Electrochimica Acta 250 (2017) 77–83

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

CuO nanowire@Co3O4 ultrathin nanosheet core-shell arrays: An

effective catalyst for oxygen evolution reaction
Xiumin Lia , Xiao Duc, Xuli Mac , Zhongde Wangc , Xiaogang Haoc , Abuliti Abudulaa ,
Akihiro Yoshidaa,b , Guoqing Guana,b,*
a
Graduate School of Science and Technology, Hirosaki University, 1-Bunkyocho, Hirosaki 036-8560, Japan
b
North Japan Research Institute for Sustainable Energy, Hirosaki University, 2-1-3 Matsubara, Aomori 030-0813, Japan
c
Department of Chemical Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024, PR China

A R T I C L E I N F O A B S T R A C T

Article history:
Received 23 May 2017 Well-aligned CuO nanowire@Co3O4 nanosheet core-shell array was successfully fabricated on carbon
Received in revised form 2 August 2017 fibers by multi-step electrodeposition combined with thermal treatment and applied as the binder- and
Accepted 10 August 2017 conductive-agent-free anode for oxygen evolution reaction (OER) in water electrolysis process. Such an
Available online 12 August 2017 anode revealed an overpotential of 258  3.2 mV at a current density of 10 mA cm 2 in 1.0 mol L 1 KOH
solution, which is much lower than that of pure CuO nanowires or Co3O4 nanosheets based electrode.
Keywords: This should be attributed to the smart hybridization of CuO nanowires and Co3O4 nanosheets into
CuO nanowire hierarchical core/shell array configuration which could largely increase the amount of contact areas
Co3O4 nanosheet
between electrolyte and active sites. Moreover, it is found that the Cu2+ in CuO/Co3O4 composite was
core-shell structure
oxidized to Cu3+ components during the OER process, which should serve as the new catalytic active sites
electrocatalyst
oxygen evolution reaction for OER. It is expected to provide a novel route to prepare such a core-shell electrocatalyst with high
performance for water splitting.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction Co(OH)2 was easily oxidized to CoOOH and Co3O4 by electro-

Electrochemical water splitting is being attracted extensive
attention due to its high efficiency and good flexibility. It can
produce hydrogen and oxygen with almost 100% purity. However,
for both hydrogen evolution reaction (HER) and oxygen evolution
reaction (OER), if the overpotential is too high, the water
electrolysis efficiency will be reduced to a great extent [1–3]. In
general, the anode side for oxygen evolution suffers more
significant overpotential due to its complexes of four-electron
transition process. Therefore, the development of highly active
electro-catalyst based electrode to reduce the overpotential of OER
is one of the main topics nowadays.
Transition metal oxides are proved to be one class of the most
efficient OER electrocatalysts. Especially, Ni- and Co-based oxides
attract much broader interesting [4,5]. Recently, Switzer et al. [6]
deposited Co(OH)2 on an Au coated glass electrode and found that
* Corresponding author at: North Japan Research Institute for Sustainable Energy,
Hirosaki University, 2-1-3 Matsubara, Aomori, 030-0813, Japan. Tel.: +81-17-762-
7756; fax: +81-17-735-5411.
E-mail address: guan@hirosaki-u.ac.jp (G. Guan).
chemical oxidization and thermal treatment respectively. As a
result, the obtained Co3O4 based electrode exhibited high catalytic
activity for OER. Further studies indicated that the abundant and
diversiform d-orbitals in cobalt oxides endowed the highly active
sites for OER [7,8]. To date, various nanostructured Co3O4 materials
with large surface areas and excellent OER catalytic activity have
been developed [1,2,5]. However, the activity of Co3O4 based
electrocatalysts still needs to be improved. One way is to design
and fabricate a catalyst with a special core-shell three dimensional
(3D) heterostructure, which could increase the surface area and
active sites to a greater extent, and simultaneously facilitate the
diffusions of the reactants and the generated gas. Moreover, such a
heterogeneous catalyst may reveal synergetic properties through
the reinforcement or modification of the core and shell materials.
Besides active components, the support material is also
important for the fabrication of core-shell structure, which should
not only serve as physical support but also provide enough
channels for electron transport. To date, various supports such as
carbon-based materials, transition metal oxides, sulfide and
phosphide have been utilized for this purpose [1,2,9]. The density
kinetic model, quantum chemical study and functional theory
indicated that transition metal oxides are the ideal materials for

http://dx.doi.org/10.1016/j.electacta.2017.08.063
0013-4686/© 2017 Elsevier Ltd. All rights reserved.
78 X. Li et al. / Electrochimica Acta 250 (2017) 77–83
supporting the oxide-based catalysts due to the synergistic effects
among the composite components [10–13]. To date, many support
materials show high surface area, good stability and good electro-
activity. However, it is still required to find new support materials
with better performance. Copper oxide is a well-known semicon-
ductor and abundant on earth. Recently, CuO as a conductive
support material has been attracted considerable attention in the
fields of supercapacitors and lithium-ion batteries. For instances,
Liu et al. [14] prepared a hierarchical CuO@MnO2 core-shell
composite for supercapacitors, which showed remarkably en-
hanced capacitive behaviors. Zhang et al. controllably synthesized
CuO@Co3O4 [15] and CuO@CoO [16] materials for lithium-ion
batteries, which exhibited high capacities of 1191 mA h g 1 and
1364 mA h g 1, respectively. They believed that the high
performance should be due to the synergetic contribution of the
well-aligned core-shell and the ordered array architecture. To date,
CuO as an OER electro-catalyst also attracted researcher’s
attention. For instance, Sun et al. synthesized Cu nanorod @(Cu
(OH)2-CuO) nanosheet material on Cu foil, which needed an
overpotential of 417 mV to drive a current density of 10 mA/cm2 for
OER [17].
In this work, highly ordered Cu(OH)2 nanowire arrays were
fabricated by electro-oxidization of electrodeposited Cu film on
carbon fibers at first, and then Co(OH)2 nanosheets were
controllably electrodeposited on the Cu(OH)2 nanowire arrays.
After subsequently thermal treatment, a well-aligned CuO nano-
wire@Co3O4 nanosheet core-shell array based electrode was
obtained and used for OER. It is expected that this strategy could
be a general way to prepare electrocatalysts with high perfor-
mance for water electrolysis
2. Experimental
2.1. Chemicals
Cobalt nitrate and copper nitrate (Wako, Japan) with analytical
grade were used as chemicals for the preparation of electro-
catalysts on the electrode. Potassium hydroxide and potassium
sulfate (Sigma-Aldrich, Japan) were dissolved in deionized water as
electrolyte for electrochemical characterization of electrodes.
Carbon paper (CP) was provided by Toray Industries Inc., Japan.
2.2. Preparation of CuO/Co3O4 film coated electrode
Potentiostat operated with VersaStudio software was applied to
controllably deposit Cu(OH)2/Co(OH)2 composite precursor and
characterize the electrochemical properties of the as-fabricated
electrode. Three electrodes of a platinum wire, Ag/AgCl/saturated
KCl reference and CP substrate were used as counter electrode,
reference electrode and working electrode, respectively. Here, CP
was pretreated in ethanol for 3.0 h and 1.0 M sulfuric acid for 1.0 h
respectively to improve its hydrophilicity. The efficient deposition
area was 1.0 cm2. Firstly, metallic Cu was deposited on the
pretreated carbon paper by a facile unipolar pulse electro-
deposition (UPED) [18,19] in 0.05 M Cu(NO3)2. Here, the applied
potential during the on-time operation was 1.0 V. Pulse durations
of on-time and off-time were fixed at 1.0 s while the pulse times
were 500. Then, the obtained Cu/carbon fiber (CF) electrode was
oxidized by galvanostatic anodization in 3.0 M KOH solution for
1200 s under 10 mA/cm2 to form Cu(OH)2/CF. Thereafter, Co(OH)2
material was deposited on Cu(OH)2/CF substrate by UPED in 0.1 M
Co(NO3)2 solution. The applied potentials during the on-time
operation were ranged from 0.6 to 1.2 V. Both pulse durations of
on-time and off-time were fixed at 1.0 s, and the electric quantity of
electrodeposition was controlled at 2.6C. the electrode obtained in
each step was washed by distilled water completely. Finally, the
electrodes were heated at a rate of 5  C/min to final calcination
temperature of 300  C and held for 3.0 h.
2.3. Characterization
The electrolysis performance was tested using the linear sweep
voltammetry (LSV, scan rate: 2 mV/s). The electrolytes with various
pH values were prepared by K2SO4 and KOH, but maintained the
same concentration of K+ ions. Electrochemical impedance
spectroscopy (EIS) was performed within a frequency range of
0.02 Hz-0.1 M Hz in 1.0 M KOH solution. The morphology and
element compositions were investigated by a scanning electron
microscope (SEM, Hitachi SU8010) equipped with a Horiba
Scientific energy dispersive spectrometer (EDS) analyzer. The
crystal structures were determined by X-ray diffraction (XRD,
Rigaku SmartLab X-Ray Diffractometer) using a Cu-Ka
(l=1.5405 Å) radiation source. X-ray photoelectron spectroscopy
(XPS) scan was acquired with a VG Scientific ESCALab250i-XL unit
(UK). Transmission electron microscope (TEM) images were
collected on a JEOL JEM-2100F transmission electron microscope.
3. Results and discussion
1.1 Designing of homogeneous and ordered CuO nanowire core
should be crucial for fabricating a rational core-shell hetero-
structure. Here, carbon fiber (CF) was selected as the original
substrate because of its high surface area, good resistance to
electrochemical and chemical corrosion. As shown in Fig. 1,
metallic Cu particles were deposited on carbon fiber by reduction
of Cu2+ ions at 1.0 V (reaction 1). Then, these Cu particles were
oxidized back to Cu2+ in 3.0 M KOH solution by galvanostatic
technique, and subsequently the produced Cu2+ ions reacted with
OH ions to form Cu(OH)2 material (reaction 2). Interestingly,
during the above oxidization process,
the dense and large-size Cu particles were dissolved and rebuilt
to the ordered Cu(OH)2 nanowires. Thereafter, the Cu(OH)2
nanowire/CF composites were further used as the substrate and
the electroactive Co(OH)2 nanosheets were electrochemically
deposited around Cu(OH)2 nanowires in Co(NO3)2 solution. The
details for such an electrodeposition process of Co(OH)2 were
described elsewhere [19,20]. In brief, as shown in reactions 3-5, the
applied negative potential resulted in the formation of OH ions at
the surface of Cu(OH)2 nanowire due to the reduction of NO3 ions,
Fig. 1. Schematic diagram to illustrate the formation mechanisms of Cu(OH)2
nanowire and CuO@Co3O4 core-shell heterostructure.
 X. Li et al. / Electrochimica Acta 250 (2017) 77–83 79

and the generated OH ions reacted with Co2+ ions in the support active Co3O4 materials. Fig. 2G–J show the morphology of
electrolyte. As a result, cobalt hydroxide nanosheets were final CuO/Co3O4 composite. It is obvious that the deposited Co3O4
deposited on the Cu(OH)2 nanowires. Finally, the Cu(OH)2@Co nanosheets convolved around the nanowires and wrapped the CF
(OH)2 core-shell precursor was calcined at 300  C. As such, the Cu uniformly. In addition, the space among the Co3O4 nanosheets
(OH)2 was decomposed to CuO while Co(OH)2 was oxidized to should be in favor of the diffusion of reactants and generated gas,
Co3O4 (reactions 6-7). Finally, a novel CuO nanowire@Co3O4 and meanwhile, the ultrathin morphology of nanosheets should be
nanosheet core-shell array was obtained. benefit for exposing
SEM images of the materials during each fabrication process of more catalytic active sites.
CuO nanowire@Co3O4 nanosheet with the optimized condition are The composition and crystal form of CuO/Co3O4 composites
shown in Fig. 2. After electro-deposition of Cu, the metallic Cu were systemically characterized by EDS, XRD and TEM. As revealed
particles grew around CF, and the particles had rather large size in Fig. 3A-D, the Co element distributed homogeneously over the
(several micrometers) and dense morphology. In contrary, after the backbone and branch area while the Cu element only appeared in
electro-oxidization process, Cu dense particles were reconstructed
to the uniform Cu(OH)2 nanowires with about 200 nm in diameter
and several micrometers in length. As shown in Fig. 2C and D, the
highly ordered Cu(OH)2 nanowires wrapped the CF well and each
nanowire was decentralized, which provided enough space among
each nanowire for the further deposition of active materials. In
addition, as revealed in Fig. 2 E and F, the root part of nanowires
showed a pyramid-like microstructure, indicating a good contact
interface between Cu(OH)2 nanowires and CF current collector. The
Cu(OH)2 nanowire arrays were further used as ideal substrate to

Fig. 3. SEM images (A) and corresponding element mapping (B, C and D), XRD
patterns of CuO/Co3O4 composite catalyst before and after calcination(E), and TEM
Fig. 2. Different magnification SEM images of Cu particles (A, B), Cu(OH)2 nanowire image of Co3O4 (F), CuO (G and H), and CuO@Co3O4 core-shell composite catalysts (I
matrix (C, D, E, F), and CuO nanowire@ Co3O4 nanosheet composite (G, H, I, J). and J).
80 X. Li et al. / Electrochimica Acta 250 (2017) 77–83
backbone area, indicating that the Co-based species wrapped Cu-
based species well. The crystal information of CuO/Co3O4
composites before and after calcination is shown in Fig. 3E.
Obviously, the composite before the thermal treatment included
all of the characteristic peaks of Cu(OH)2 [17] as well as Co(OH)2
[21]. However, after the calcination, the composite was trans-
formed to CuO [17] and Co3O4 [7] composite materials. Thus,
combined with EDS results, one can confirm that the composite
was composed of CuO nanowire backbone and Co3O4 nanosheet
shell. Further information on the images of CuO/Co3O4 composite
and its corresponding pure CuO and Co3O4 materials were
provided by TEM measurement. As shown in Fig. 3F and G, the
electro-deposited Co3O4 material had a thin nanosheet structure
while the CuO had a nanowire structure, which was consistent
with the SEM image. Furthermore, as revealed by the high
resolution TEM image in Fig. 3H, the well-resolved lattice fringes
with the interplanar spacing of 0.233 nm just corresponded to the
(111) plane of CuO [17]. Fig. 3I and J show the TEM images of CuO/
Co3O4 composites. Obviously, the composite had a nanosheet@-
nanowire core-shell structure, and the nanosheet was consisted of
a uniform layer with a particle diameter of 5–10 nm, in which only
a little space among the particles. The lattice fringes in both of the
nanowire and nanosheet regions are shown in Fig. 3J, in which the
well-resolved lattice fringes with the interplanar spacing of
0.233 nm and 0.46 nm just corresponded to the (111) plane of
CuO and the (111) plane of Co3O4 [7].
The morphology of CuO/Co3O4 composite was found to be
highly dependent on the electro-deposition potentials for Co3O4
nanosheets. As shown in Fig. 1, the crucial step of Co3O4 materials
deposition should be the reduction of nitrate ions, in which the
reaction rate was controlled by the applied potential. As revealed
by Fig. 4A and B, when the applied potential was as low as 0.6 V,
the deposited Co3O4 materials with dot-like structure grew on the
surface of CuO nanowire. It is possible that the reaction rate was
too low so that the obtained materials had no nanosheet structure
at 0.6 V. When the applied potential value was increased to
0.8 V, a nanosheet-like morphology was observed in the shell
part of CuO/Co3O4 composite. However, it should be noted that the
Fig. 4. Different magnification SEM images of CuO/Co3O4 composites prepared at
different Co3O4 deposition potentials: 0.6 V (A, B), 0.8 V (C, D), 1.2 V (E, F).
nanosheet seemed to be accumulated together. Such a dense
distribution should not be good for the diffusion of reactant. In
contrary, as shown in Fig. 2, the composite prepared at 1.0 V had a
well-aligned CuO nanowire@ Co3O4 nanosheet core-shell array
which could provide more active sites, and the space among Co3O4
nanosheets was also good for the diffusions of ions and the
generated bubbles. However, if the applied potential was too
negative, the deposition rate of Co3O4 materials should be also very
fast. That is why a dense and accumulational microstructure was
formed.
The OER catalytic activity of CuO/Co3O4 composite electrodes
prepared by using different potentials for the Co3O4 deposition
were analyzed based on linear sweep voltammetry. As shown in
Fig. 5A, the performance was highly dependent on the applied
potential, and the optimized potential was 1.0 V. It is obvious that
such a property was resulted from the different morphologies of
CuO/Co3O4 composites. At the deposition potentials of 0.6 V and
0.8 V, the obtained Co3O4 materials had no ideal porous
microstructure so that less number of active sites were provided
for the
reactions. Here, the morphology of composite prepared at
1.2 V had an accumulational microstructure, which should hinder
the diffusions of reactants and the generated gas. The overpotential
required to achieve a current density of 10 mA cm 2 is an
important performance index for an OER catalyst because it is
approximately the current density for a 10% efficient solar-to-fuel
conversion device. And the 10% efficiency is an important metric,
which is the “upper limit” for two-photon configurations (solar
energy to chemical potential energy stored as H2) [22,23]. In order
to compare the OER activities of different electrodes correctly, the
LSV curves with IR correction for the optimized CuO/Co3O4
composite and the corresponding pure CuO and Co3O4 electrodes
are shown in Fig. 5B. One can see that the CuO and Co3O4
electrodes also had obvious OER activity and required 305 and
277 mV overpotentials to afford 10 mA cm 2 current density,
respectively. On the contrary, CuO/Co3O4 composite revealed a
more significantly enhanced OER activity, and at the same applied
potential, it exhibited a much higher current density than the
corresponding pure ones. In addition, CuO/Co3O4 composite
needed only 258  3.2 mV overpotential to support 10 mA cm 2
current density. This overpotential is also lower than those most
reported transition metal oxides and other Co-based OER catalysts
in alkaline conditions, including IrO2/C (470 mV) [24], IrO2
(450 mV) [25], Ir/C (300 mV) [26], Co3O4 (270 mV) [27], NiCo2O4
(340 mV) [28], Co3V2O8 (350 mV) [29], CoMoO4 (312 mV) [30],
CuCo2O4/NrGO (360 mV) [31], Co4N/CC (257 mV) [32], CoP
(360 mV) [33], CoS/Ti (361 mV) [34].
Here, Tafel slope was also used to evaluate the OER kinetics of
CuO/Co3O4 composite and the corresponding pure catalysts since it
can reflect the effect of overpotential on the steady-state current
density. As shown in Fig. 5C, the estimated Tafel data of the CuO/
Co3O4 composite coated electrode was much lower than those of
CuO and Co3O4 coated electrodes, indicating its favorable OER
kinetics and fast catalytic rate [35]. Meanwhile, as shown in Fig. 5
D, O2 productivity of CuO/Co3O4 composite electrode was also
measured, which showed a Faraday efficiency as high as 94%,
indicating that the electrical energy can be efficiently utilized and
converted to chemical energy with the as-prepared electrocatalyst.
This enhanced performance should be resulted from the
advantages of the well-aligned CuO nanowire@Co3O4 nanosheet
core-shell structure. Firstly, the facile electro-chemical synthesis
ensured a good interface connection, which should be benefit for
the charge-transition among the CuO and Co3O4 materials and
carbon fiber current collector. Moreover, the CuO nanowires not
only served as the physical support for the nanoarrays but also
provided the channels for the electron transmission. In addition,
 X. Li et al. / Electrochimica Acta 250 (2017) 77–83 81

Fig. 5. Polarization curves of CuO/Co3O4 composite electrodes prepared by different potentials (A), the comparison of CuO/Co3O4 composite and corresponding CuO, Co3O4
and pure carbon fiber electrodes, the corresponding imaginary line are IR-corrected polarization curves, and the orange imaginary line reflects the position of 10 mA cm 2
current density (B), Tafel slopes of the fresh and intercalated NiFe LDH coated electrodes with IR correction (C), theoretical oxygen evolution amount and the measured oxygen
evolution amount during the course of electrolysis using CuO/Co3O4 composite electrode (D).

the 3D core-shell array should greatly increase the amount of
catalytic active sites per geometric area, and enlarge the contact
area between catalyst and reactant. Meanwhile, the open spaces
among Co3O4 nanosheets and between neighboring composite
branches facilitated the diffusion of electrolyte and the generation
of oxygen.
It is always desirable to obtain an electrocatalyst that can work
equally well under different pH conditions. Especially, if it can
work well in neutral electrolytes, it would be a big leap. In this
work, the prepared CuO nanowire@Co3O4 nanosheet composite
were found to be stable in the neutral and base solutions, but
suffered serious chemical corrosion in the acid solution. Here, the
OER activities of CuO nanowire@Co3O4 nanosheet coated electro-
des in neutral and base solutions, i.e., pH values were fixed at 7, 13
and 14, respectively, were compared. The corresponding polariza-
tion curves are shown in Fig. 6. It is observed that the CuO
nanowire@Co3O4 nanosheet catalyst worked considerably well in
different pH values and the performance improved with the
increase in pH value.
Cu-based species, such as Cu, Cu2O, Cu(OH)2 and CuO can be
used as electroactive materials, and the state of Cu element is
Fig. 6. Linear polarization curves for optimized CuO nanowire@Co3O4 nanosheet
coated electrode in electrolytes with different pH values.
usually variable due to its mixed-valence feature. During OER
process, these Cu-based species could be transformed to or
remained as Cu(OH)2 and CuO, and at higher potential, CuO could
be further oxidized to unstable Cu3+ based materials [36]. As
shown in Fig. 7A, the existences of O, Co and Cu elements further
indicated the formation of CuO and Co3O4 materials. Moreover, the
peaks located at 933.8 eV and 934.7 eV in Fig. 7B corresponded to
the Cu2+ and Cu3+ species, respectively. Obviously, after the
continuous oxidization at 1.8 V vs RHE for 1 h, the peak of Cu2p3/2
shifted to the higher binding energy, indicating that the Cu2+ in
CuO/Co3O4 composite was transformed to Cu3+ components
[37,38]. It is believed that the generated Cu3+ component was
the new catalytically active species for OER [36].
The resistances of CuO, Co3O4 and CuO/Co3O4 coated electrodes
for OER process were analyzed by electrochemical impedance
spectroscopy technique. As shown in Fig. 8A, the resistance in the
high frequency region is corresponding to the ohmic resistance Rs.
Here, the charge transfer resistance
(signed as Rct) was calculated from the arc radius of the Nyquist
plot. One can see that the CuO, Co3O4 and CuO/Co3O4 electro-
catalysts coated electrodes had the similar ohmic resistance Rs, i.e.,
1.68, 1.58 and 1.57 V, respectively. However, CuO nanowire coated
electrode had significantly higher charge transfer resistance
(Rct = 4.3 V) which should be due to the relative low intrinsic
activity of CuO catalyst. In contrary, the charge transfer resistance
of Co3O4 nanosheet coated electrode was as low as 0.8 V,
indicating that its interface had good affinity with the charges
and reactants, which should be also attributed to the smart core-
shell heterostructure. On the other hand, CuO/Co3O4 composite
coated electrode had lower charge transfer resistance (0.5 V),
which was also related with its high OER catalytic activity. Fig. 8B
shows the durability of CuO/Co3O4 composite coated electrode,
which was collected by potentiostatic method at 1.6 V vs RHE
where the cell showed a high oxygen evolution rate.
Obviously, the composite electrode had an excellent long-term
stability for durable oxygen evolution with only a slight fluctuation
observed during 12 h test, and the polarization curves before and
after durability test remained almost unchanged. Hence, the CuO
82 X. Li et al. / Electrochimica Acta 250 (2017) 77–83
Fig. 7. (A) XPS spectra of CuO/Co3O4 composite catalysts for O, Co and Cu elements, (B) XPS spectra of the Cu element before and after potentiostatic process at 1.8 V.
Fig. 8. (A) Nyquist plots of CuO, Co3O4 and CuO/Co3O4 coated electrodes. (B) Polarization curves of CuO/Co3O4 composite electrode before and after 12 h electrolysis. Inset:
Time dependence of current density for the CuO/Co3O4 composite coated electrode in 1 M KOH electrolyte at 1.6 V vs RHE over 12 h.
nanowire@Co3O4 nanosheet should be an ideal alternative
electrocatalyst for water oxidization.
4. Conclusions
In summary, a highly ordered Cu(OH)2 nanowire array and a
well-aligned CuO nanowire@Co3O4 nanosheet core-shell array
were successfully fabricated on carbon fibers by multi-step
electrodeposition combined with the thermal treatment method.
The smart hybridization of CuO nanowire and Co3O4 nanosheets
into hierarchical core/shell array configuration provided more
contact areas between electrolyte and active sites. In addition, the
Co3O4 ultrathin nanosheet was found to be consisted of monolayer
particles, which should expose more active sites. Moreover, the Cu2
+
in CuO/Co3O4 composite was found to be oxidized to Cu3+
components during OER process. As expected, the composite
showed remarkably enhanced catalytic property when compared
with pure CuO nanowire or Co3O4 nanosheets, and revealed an
overpotential of 258  3.2 mV at the current density of 10 mA cm 2.
Acknowledgements
This work is supported by Sekihiyo Facility Industrial Co., Ltd.,
Japan. The authors also gratefully appreciate Ms Baoyi Shen at the
Department of Arts, Taiyuan University of Technology, China, for
drawing Fig. 1 included in this manuscript.
References
[1] X. Li, X. Hao, A. Abudula, G. Guan, Nanostructured catalysts for electrochemical
water splitting: current state and prospects, J. Mater. Chem. A 4 (2016) 11973.
[2] M.I. Jamesh, Recent progress on earth abundant hydrogen evolution reaction
and oxygen evolution reaction bifunctional electrocatalyst for overall water
splitting in alkaline media, J. Power Sources 333 (2016) 213.
[3] X. Li, X. Hao, Z. Wang, A. Abudula, G. Guan, In-situ intercalation of NiFe LDH
materials: An efficient approach to improve electrocatalytic activity and
stability for water splitting, J. Power Sources 347 (2017) 193.
[4] X. Jia, S. Gao, T. Liu, D. Lia, P. Tang, Y. Feng, Controllable synthesis and Bi-
functional electrocatalytic performance towards oxygen electrode reactions of
Co3O4/N-RGO composites, Electrochim. Acta 226 (2017) 104.
[5] E. Fabbri, A. Habereder, K. Waltar, R. Kötz, T.J. Schmidt, Developments and
perspectives of oxide-based catalysts for the oxygen evolution reaction, Catal.
Sci. Technol 4 (2014) 3800.
[6] Y. Liu, J. Koza, J.A. Switzer, Conversion of electrodeposited Co(OH)2 to CoOOH
and Co3O4, and comparison of their catalytic activity for the oxygen evolution
reaction, Electrochim. Acta 140 (2014) 359.
[7] Z. Zhuang, W. Sheng, Y. Yan, Synthesis of monodispere Au@Co3O4 core-shell
nanocrystals and their enhanced catalytic activity for oxygen evolution
reaction, Adv. Mater 26 (2014) 3950.
[8] G. Mattioli, P. Giannozzi, A. Amore Bonapasta, L. Guidoni, Reaction pathways
for oxygen evolution promoted by cobalt catalyst, J. Am. Chem. Soc 135 (2013)
15353.
[9] M. Zeng, Y. Li, Recent advances in heterogeneous electrocatalysts for the
hydrogen evolution reaction, J. Mater. Chem. A 3 (2015) 14942.
[10] S. Li, H. Zhai, L. Wang, D.A. Dixon, Structural and electronic properties of
reduced transition metal oxide clusters, M4O10 and M4O10–(M = Cr, W), from
photoelectron spectroscopy and quantum chemical calculations, J. Phys.
Chem. A 116 (2012) 5256.
[11] A. Getsoian, A.T. Bell, The influence of functionals on density functional theory
calculations of the properties of reducible transition metal oxide catalysts, J.
Phys. Chem. C 117 (2013) 25562.
[12] F. Li, S. Luo, Z. Sun, X. Bao, L. Fan, Role of metal oxide support in redox reactions
of iron oxide for chemical looping applications: experiments and density
functional theory calculations, Energy Environ. Sci. 4 (2011) 3661.
[13] A. Chaudhary, M.P. Nag, N. Ravishankar, T. Thomas, M. Jain, S. Raghavan,
Synergistic effect of Mo + Cu codoping on the photocatalytic behavior of
metastable TiO2 solid solutions, J. Phys. Chem. C 118 (2014) 29788.
[14] M. Huang, Y. Zhang, F. Li, Z. Wang, N. Hu, Z. Wen, Q. Liu, Merging of Kirkendall
growth and Ostwald ripening: CuO@ MnO2 core-shell architectures for
asymmetric supercapacitors, Sci. Rep. 4 (2014)4518.
[15] J. Wang, Q. Zhang, X. Lia, D. Xu, Z. Wang, H. Guo, K. Zhang, Three-dimensional
hierarchical Co3O4/CuO nanowire heterostructure arrays on nickel foam for
high-performance lithium ion batteries, Nano Energy 6 (2014) 19.
[16] J. Wang, Q. Zhang, X. Lia, B. Zhang, L. Mai, K. Zhang, Smart construction of
three-dimensional hierarchical tubular transition metal oxide core/shell
heterostructures with high-capacity and long-cycle-life lithium storage, Nano
Energy 12 (2015) 437.
[17] N. Cheng, Y. Xue, Q. Liu, J. Tian, L. Zhang, A.M. Asiri, X. Sun, Cu/(Cu(OH)2-CuO)
core/shell nanorods array: in-situ growth and application as an efficient 3D
oxygen evolution anode, Electrochim. Acta 163 (2015) 102.
[18] X. Li, G. Guan, X. Du, J. Cao, X. Hao, X. Ma, A.D. Jagadale, A. Abudula, A sea
anemone-like CuO/Co3O4 composite: an effective catalyst for electrochemical
water splitting, Chem. Commun. 51 (2015) 15012.
 X. Li et al. / Electrochimica Acta 250 (2017) 77–83
[19] X. Li, G. Guan, X. Du, A.D. Jagadale, J. Cao, X. Hao, X. Ma, A. Abudula, Homogeneous
nanosheet Co3O4 film prepared by novel unipolar pulse electro-deposition
method for electrochemical water splitting, RSC Adv. 5 (2015) 76026.
[20] A.D. Jagadale, V.S. Kumbhar, R.N. Bulakhe, C.D. Lokhande, Influence of
electrodeposition modes on the supercapacitive performance of Co3O4
electrodes, Energy 64 (2014) 234.
[21] X. Li, G.L. Xu, F. Fu, Z. Lin, Q. Wang, L. Huang, J.-T. Li, S.G. Sun, Room-
temperature synthesis of Co(OH)2 hexagonal sheets and their topotactic
transformation into Co3O4 (1 1 1) porous structure with enhanced lithium-
storage properties, Electrochim. Acta 96 (2013) 134.
[22] M.G. Walter, E.L. Warren, J.R. McKone, S.W. Boettcher, Q. Mi, E.A. Santori, N.S.
Lewis, solar water splitting cells, Chem. Rev. 110 (2010) 6446–6473.
[23] C.C.L. McCrory, S. Jung, J.C. Peters, T.F. Jaramillo, Benchmarking heterogeneous
electrocatalysts for the oxygen evolution reaction, J. Am. Chem. Soc. 135 (2013)
16977–16987.
[24] T. Ma, J. Cao, M. Jaroniec, S. Qiao, Interacting carbon nitride and titanium
carbide nanosheets for high-performance oxygen evolution, Angew. Chem. Int.
Ed. 55 (2016) 1138–1142.
[25] Y. Zhu, W. Zhou, Z.G. Chen, Y. Chen, C. Su, M.O. Tadé, Z. Shao, SrNb
0.1Co0.7Fe0.2O3-d perovskite as a next-generation electrocatalyst for oxygen
evolution in alkaline solution, Angew. Chem. Int. Ed. 54 (2015) 3897–3901.
[26] M. Gong, Y. Li, H. Wang, Y. Liang, J. Wu, J. Zhou, J. Wang, T. Regier, F. Wei, H. Dai,
An advanced Ni–Fe layered double hydroxide electrocatalyst for water
oxidation, J. Am. Chem. Soc. 135 (2013) 8452–8455.
[27] R. Li, D. Zhou, J. Luo, W. Xu, J. Li, S. Li, P. Cheng, D. Yuan, The urchin-like sphere
arrays Co3O4 as a bifunctional catalyst for hydrogen evolution reaction and
oxygen evolution reaction, J. Power Sources 341 (2017) 250–256.
[28] X. Lv, Y. Zhu, H. Jiang, X. Yang, Y. Liu, Y.H. Su, J. Huang, Y. Yao, C. Li, Hollow
mesoporous NiCo2O4 nanocages as efficient electrocatalysts for oxygen
evolution reaction, Dalton Trans. 44 (2015) 4148–4154.
[29] S. Hyun, V. Ahilan, H. Kim, S. Shanmugam, The influence of Co3V2O8
morphology on the oxygen evolution reaction activity and stability,
Electrochem. Commun. 63 (2016) 44–47.
83
[30] M. Yu, L. Jiang, H. Yang, Ultrathin nanosheets constructed CoMoO4 porous
flowers with high activity for electrocatalytic oxygen evolution, Chem.
Commun. 51 (2015) 14361–14364.
[31] S.K. Bikkarolla, P. Papakonstantinou, CuCo2O4 nanoparticles on nitrogenated
graphene as highly efficient oxygen evolution catalyst, J. Power Sources 281
(2015) 243–251.
[32] P. Chen, K. Xu, Z. Fang, Y. Tong, J. Wu, X. Lu, X. Peng, H. Ding, C. Wu, Y. Xie,
Metallic Co4N porous nanowire arrays activated by surface oxidation as
electrocatalysts for the oxygen evolution reaction, Angew. Chem. 127 (2015)
14923–14927.
[33] J. Ryu, N. Jung, J.H. Jang, H.J. Kim, S.J. Yoo, In situ transformation of hydrogen-
evolving CoP nanoparticles: toward efficient oxygen evolution catalysts
bearing dispersed morphologies with Co-oxo/hydroxo molecular units, ACS
Catal. 5 (2015) 4066–4074.
[34] T. Liu, Y. Liang, Q. Liu, X. Sun, Y. He, A.M. Asiri, Electrodeposition of cobalt-
sulfide nanosheets film as an efficient electrocatalyst for oxygen evolution
reaction, Electrochem. Commun. 60 (2015) 92–96.
[35] T. Shinagawa, A.T. Garcia-Esparza, K. Takanabe, Insight on Tafel slopes from a
microkinetic analysis of aqueous electrocatalysis for energy conversion, Sci.
Rep. 5 (2015)13801.
[36] Y. Deng, A.D. Handoko, Y. Du, S. Xi, B.S. Yeo, In Situ Raman spectroscopy of
copper and copper oxide surfaces during electrochemical oxygen evolution
reaction: identification of CuIII oxides as catalytically active species, ACS Catal.
6 (2016) 2473.
[37] N. Padmavathy, R. Vijayaraghavan, G.U. Kulkarnib, Solution based rapid
synthesis of AgCuO2 at room temperature, RSC Adv. 4 (2014) 62746.
[38] P. Steiner, V. Kinsinger, I. Sander, B. Siegwart, S. Hüfner, C. Politis, R. Hoppe, H.P.
Müller, The Cu valence in the high Tc superconductors and in monovalent,
divalent and trivalent copper oxides determined from XPS core level
spectroscopy, Zeitschrift für Physik B Condensed Matter 67 (1987) 497.