific active area to facilitate OER. The
second method to generate pores in electrodes is introducing
3D substrates, such as metal foams and conductive carbon-
based materials, to load the electrocatalysts.[33–36] Zhao and co-
workers electrodeposited NiFe thin films on nickel foam by a
potentiostatic technique.[37] Owing to the distinctive macro-
scopic 3D skeleton, it can support massive catalysts to provide
more available active sites. Ren’s group fabricated FexN films
on 3D graphene/Ni foam by a similar strategy.[38] The third
method is constructing intrinsic pores in bulk materials. Re-
cently, Dong’s group prepared porous Ni2.0Mo0.26@NC compo-
sites by one-step annealing.[39] The mesoporous structure en-
larged the active surface area, and therefore improved catalytic
properties. Our group obtained porous NiFe mixed oxides
through the evaporation of surfactants at relatively low tem-
peratures.[20] For the porous materials to be discussed in this
Review, we will focus on the materials with intrinsic pores.
1.3. Scope of this review
Compared with bulk materials, the porous counterparts can
lower mass transfer resistance and increase specific current
densities in OER. Scientists have made remarkable progress in
recent years in methodologies for preparing diverse porous
structures. In the following sections of this Review, we will dis-
cuss the general methods reported in recent literatures to pre-
pare porous materials for electrocatalytic OER. The methods in-
troduced in this Review include the thermal decomposition,
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electrochemical deposition, template-assisted synthesis, chemi-
cal etching and other special methods. The content will focus
on cheap element-based materials, including cheap transition
metal-based (Ni, Co and Fe) materials and metal-free carbon-
based materials. The relevant advantages and disadvantages of
different synthetic methods and the specific effects of pores in
electrocatalytic processes are summarized. According to the
major element in the materials, the porous samples prepared
by similar methods are classified into subsections, which are
metal-free, Co-based, Ni-based, Fe-based and mixed metal-
based porous OER electrocatalysts.
2. Thermal Decomposition to Prepare Porous
Materials
During heat treatment, thermal decomposition of material pre-
cursors with the escape of gases or the removal of surfactants
is the major reason for the generation of pores.[20] In addition,
the unmatched crystal domains have been reported to com-
pose porous nanostructures by calcination.[40] Annealing tech-
nique, owing to its simplicity and reliability, is a universal ap-
proach to produce pores in solid materials. However, thermal
treatment usually causes a reduced surface area with an in-
creased crystallinity. The smaller surface area is not beneficial
for catalysis, whereas the crystallinity has uncertain effects on
the catalytic performance. In this section, representative
porous materials prepared from thermal decomposition
method are discussed for electrocatalytic OER.
2.1. Metal-free porous materials for OER
The metal-free materials are promising electrocatalysts, which
are low-cost and readily available.[41, 42] Until now, most articles
are reporting metal-based materials for electrocatalytic OER.
There are few reports on metal-free carbon-based electrocata-
lysts due to their relatively low activity. However, carbon-based
materials can be bifunctional for not only OER but also other
small molecular activation reactions, such as hydrogen evolu-
tion reaction and oxygen reduction reaction.[43, 44] Moreover,
some carbon-based electrocatalysts have a wide tolerance of
Figure 1. The preparation of N and P co-doped mesoporous nanocarbon (NPMC) foams from the polymerization of aniline and phytic acid, followed by pyrol-
ysis in Ar. Reproduced with permission.[45] Copyright 2015, Macmillan Publishers Limited.
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the pH of the electrolyte. The doping of other nonmetal ele-
ments can significantly improve the electrocatalytic per-
formance of native carbon-based materials. Dai’s group fabri-
cated metal-free N and P co-doped mesoporous nanocarbon
(NPMC) foams via thermal decomposition (Figure 1).[45] First,
aniline and phytic acid reacted to form polyaniline aerogels
with a macroporous structure. Next, the aerogels were subject-
ed to pyrolysis at high temperature to form the nanocarbon
foam. During the pyrolysis process, the macroporous structure
contracted and the overlapped mesoporous structure turned
to be hierarchical. Meanwhile, the material gave off carbona-
ceous gases to create smaller pores. The sample pyrolyzed at
1000 8C (NPMC-1000) with ample pores was characterized by
N2 adsorption/desorption isotherms. The specific surface area
is determined to be 1548 m2 g@1 with a high pore volume at
about 1.1 cm3 g@1. In 0.1 m KOH solution, the NPMC-1000
coated electrode exhibited a small onset potential at around
1.3 V vs. the reversible hydrogen electrode (RHE) in the linear
scan voltammogram (LSV) curve for OER. Its porous structure
facilitated efficient oxygen diffusion and full access between
catalytic sites and electrolyte.
Recently, Li and co-workers reported the nitrogen-doped
mesoporous carbon nanosheet/carbon nanotube hybrids (N-
MCN/CNTs) prepared by a simple pyrolysis method
(Figure 2).[46] The final sample was obtained by the calcination
of a mixture of urea, glucose and CNTs under Ar at high tem-
perature. The generated ammonia and carbon nitride gases
were the cause of pores during the annealing process. The cor-
responding electrocatalytic activity was detected in a 0.1 m
KOH. The hybrids only need an overpotential of 320 mV to
reach a current density of 10 mA cm@2. The porous morphology
and the high specific surface area provided abundant catalytic
sites to promote OER. Moreover, porous structure can facilitate
oxygen emission and electrolyte flow through low-resistant
pathways.
2.2. Co-based porous materials for OER
Porous Co-based materials are widely reported to exhibit good
electrocatalytic activity and stability for OER.[7] Recently,
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Figure 2. The preparation of mesoporous N-doped carbon nanosheets
loaded on CNTs from the pyrolysis of a mixture of glucose, urea and CNTs in
Ar. Reproduced with permission.[46] Copyright 2016, The Royal Society of
Chemistry.
Zhang’s group fabricated mesoporous Co3O4 nanotubes via a
facile annealing strategy (Figure 3).[47] When heated in air, the
cobalt-aspartic acid nanowire precursors were oxidized rapidly
with the release of gases. The final sample retained the macro-
pores of the tubular structure and contained abundant meso-
pores on the wall. The specific surface area is approximately
87.8 m2 g@1, and the mesopore size is around 5.5 nm. The
nanotubes with hierarchical pore structures exhibited an en-
hanced OER performance with good stability in alkaline solu-
tions, reaching the current density of 10 mA cm@2 at 1.62 V (vs.
RHE) in a 0.1 m KOH. In addition, the unique mesoporous walls
and novel open-ended tubes promoted electrolyte penetration
and afforded more catalytic sites to benefit OER.
Qiao’s group reported that carbonization of metal complex
precursors is a versatile method to generate pores in metal-
carbon hybrid materials (Figure 4).[48] Hybrid Co3O4-carbon
porous nanowire arrays (Co3O4C-NA) were synthesized through
the carbonization of a Co-based metal-organic framework
(MOF) in N2 atmosphere. Nitrogen adsorption and desorption
isotherms of Co3O4C-NA indicate a high surface area of
251 m2 g@1, and the pore size is mainly distributed around
5 nm. Carbonization process dramatically increased the surface
area and porosity. On the basis of the double layer capacitance
(209.7 mF cm@2), the roughness factor (RF) can be deduced
with a high value of 371. The Co3O4C-NA is a highly efficient
OER electrocatalyst, which can deliver a current density of
10 mA cm@2 at a small potential of 1.52 V (vs. RHE) in a 0.1 m
Figure 3. The illustration of the formation process of the Co3O4 mesoporous nanotubes from the oxidation and diffusion of species in the cobalt-aspartic acid
nanowire (Co-Asp) precursor. Reproduced with permission.[47] Copyright 2016, Wiley-VCH.
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Figure 4. The illustration of the synthesis of nanowire arrays of porous
Co3O4-carbon hybrids from the carbonization of nanowire arrays of Co-
based MOFs in N2. Reproduced with permission.[48] Copyright 2014, Ameri-
can Chemical Society.
KOH. In contrast to ordinary planar films, Co3O4C-NA has a
larger active surface area to expose more catalytic sites. At the
same time, the open spaces between the nanowires and the
porous structure within the nanowires are beneficial for gas
diffusion and mass transfer.
2.3. Ni-based porous materials for OER
Ni-based materials are also widely reported as efficient OER
electrocatalyst. The nickel oxides/hydroxides are typically less
active than Co-based analogues.[11] However, the nickel phos-
phides and chalcogenides are active OER electrocatalysts,
mainly due to the much enhanced electronic conductivity.[33]
Paik and Lou and co-workers reported the fabrication of
porous nanoplates using Ni(H2O)2[Ni(CN)4] Prussian blue ana-
logue (NiNi-PBA) nanoplates as the template.[49] Carbon coated
porous nickel phosphide nanoplates were prepared through
low-temperature phosphidation with NaH2PO2 under Ar. The
roughness and pores can be clearly detected on the surface of
Ni-P nanoplates. The measured specific surface area is
35 m2 g@1. The Ni-P porous nanoplate electrode delivered a cur-
rent density of 10 mA cm@2 at only 1.53 V (vs. RHE) in a 1 m
KOH. One reason for the efficient OER activity is that the nickel
phosphates can quicken mass transfer. The porous nanoplate
could bring about more catalytic sites, which further improved
water oxidation activity. The calcination of the precursor with-
out NaH2PO2 resulted in porous NiO sample with a worse activ-
ity for OER, as compared with Ni-P nanoplates.
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Figure 5. The formation process of hollow NiS with porous walls by a reduc-
tive pyrolysis of a hydrothermal-synthesized hollow NiS2 precursor. Repro-
duced with permission.[50] Copyright 2017, American Chemical Society.
Recently, Wang’s group developed NiS2 hollow mi-
crospheres by a simple hydrothermal process
(Figure 5).[50] The subsequent NiS porous hollow mi-
crospheres were obtained by annealing the NiS2
sample under H2/Ar atmosphere. Mesoporous NiS is
determined to be a superior electrocatalyst for OER,
requiring an overpotential of 320 mV at a current
density of 10 mA cm@2. The NiS porous texture was
obtained during the lattice reorganization from the
conversion of NiS2. This porous material has a specif-
ic surface area of 52.3 m2 g@1 and a pore volume of
0.218 cm3 g@1. The pores played a crucial role in en-
hancing the OER activity. The porous microstructure
is an efficient pattern to enlarge the active surface
area and accelerate the ion diffusion.
2.4. Fe-based porous materials for OER
Ren and co-workers revealed nanoporous iron nitride film on
3D macroporous graphene/Ni foam.[38] First, the graphene was
coated on the Ni foam. Subsequently, the precursor of
Fe(NO3)3 dissolving in DMF was loaded on the Ni foam-gra-
phene network. The DMF solvent was slowly removed by heat-
ing. Then, the sample was annealed at 400 8C under Ar for
30 min and NH3/Ar for 1 h in sequence. As a comparison, the
iron oxide film on graphene/Ni foam was synthesized under
the same condition except the nitridization under NH3/Ar. After
the annealing treatment, observable pores were detected from
the removal of the DMF solvent. Without DMF solvent, a uni-
form dense film will be generated. Furthermore, only the accu-
mulated iron nitride without any porosity was observed when
DMF was replaced by ethanol. The nature of the solvent mole-
cules has impact on the formation of the porous structure. The
as-obtained FexN film/graphene hybrid displayed high electro-
catalytic performance for OER in 1 m KOH aqueous solution.
The nanoporous FexN film displayed a current density of
10 mA cm@2 at an ultra-low overpotential of 238 mV. In addi-
tion, nanoporous film showed faster charge transfer in OER by
electrochemical impedance spectroscopy. The electrochemical
active surface area of the catalyst was inferred from the
double-layer capacitance, indicating a larger active surface area
of the FexN electrode. The nanopores in the materials guaran-
teed a large contact area and rapid reactant transport. The re-
ports on correlative Fe-based porous OER electrocatalysts are
less than Co-based and Ni-based systems. This work proved
that Fe-based porous materials are promising substitutes for
OER. The introduction of common solvent molecules is inter-
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esting for the preparation of porous materials under low tem-
peratures.
Wang and co-workers synthesized pore-rich FeP nanorods
on carbon nanotube (CNT) backbone by a bottom-up assem-
bly and phosphorization (Figure 6).[51] The pore-rich structure
stemmed from the reduced phase volume during solid/gas
phase phosphorization. Thus, the volume change caused by
the phase conversion leads to the porosity. TEM image indicat-
Figure 6. The synthesis of porous FeP on CNTs from a two-step solvothermal growth and
phosphorization strategy and the corresponding SEM image of the FeP@CNT hybrid. Re-
produced with permission.[51] Copyright 2016, The Royal Society of Chemistry.
ed that FeP@CNT have abundant holes and cavity space. The
specific surface area of FeP nanorods is about 98 m2 g@1, which
is larger than that of the precursor of FeO(OH)@CNT. The
FeP@CNT could achieve a current density of 10 mA cm@2 at
about 300 mV overpotential with a low Tafel slope of
53 mV dec@1. Pore-rich morphology is a reason for the remark-
able activity. Specifically, it can increase accessible active sites
and promote the ion diffusion in OER.
2.5. Mixed metal-based porous materials for OER
In addition to single metal electrocatalyst, the mixed metal-
based materials displayed excellent OER activity. In some cases
such as the NiFe system, the doped materials have significantly
enhanced OER performance compared with their single metal
counterparts.[20] Mixed metal porous materials based on the
cheap transition metals have also been developed. The ther-
mal decomposition methodology is similar with the systems in-
troduced above. It is noteworthy that the nature of the precur-
sor mixture is important to uniformly distribute the different
metal elements in the final pyrolyzed sample.[52] Recently,
Zheng’s group designed CuCo hybrid oxides via a facile hydro-
thermal growth and annealing under Ar.[53] Porous CuCo
hybrid oxides acted as a highly reactive electrocatalyst for OER.
Recently, Lou’s group synthesized mixed-metal oxyphosphide
particles with porous shells through thermal treatment.[54] The
porosity could increase the number of catalytic sites, which is
conducive to OER catalysis.
Our group developed a novel evaporation method to pre-
pare highly efficient NiFe oxides for electrocatalytic OER
(Figure 7).[20] In conventional thermal decomposition methods
to prepare porous materials, the final materials have very low
surface areas after the thermal treatment at high temperatures.
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Figure 7. The formation evolution of the NiFe mixture under different tem-
peratures. Reproduced with permission.[20] Copyright 2015, Wiley-CVH.
Meanwhile, the NiFe mixture will be converted into inactive
ferrate at high temperatures. To overcome this limitation, a
Tween surfactant was used to prepare the NiFe precursor. This
surfactant molecule can be removed by simple evaporation at
around 200 8C to construct the porosity. At this perfect temper-
ature, the mixture has a phase of Fe-doped NiO, which is the
efficient phase for OER. This work proves that the selection of
suitable surfactant is critical to prepare active porous catalysts.
To summarize this section, thermal decomposition is fre-
quently used as a convenient method in achieving multiaper-
ture materials. The prepared samples tend to be chemically
stable, reproducible and highly crystalline. However, the clear
defects are the significantly reduced surface areas, the large
energy consumption and poor safety performance at high
temperatures. There are still much room for improvement in
the selection of suitable precursors and surfactants to prepare
porous samples from thermal decomposition at relatively low
temperatures.
3. Electrochemical Deposition to Prepare
Porous Materials
Electrochemical deposition of catalyst films on charge collec-
tors has proven to be a convenient method to make electro-
des for electrocatalysis.[55] It is a process to load active species
directly onto the electrode surface via cathodic/anodic electrol-
ysis of a catalyst-precursor solution (salts or complexes).
During the deposition, the in situ formed bubbles under polar-
ization conditions and the penetration of ions assist in the for-
mation of the pores within the deposited film. Electrodeposi-
tion is a simple and convenient method with low energy-con-
sumption to prepare active electrodes for catalysis.[56] Mean-
while, the film composition, thickness and morphology can be
easily and fine tuned by simply controlling the deposition po-
tential and time. Thus, electrodeposition has received great at-
tention in electrocatalysis. Porous films prepared by electrode-
position have also been widely reported.
3.1. Co-based porous materials for OER
During electrochemical treatment, the samples were readily
precipitated with or without the production of gases at an ap-
plied voltage on the electrode. Tour’s group constructed
porous Co oxide thin film by an anodization method
(Figure 8),[57] which generated pores with an average pore size
of 80 nm in the film. Next, the porous film reacted with phos-
phorous vapor to prepare the Co phosphide/Co phosphate
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Figure 8. (a) The fabrication of the Co phosphide/Co phosphate thin film
(PCPTF) from the phosphorization of an electrodeposited porous Co oxide
film. (b–d) The SEM images of the porous PCPTF films. Scale bars are all
500 nm. Reproduced with permission.[57] Copyright 2015, Wiley-CVH.
thin film (PCPTF). The porosity of the electrodeposited film was
retained during the phosphidation. The morphology of the
prepared PCPTF was determined by SEM and TEM, showing a
highly porous feature. The roughness factor is positively associ-
ated with the electrochemical surface area. After the anodiza-
tion treatment, the roughness factor increased significantly to
result in more exposed active sites. The OER activity was
tested in a 1 m KOH aqueous solution, where PCPTF was an
electrochemically active sample with a small overpotential of
330 mV at 30 mA cm@2. In contrast, the compact film exhibited
a higher onset potential, lower kinetic current density, and
larger Tafel slope. The OER activity of the porous Co-based thin
film was clearly superior to the compact film, because PCPTF
possessed highly ordered porous structures. In this system, the
porous feature could afford more catalytic sites with a low
loading to favor OER. It is difficult to get porous metal phos-
phides from direct electrodeposition. This work proves the
concept of generation of a porous oxide film as the precursor
to construct porous phosphides.
A recent article reported hydrophilic porous CoS2/carbon
nanotube composites (CNT-CoS2) via a one-step cyclic voltam-
metry electrodeposition and dissolution by Huang’s group
(Figure 9).[58] The film was generated on the CNT-modified
glassy carbon electrode using dissolved cobalt chloride and
thiourea. The prepared electrode achieved a high OER activity
and stability under alkaline conditions with a small overpoten-
tial of merely 290 mV to reach a current density of 10 mA cm@2.
Two oxidation peaks were found in the cyclic voltammetry
electrodeposition, indicating the oxidation and dissolution
phenomena of the CoS2 film. The repeated transformation pro-
cess resulted in the porous nanostructure, which could enlarge
the active area and accelerate mass and charge transport.
Pores can originate from the emerged nanosheets piling
through self-templated electrodeposition strategy. Pore struc-
tures, derived from this method, are random and uneven.
Qiao’s group developed hollow Co3O4 microtube arrays (Co3O4-
MTA) with porosity by self-templating electrodeposition
(Figure 10).[59] This unique porous shell initiated OER at a low
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Figure 9. The illustration of the operation of the porous CoS2 on CNT networks for OER
based on an electrodeposition and electrooxidation/dissolution process. Reproduced
with permission.[58] Copyright 2017, The Royal Society of Chemistry.
Figure 10. The SEM images of the highly porous and hollow Co3O4 micro-
tube arrays. Reproduced with permission.[59] Copyright 2017, Wiley-VCH.
onset potential and achieved a rapid rise in the current density.
Co3O4-MTA had hollow structures and sufficient pores with a
high surface area of 233 m2 g@1. The pores and the hollow ar-
chitecture could provide abundant active sites, helping the
transport of electrolyte and gases.
Figure 11. The SEM images of the porous microsphere superstructures on 3D porous nickel foam prepared from a cathodic electrodeposition in an electrolyte
containing NiCl2. Reproduced with permission.[61] Copyright 2016, American Chemical Society.
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Yuan’s group created Co-phosphide mesoporous
nanorod arrays (CoP-MNA) with mesopores on the
conductive Ni foam by conventional chronoamper-
ometry.[60] The mesopores are clearly formed as a
result of the packing of nanoparticles. The N2 adsorp-
tion-desorption results are in good agreement with
TEM images, indicating a specific surface area of
148 m2 g@1 and a pore volume of 0.224 cm3 g@1. The
CoP-MNA was demonstrated to be an effective OER
catalyst with a low applied potential of 1.52 V (vs.
RHE) at a current density of 10 mA cm@2. The subsis-
tent pores can be accountable for rapid diffusion of
reactants/products and provide abundant catalytic
sites to improve OER activity.
3.2. Ni-based porous materials for OER
Sun’s group prepared porous urchin-like Ni2P microsphere sup-
ported on nickel foam (Ni2P/Ni/NF) through a cathodic electro-
deposition and a following phosphidation (Figure 11).[61] Plenti-
ful macropores were found on the electrodeposited film as a
result of the generation of hydrogen bubble during the elec-
trolysis process. The surface morphology and the pore struc-
ture remained unchanged after a low-temperature phosphida-
tion. The open macropore structures were in favor of excellent
oxygen detachment and ion diffusion for OER. The correspond-
ing CV curves showed that Ni2P/Ni/NF released oxygen rapidly
at 1.42 V (vs. RHE) in a 1 m O2-saturated KOH. This highly active
film needs a very small overpotential of 200 mV to achieve a
current density of 10 mA cm@2.
3.3. Mixed metal-based porous materials for OER
Zhao’s group applied a combination of hydrothermal method
and electrochemical treatment to synthesize porous NiFe/
NiCo2O4/Ni foam composite electrode.[62] The porous 3D nickel
foam substrate has many advantages. For instance, it exposes
large active surface area to electroplate mesoporous NiFe
nanosheets, accelerates the mass transfer and gas diffusion.
The hydrothermal deposited NiCo2O4 exhibited a nanoporous
flake structure, and the electrochemical deposited NiFe double
hydroxide nanosheets existed massive mesopores. This hier-
archical pore structure ensured abundant available catalytic
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Figure 12. The illustration of the porous NiFeS-based ultrathin nanosheets on Ti plate
from a combined process of electrodeposition, calcination in air and electrochemical
tuning. Reproduced with permission.[63] Copyright 2016, Wiley-VCH.
sites to achieve high OER activity. NiFe nanosheets were elec-
trodeposited on NiCo2O4 by strong interactions, which realized
a high stability during a 10-h constant current electrolysis.
Zhang’s group reported amorphous Ni-Fe-S ultrathin nano-
sheets anchored on Ti plate (Figure 12).[63] The experimental
procedure consisted of three steps. First, Ni-Fe-S nanosheets
(NFS) were electrodeposited on the substrate. Next, the film
was calcinated to obtain oxygen-incorporated Ni-Fe-S ultrathin
nanosheets (O-NFS). Finally, the film was subject to electro-
chemical tuning to form the highly active OER film (O-NFS-
ECT). Electrochemical deposition played a significant role in
forming porous nanosheets. The O-NFS-ECT exhibited a com-
paratively high OER activity in a 1 m KOH, requiring an overpo-
tential of 300 mV to reach a large current density of
@2
500 mA cm and maintaining at a stable current density of
1100 mA cm@2 for 12 h. The special open framework was bene-
ficial to create plentiful active compounds and fast mass trans-
fer channels.
Our group recently reported a novel stepwise electrodeposi-
tion method to prepare NiFe-based porous untra-thin film for
highly efficient electrocatalytic OER (Figure 13).[56] First, a Ni-
based film was deposited via cathodic electrolysis. The result-
ing film has isolated Ni-based nanoplates. Second, the Fe spe-
cies was integrated into the Ni-based film via anodic CV scans.
The amount and composition of Ni and Fe species on the elec-
trode can be controlled by the electrolysis time and the CV
cycle numbers. Interestingly, after the second step of Fe-incor-
poration, an interconnected reticular film with abundant pores
is generated. This porous and reticular structure resulted from
stepwise deposition is beneficial for the electrocatalytic OER by
assisting both mass and charge transfer. Owing to the intrinsic
Figure 13. The illustration of the preparation of NiFe-based ultrathin porous
reticular film from a stepwise electrodeposition method, including a catho-
dic deposition of Ni species and a CV deposition of Fe species. GC: glassy
carbon. Reproduced with permission.[56] Copyright 2017, Wiley-VCH.
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high activity of the NiFe mixture, the porous struc-
ture and ultra-low loading amounts of the active
species on the electrode, this system displayed a
super high turnover frequency of 8.7 s@1 for OER at
an overpotential of 329 mV.
To summarize this section, the electrochemical
deposition technique is a simple and convenient ap-
proach for generating multi-aperture materials with
simplicity, sensitivity, convenience, fastness, and inex-
pensiveness. However, it still has some deficiencies.
For instance, the synthetic morphology is usually difficult to
control. The electrodeposited film is usually amorphous, which
has high surface area but poor crystallinity. The poor crystallini-
ty may cause serious film evolution and dissolution during the
OER process. Some porous materials have been achieved by
electrochemical synthesis, but there is some distance away
from universal application to prepare unique metal phos-
phides, nitrides, carbides and chalcogenides, etc.
4. Template-Assisted Methods to Prepare
Porous Materials
The template-assisted method has long been recognized as a
crucial strategy for the synthesis of porous structures.[64] The
synthesis route begins with the introduction of various precur-
sors into the pores and onto the surfaces of templating
agents. Next, the mixture is heat-treated to obtain oxides or
other phases. Lastly, the templates are removed by chemical
methods, and open spaces are left in the resulting materials.
Nowadays, researchers developed a large quantity of porous
materials via the template-assisted method. The conventional
templates consist of mesoporous silica, metal-organic frame-
works and SiO2 microspheres, etc..
4.1. Metal-free porous materials for OER
Metal-free carbonous materials can be readily synthesized
using templates. Dai’s group used a mixture of melamine-
nickel sulfate complex and KCl to prepare the KCl and Ni incor-
porated graphitic sheets by calcination under Ar (Figure 14).[65]
The Ni and KCl seeds were removed by the treatment in an
aqua-regia solution. N, S co-doped graphitic sheets with ster-
eoscopic holes (SHG) were finally obtained by another high
temperature calcination under Ar. The stereoscopic holes not
only helped ionic and electronic transport, but also afforded
open sites to catalyze OER. The sample exhibited a current
density of 10 mA cm@2 at 1.56 V (vs. RHE) and a low Tafel slope
of 71 mV dec@1 in a 0.1 m KOH solution. Mesopores with diame-
ters between 3 and 30 nm and a pore volume of 1.40 cm3 g@1
are determined for the porous graphite material. This material
can not only electrocatalyze OER, but also facilitate the hydro-
gen evolution and oxygen reduction reactions.
4.2. Co-based porous materials for OER
Teysez’s group designed ordered mesoporous Co3O4 by adopt-
ing KIT-6 as a hard template.[64] In the preparation, KIT-6 was
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Figure 14. (a) The illustration of the formation of N, S co-doped graphitic sheets with stereoscopic holes (SHG) from the removal of the KCl-Ni particles.
(b) SEM and (c,d) TEM images of the SHG, showing abundant pores. Reproduced with permission.[65] Copyright 2017, Wiley-VCH.

immersed in the precursor solution to produce a mixture,

which was subject to calcination to generate Co3O4. The KIT-6
was removed in a hot 2 m NaOH to obtain the ordered meso-
porous Co3O4. Based on the nitrogen adsorption isotherm, the
surface area is 141 m2 g@1 and the mesopore volume is
0.471 cm3 g@1. Electromicroscopic images also confirmed the
existence of holes, and the visual pore size is about 11 nm. The
linear sweep voltammetry showed that Co3O4 was an efficient
catalyst with enhanced OER activity in a 0.1 m KOH electrolyte.
On the one hand, holes improved the availability of surface
sites. On the other hand, rich pores prevented Co3O4 from con-
gregating in basic solution toward an enhanced stability. Simi-
larly, hierarchical mesoporous cobalt oxide was synthesized by Figure 15. The illustration of the preparation of mesoporous Ni sphere
arrays from a silica-templating method. Reproduced with permission.[67]
Jiao’s group.[66] In the experimental process, template-assisted Copyright 2016, American Chemical Society.
method is adopted to fabricate porous Mg-substituted Co3O4
by removing the silica template and selective etching Mg ions.
The catalyst exhibited a relatively high specific surface area tended more channels to transfer reactants. This approach in-
and markedly increased electrocatalytic properties. creased the superficial area and conductivity simultaneously,
and the formative interconnected porous structure has guid-
ance in optimizing OER catalysts.
4.3. Ni-based porous materials for OER
More complicated templating method was introduced by
4.4. Mixed metal-based porous materials for OER
Chen’s group to fabricated 3D ordered mesoporous Ni sphere
arrays (3D-OMNiSA) (Figure 15).[67] The methyl methacrylate Metal-organic frameworks (MOFs) are emerging as new materi-
(MMA) was polymerized on the surface of ordered silica sphere als for catalysis because of their abundant configurations and
arrays. Then, poly(methyl methacrylate) (PMMA) inverse opal unusual properties.[68–71] Nowadays, MOFs were frequently used
was obtained through HF etching to remove the silica core. as template in preparation of novel porous materials. The FeNi
Next, the nickel chloride precursor was filled into the void of alloys/NiFe2O4@NC microboxes with ample pores were pre-
the PMMA. After the reduction of the Ni salt into Ni metal, the pared by a template-assisted method.[72] The MOF structure is
PMMA template was eliminated to get the final 3D mesopo- the template to construct the final boxes. This method is simi-
rous Ni spheres. The as-prepared Ni spheres displayed typical lar with thermal decomposition method. The differences lies in
mesoporous structures. The computational surface area is the remain of the MOF structure in the final pyrolyzed material.
108 m2 g@1 and its pore sizes mainly distributed in 3–5 nm. The This material displayed high activity for electrocatalytic OER,
3D-OMNiSA had a smaller onset potential than that of 20 wt % delivering a current density of 10 mA cm@2 at an overpotential
Pt/C in a 0.1 m KOH for OER. The Nyquist plot indicated that of 316 mV. To prepare similar NiFe-based porous material,
the 3D-OMNiSA offered a low resistance during OER. The spe- Wei’s group adopted a sacrificial SiO2 template to synthesize
cial porosity is the primary reason for the excellent OER activi- mesoporous NiFe-layered double hydroxide (NiFe-LDH) hollow
ty. Pores exposed a higher active area to catalyze OER and ex- microspheres (HMS) (Figure 16),[73] whose hole features were

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Figure 16. (left) The illustration of the preparation of porous NiFe-based hollow spheres from a silica-templating method. (right) The electromicroscopic
images of the silica spheres (A, D) and the porous NiFe spheres (B, C, E, F). Reproduced with permission.[73] Copyright 2016, American Chemical Society.
clearly observed. The SiO2 nanospheres are crucial to control
and guide the formation of porous hollow material. The de-
tailed electrochemical properties were determined, realizing a
current density of 10 mA cm@2 at a very small overpotential of
239 mV. Owing to its large active area and special mesopores,
the NiFe-LDH HMS material is an efficient OER catalyst to re-
lease oxygen.
To summarize this section, the template-assisted method is a
classical method to design porous materials and brings about
dramatic progresses in the field of OER. Using hard templates,
the freshly prepared porous catalysts are less prone to aggre-
gate comparing with other nanoparticles. Furthermore, the
samples are highly flexible by template-based method, with
which researchers can control regular materials with different
morphologies. This approach has several downsides in the pro-
cess of preparation, which involved introducing and eliminat-
ing templates. The preparation procedure is always complicat-
ed and high-cost, and some hazardous chemicals are frequent-
ly used to remove the templates. Overall, template synthetic
route possesses many benefits to construct porous structure,
but there are some remaining problems needing to be solved.
5. Chemical Etching to Prepare Porous Materi-
als
Etching method means chemical reagents react with required
materials to produce desired pores.[74] It is similar but different
to the removing of templates as introduced in the above sec-
tion. In this section, we discuss with the removal of parts of
desired material to create pores. For the templated synthesis,
the catalysts and the templates are totally two different and
isolated components. For the chemical etching method, the
desired catalyst and the removed parts are chemically integrat-
ed. The pores created in this section are typically located
within a single crystal of the material. The traditional acid and
alkaline etching is capable of creating porous materials with
higher active surface areas.
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5.1. Metal-free porous materials for OER
To utilize ecofriendly biomass for electrocatalysts, Zheng’s
group developed egg-derived mesoporous carbon micro-
spheres (egg-CMS) with large pore volume by the traditional
alkaline etching (Figure 17).[75] Tetraethyl orthosilicate was
mixed and spray dried with eggs to prepare the precursor. The
silica in the final mixture was removed by etching to obtain
mesostructures. According to N2 adsorption and desorption re-
sults, the pore volume is 0.5 cm3 g@1 and the surface area is as
high as 970 m2 g@1. In addition, electrochemical impedance
spectroscopy also concluded that egg-CMS has porous fea-
tures with diagnostic Gerischer impedance. In a 0.1 m KOH
electrolyte, the egg-CMS achieved a current density of
74.6 mA cm@2 at 1.6 V (vs. RHE) and a Tafel slope of
59 mV dec@1. As a new environmental-friendly catalyst, the
egg-CMS with designed porous architecture could involve
more active sites in catalyzing OER. Easy preparation and low
reactant cost make this method potentially valuable for exten-
sive applications. Metal ions from proteins may exist in the
final product.
Acid etching is also a critically important way to create
pores. Tong’s group prepared 3D self-supporting monolithic
porous carbon cloth doped with N-heteroatom (3D NiD-PCC)
with concentrated hydrochloric acid etching of Ni.[74] Electromi-
croscopic images showed the 3D NiD-PCC has abundant pores
on the rough surface and uniform pores rooted in the soluble
Ni nanoparticles. The NiD-PCC catalyst acted for efficient OER,
starting to generate oxygen at a small overpotential of
250 mV. Its small Tafel slope and low resistance illustrated fa-
vorable kinetic process during OER, showing that the high-po-
rosity 3D NiD-PCC is a fine electrocatalyst for OER.
5.2. Co-based porous materials for OER
Similar etching strategy has been applied to prepare Co-based
porous materials. Wang’group synthesized cobalt nanoparticles
embedded in nitrogen doped porous carbon nanofibers (Co-
PNCNFs) by the combination of electrospinning and acid etch-
ing method (Figure 18).[76] The ample pores were produced by
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Figure 17. The illustration of the preparation of egg-derived mesoporous carbon microspheres from the carbonization of a mixture of egg and silica and the
chemical etching of the silica in the mixture.[75] Copyright 2016, Wiley-VCH.

5.3. Ni-based porous materials for OER

Recently, Xie’s group designed a b-Ni(OH)2 ultrathin nanomesh

Figure 18. The preparation of nitrogen doped porous carbon nanofibers and
the loading of Co nanoparticles.[76] Copyright 2016, The Royal Society of
Chemistry.
the reaction between 0.5 m H2SO4 solution and metallic cobalt
particles. The surface area of the obtained Co-PNCNFs was
356.6 m2 g@1, which was significantly higher than the
pure N-doped carbon nanofibers. The integrated
material was highly active to achieve a current den-
sity of 10 mA cm@2 at an overpotential of 285 mV.
This outstanding catalytic performance is partially at-
tributed to the distinctive pore architecture with
large active interfaces.
Figure 19. The preparation of porous b-Ni(OH)2 nanomesh from the chemical etching of
Al components in the NiAl-LDH nanosheet followed by the Ostwald ripening.[77] Copy-
right 2017, Wiley-VCH.
as a robust OER electrocatalyst (Figure 19).[77] First, exfoliated
Ni-Al LDH ultrathin nanosheets were obtained via ultrasonicat-
ing bulk Ni-Al LDH. Next, alkaline etching produced porosity in
the b-Ni(OH)2 nanosheets by dissolving the Al components.
After hydrothermal treatment, single-crystalline b-Ni(OH)2 ultra-
thin nanomeshes were obtained as the thermodynamically un-
stable Ni species dissolved and regrew through the process of
Ostwald ripening. During the etching process, strong base re-
acted with amorphous Al species to leave multi-aperture b-
Ni(OH)2. This 2D nanomesh sample supplied abundant exposed
sites and favorable ion penetration to enhance OER activity. Ni-
based electrocatalysts have typical poor cycling stability for
OER, owing to the structural deformation during the reversible
phase changes between the NiII and NiIII species. The abundant
and well-dispersed nanopores in the Ni-based electrocatalyst
can function as effective buffer locations for the volume
change during the redox reactions, thus avoiding structural de-
formation and delivering mechanical stability under continu-
ous OER operations. The b-Ni(OH)2 material only required a

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Figure 20. The preparation of porous FeCo-LDH nanosheets from a water-plasma exfoliation and etching method.[82] Copyright 2017, Wiley-VCH.
low overpotential of 236 mV to drive a current density of
20 mA cm@2 in a 1 m KOH solution. In contrast, nonporous b-
Ni(OH)2 nanosheets possessed smaller specific surface area and
lower electrochemical surface area than b-Ni(OH)2 nanomesh.
The catalytic sites around nanopores are likely to convert into
catalytically active b-NiOOH for efficient OER. The OER activity
enhancement was attributed to (i) the intimate nanomeshs
boosted the electron transfer; (ii) the massive nanopores en-
larged the contact volume of the electrolyte; (iii) the uniform
nanopores increased pathways to deliver oxygen and ionic
conduction.
Paik and co-workers also used alkaline etching to prepare
Ni(OH)2 porous nanoplates.[49] The ion exchange reaction could
occur when 2 m NaOH was added to the NiNi-PBA precursor.
Part of the Ni is dissolved by the strong base to form the
Ni(CN)42@ ions. The as-prepared Ni(OH)2 was an efficient transi-
tion metal hydroxide material for OER.
To summarize this section, the etching process has been suc-
cessfully applied to many mixed metal-based materials to dis-
solve one of the components for the construction of pores.
However, this method has some shortcomings. For example,
the morphologies of prepared materials are difficult to be ac-
curately controlled. The etching agent must be highly selec-
tive, and the application of this approach to generate holes is
limited to few materials. The condition of etching is rigorous
and environmental-unfriendly. For an ideal etching process, it
should be low-cost, easy, simple, applicable, and manageable.
6. Other Methods to Prepare Porous Materials
There are also some unusual ways to synthesize porous materi-
als for electrocatalytic OER, such as electrostatic interaction
stacking, microwave-assisted synthesis and pulsed laser deposi-
tion. These methods are not widely developed owing to the
special instrumentation requirements. Qiao’s group reported
two different materials through random assembly, namely
paper-based N-doped carbon films[78] and N-doped graphene
hydrogel/NiCo double hydroxide.[79] The high porosity was ap-
proved by nitrogen adsorptions. The one-step microwave-as-
sisted approach was used to fabricate porous Zn-Co LDH
nanosheets[80] and Mn2O3 nanoball[81] as efficient OER electroca-
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talysts. Although these methods could synthesize products at
a large scale, they must require specialized instruments.
In recent years, Wang’s group developed an efficient and
general method for the preparation of porous materials using
plasma etching techniques. They synthesized Co3O4 nano-
sheets with abundant oxygen vacancies and large surface area
by Ar plasma-engraving method.[16] Ar-plasma technique is
used for etching and cleaning of materials. Plasma is a state of
matter that is highly electrically conductive. By plasma-treat-
ment, the atoms can be removed from the lattices, leaving va-
cancies and porosity. Of note, Ar-plasma is very time-saving for
the creation of defects and pores. They also applied this strat-
egy for the dry exfoliation of layered materials.[83] The plasma
treatment can not only exfoliate the bulk material but also can
result in multiple pores within a single layer. By the removal of
anions in the interlayer of LDH by plasma treatment, the
stacked layers can be efficiently separated. Compared with tra-
ditional sonication method in solvents, the dry exfoliation by
plasma can produce thin layers with clean surface. From soni-
cation methods, the solvent molecules can be adsorbed on
the surface of the layers and block the effective active sites.
Later, a water-plasma etching method has been developed to
generate porous nanosheets (Figure 20).[82] This novel tech-
nique opens a new way for the efficient preparation of func-
tional materials for electrocatalytic OER.
7. Summary and Outlook
The design of efficient electrocatalyst to accelerate the kinetics
of water oxidation is of crucial importance in the sustainable
energy conversion technologies. An excellent electrocatalyst
must satisfy a number of conditions, such as high activity,
chemical and physical stability, low cost, environmental green-
ness, and convenient and safe preparation. Researchers devel-
oped and modified various methods to synthesize ideal cata-
lyst. Heterogeneous catalysis is a process happening on the in-
terfaces. Porous materials have attracted great attention and
are versatile in heterogeneous catalysis. They have the advan-
tages of large specific surface area, light weight, excellent per-
meability, low density and super adsorption capacity. The
Review discusses the merits of porous materials for electroca-
talytic OER. The advantages brought about by porosity in elec-
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trocatalytic OER can be summed up in the following aspects.
(i) The porosity increases specific surface area and electrochem-
ical active surface area to expose more catalytic sites. (ii) The
open cavities can sufficiently contact and store electrolyte to
make the catalyst robust. (iii) The loose porous structures are
useful for reactant transport and oxygen detachment. (iv) The
pore skeletons provide pathways to transfer electrons. Porous
materials can be divided into three types, including the micro-
porous materials (pore size < 2 nm), mesoporous materials
(2 nm < pore size < 50 nm) and macroporous materials (pore
size > 50 nm).[84] Especially, mesoporous samples can serve as
microreactors to catalytic OER. This Review summarized the ex-
isting synthesis methods and remarkable progresses that have
been made in recent years. However, every technique still has
its characteristic demerits. Thermal decomposition, owing to
its simplicity and reliability, is a universal approach to produce
pores in solid materials. However, thermal treatment usually
causes a reduced surface area. Electrochemical deposition is a
simple and convenient approach for generating multi-aperture
materials with simplicity, sensitivity, convenience, fastness, and
inexpensiveness. However, the synthetic morphology from
electrodeposition is usually difficult to control. The electrode-
posited film is usually amorphous, which has high surface area
but poor crystallinity. The template-assisted method and the
chemical etching method are classical methods to design
porous materials. The prepared samples are highly flexible
with pores within lattices. However, the preparation proce-
dures are always complicated and high-cost, and some hazard-
ous chemicals are frequently used to generate the pores.
The research in porous materials has gained significant pro-
gresses in electrocatalytic OER. However, the most frequent
methods incline to manufacture disordered pores. The synthe-
sis of ordered porous materials is still a great challenge. It is a
great goal to develop highly efficient and controllable method
to massively generate porous materials for OER. Researchers
are required to understand the essences of OER, thus design-
ing the catalysts from fundamentals. Water oxidation is a multi-
step reaction with complicated proton-coupled electron trans-
fer steps. The mechanism of heterogeneous catalytic OER has
uncertainties on different surfaces. Previous studies demon-
strated that electrocatalytic OER contains three typical steps:
water adsorption, water disaggregation and oxygen genera-
tion. Owing to the complex reaction process, monitoring reac-
tion pathway is difficult and concluding accurate reaction
mechanism is still in the preliminary stage. It is necessary to in-
troduce advanced experiments to ensure the real-time detec-
tion and tracking, such as in situ X-ray diffractometer, in situ
Raman spectroscopy and electrode dynamics analysis. Mean-
while, theoretical calculation is also a powerful method to ana-
lyse and predict experimental procedures.
Employing conductive substrates, doping with heteroatoms,
designing advanced porous structures are valid ways to im-
prove the performance of active materials. In the area of de-
signing porous materials, researchers need to develop ad-
vanced technologies to address the shortcomings of existed
methods. For example, MOFs are promising porous materials
with broad applications in recent years. In comparison with
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bulk materials, they have a number of distinct characteristics.
The ultra-high porosity and great specific surface area are im-
portant for the transfer and adsorption of substances. The flex-
ible metal center and organic ligand in MOFs can bring about
unique structural and functional diversity. MOFs are widely rec-
ognized as precursors to prepare advanced porous materials
for electrocatalysis. Another promising direction is the employ-
ment of porous substrates such as metal foams, which have a
3D skeleton for excellent mass diffusion and high electronic
conductivity for electron transfer. It will be promising to grow
active species directly on the skeletons to prepare integrated
electrodes.
To carry through the technological advancements of
humans, electrocatalytic water splitting is of great importance
for sustainability. The development of highly efficient materials
to electrocatalyze water splitting plays a crucial role in realizing
the high energy conversion efficiency. Porous materials are
promising candidates for this important process. Devotions
from not only chemists and material scientists but also engi-
neers of relevant research areas are still needed to construct
highly efficient, durable, cheap and environmental-friendly
electrodes based on porous materials.
Acknowledgements
We are grateful for the support from the Fundamental Research
Funds for the Central Universities (2017CBZ003, and
GK201603037), the Starting Research Funds of Shaanxi Normal
University, the National Natural Science Foundation of China
under grant nos. 21101170, 21503126 and 21573139, and the
“Thousand Talents Program” of China.
Conflict of interest
The authors declare no conflict of interest.
Keywords: electrocatalysis · electrochemistry · oxygen
evolution · porous material · water oxidation
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Manuscript received: October 13, 2017
Revised manuscript received: November 2, 2017
Accepted manuscript online: November 3, 2017
Version of record online: February 8, 2018
T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim