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Hierarchical Cu2O/CuO/Co3O4 core-shell nanowires: synthesis and electrochemical

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2015 Nanotechnology 26 304002

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 Nanotechnology

Nanotechnology 26 (2015) 304002 (9pp) doi:10.1088/0957-4484/26/30/304002

Hierarchical Cu2O/CuO/Co3O4 core-shell

nanowires: synthesis and electrochemical
properties
Min Kuang1, Tong Tao Li1, Hao Chen1, Sheng Mao Zhang2, Li Li Zhang3 and
Yu Xin Zhang1,4
1
College of Material Science and Engineering, Chongqing University, Chongqing 400044, People’s
Republic of China
2
Laboratory for Special Functional Materials, Henan University, Kaifeng 475004, People’s Republic of
China
3
Institute of Chemical and Engineering Sciences, A*STAR, 1 Pesek Road, Jurong Island, 627833,
Singapore
4
National Key Laboratory of Fundamental Science of Micro/Nano-Devices and System Technology,
Chongqing University, Chongqing 400044, People’s Republic of China

E-mail: zhangyuxin@cqu.edu.cn and zhang_lili@ices.a-star.edu.sg

Received 8 February 2015, revised 22 April 2015

Accepted for publication 21 May 2015
Published 7 July 2015

Abstract
We prepared hierarchical Cu2O/CuO/Co3O4 core–shell nanowires (NWs) via a facile chemical
deposition method followed by calcination for use as the electrode of supercapacitors. The
Cu2O/CuO/Co3O4 electrode showed a specific capacitance of 318 F g−1 at a current density of
0.5 A g−1. 80% of the original specific capacitance was retained after 3000 cycles at a current
density of 5 A g−1. An asymmetric supercapacitor cell using Cu2O/CuO/Co3O4 NWs as the
positive electrode and activated graphene as the negative electrode exhibited a maximum energy
density of 12 Wh kg−1. The electrochemical properties of the electrode were strongly related to
the hierarchical nanostructure, which not only provided rich active sites but also shortened ion
transport pathways.

S Online supplementary data available from stacks.iop.org/NANO/26/304002/mmedia

Keywords: core/shell structure, copper oxide, cobaltosic oxide

(Some figures may appear in colour only in the online journal)

1. Introduction good chemical and structural stability, cheap production, etc.

Supercapacitors, also known as electrochemical capacitors or
ultracapacitors, are promising energy storage devices [1–4].
Recently, supercapacitors have sparked tremendous research
interest due to their ultrahigh power delivery, high rate cap-
ability, exceptional cycle life and safety [5–7]. The charge in
a supercapacitor is either from pure ion adsorption at an
electrode/electrolyte interface or from fast and reversible
redox reactions [8–10]. The key challenges in the develop-
ment of supercapacitors are the design and synthesis of
appropriate electrode materials with desirable properties, such
as high surface area, good conductivity, small resistance,
Redox-active transition-metal oxides, including NiO [11],
MnO2 [12], TiO2 [13], CuO [14], RuO2 [15], V2O5 [16] and
Co3O4 [17] have been considered as promising electrode
materials.
In particular, CuO has drawn tremendous interest as a
promising electrode material for supercapacitors due to its
natural abundance, low cost, chemical stability and environ-
mental benignity [18–20]. Pendashteh et al [21] have fabri-
cated CuO nanoparticles that were anchored on the surface of
graphene oxide. The composite electrode showed a specific
capacitance of 245 F g−1 at a current density of 0.1 A g−1;
Dubal et al [19] reported micro-woolen-like CuO nanoflakes

0957-4484/15/304002+09$33.00 1 © 2015 IOP Publishing Ltd Printed in the UK

Nanotechnology 26 (2015) 304002
that displayed a special capacitance of 279 F g−1 at a scan rate
of 5 mV s−1; Shaikh et al [22] described the fabrication of
CuO–PAA hybrid films that gave a specific capacitance of
65 F g−1 at a scan rate of 20 mV s−1; Li et al [23] demon-
strated that nanostructured CuO directly grown on Cu foam
exhibited a specific capacitance of 212 F g−1 at a current
density of 0.41 mA mg−1. However, the main issue that
greatly restricts the practical application of Cu oxide-based
electrode materials is still its poor electrical conductivity,
which leads to a low specific capacitance and poor rate
capacity. It is widely believed that the electrical conductivity
can be improved by introducing other semiconductors and
controlling the morphology and structure of the active mate-
rials [24, 25]. Compared with single-phased material, the
hybrid materials with hierarchical nanostructure can provide
short ion transport pathways, offer synergetic effects from
multiple active components and have easily accessible elec-
troactive sites for the electrolyte ions [26], leading to
enhanced capacitive performance. For example, Zhang et al
[27] reported MnO2-coated CuO flower-like nanostructures
with a specific capacitance of 167.2 F g−1 at a current density
of 0.3 A g−1; Wang et al [28] synthesized the Cu2O/CuO/
RGO nanocomposite, which showed a specific capacitance of
173.4 F g−1 at 1 A g−1; Huang et al [29] demonstrated the NiO
nanoflake-coated CuO flower core–shell nanostructures, and
the composite electrode showed a specific capacitance of
280 F g−1 at 1 A g−1. Despite those research efforts, the
development of multi-component Cu oxide-based electrode
materials with good performance and a facile synthetic route
is still challenging.
We report a facile and eco-friendly approach to fabricate
porous Cu2O/CuO/Co3O4 core–shell nanowires (NWs). The
key to the preparation of the multi-component metal oxide is
the initial formation of the CuO layer on the surface of Cu
NWs, which induces the growth of Co3O4 nanoflakes. The
Cu2O/CuO/Co3O4 core–shell NW-based electrode shows a
specific capacitance of 318 F g−1 at a current density of
0.5 A g−1 with good stability. An asymmetric supercapacitor
cell using Cu2O/CuO/Co3O4 NWs as the positive electrode
and the activated graphene (AG) as the negative electrode
exhibits a maximum energy density and power density of
12 Wh kg−1 and 1 kW kg−1, respectively.
2. Experimental section
2.1. Material synthesis
All reagents were of analytical grade and used after purchase
without any further purification. Cu NWs were obtained from
Henan Engineering Technology Research Center for Nano-
materials. In a typical synthesis, Co(NO3)2.6H2O (2.0 mmol),
NH4F (2 mmol) and urea (5 mmol) were mixed with 80 mL of
ethanol and 80 mL of distilled water to form a pink mixture.
Then 100 mg Cu/CuO NWs (obtained by the heat treatment
of pure Cu NWs at 60 °C for 2 h) was added to the above
solution under stirring for ∼15 min. The solution was then
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M Kuang et al
transferred to a round-bottom flask and maintained at 90 °C
for 8 h. Then the dark precipitate was collected through fil-
tration, washed several times with ethanol and distilled water,
respectively, and finally dried in air. The product was further
calcined at 300 °C for 2 h to obtain the hierarchical porous
Cu2O/CuO/Co3O4 NWs.
2.2. Materials characterization
The as-prepared products were characterized by x-ray dif-
fraction (XRD, D/max 1200, Cu Kα). Scanning electron
microscopy (SEM) analysis was carried out using a focused
ion beam SEM (ZEISS AURIGA FIB/SEM). X-ray photo-
electron spectroscope (XPS) was investigated by means of
Kratos XSAM800 XPS with an Al Kα excitation source
(1486.6 eV). The structure of the NWs was achieved on a
transmission electron microscopy (TEM, ZEISS LIBRA 200).
Nitrogen adsorption/desorption was carried out using micro-
meritics ASAP 2020.
2.3. Electrochemical measurements
A series of electrochemical measurements, including cyclic
voltammetry (CV), galvanostatic charge–discharge and elec-
trochemical impedance spectroscopy (EIS) for both three- and
two-electrode system, was performed with a CHI 660E
electrochemical workstation in a 3 M KOH electrolyte. The
working electrode was prepared by mixing the active mate-
rial, carbon black and polyvinylidene fluoride in a mass ratio
of 85:15:5 with N-methyl-2-pyrrolidone as the solvent to
make slurry. The slurry was then coated onto a nickel foam
current collector (1 × 1 cm2), and the final electrode was
obtained after drying at 120 °C for 10 h to evaporate the
solvent.
In a three-electrode cell configuration, the Cu2O/CuO/
Co3O4 NWs, Ag/AgCl and platinum were used as the
working electrode, reference electrode and counter electrode,
respectively. An asymmetric device was assembled using
Cu2O/CuO/Co3O4 NWs as the positive electrode and AG as
the negative electrode and polypropylene film as the separa-
tor. To obtain a stable asymmetric supercapacitor, it is
necessary to balance the charges (Q) that are stored at both
electrodes, based on the relationship Q+ = Q−. The stored
charges are proportional to the specific capacitance (Cm), the
potential window (V) and the mass (m) of the electrode, i.e.,
Q = Cm × V × m. Thus, the mass ratio of (m) Cu2O/CuO/
Co3O4//(m) AG was optimized to be 0.74.
The specific capacitance (Cm, F g−1) of the electrodes was
calculated from the galvanostatic charge–discharge curves
using equation (1) shown below. The energy density (E, Wh
Kg−1) and power density (P, W Kg−1) of the asymmetric
device was calculated from equations (2) and (3), respec-
tively.
Cm = I ⋅ Δt m ⋅ ΔV (1)
E = 0.5 ⋅ Cm ⋅ (ΔV )2 3.6 (2)
P = E ⋅ 3600 Δt (3)
Nanotechnology 26 (2015) 304002
Figure 1. (a) XRD pattern; (b) Co 2p XPS spectrum; (c) Cu 2p XPS spectrum and (d) O 1s XPS spectrum of the Cu2O/CuO/Co3O4 NWs.
I is the discharge current density (A g−1), m is the load
mass of the active materials (g), Δt is the discharging time (s)
and ΔV is the discharging potential range excluding the initial
drop (V).
3. Results and discussion
The XRD pattern of Cu2O/CuO/Co3O4 NWs is shown in
figure 1(a). The diffraction peaks from Co3O4 in the XRD
pattern can be indexed to (111), (220), (311), (222), (331),
(511) and (400) crystal faces of the cubic spinel Co3O4
(JPCDS: 43-1003). The diffraction peaks due to Cu2O
(indexed to (110), (111), (200), (220) and (311) planes
(JPCDS: 05-0667)) and CuO (indexed to (002), (111), (20-2)
and (11-3) planes (JPCDS: 48-1548)) are observed, suggest-
ing the coexistence of Cu2O and CuO in the annealed pro-
duct. The XPS spectra in figures 1(b)–(d) further demonstrate
the presence of Cu2O, CuO and Co3O4 in the composite. As
shown in figure 1(b), two prominent peaks at the binding
energies of 795.2 eV and 779.6 eV are observed,
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M Kuang et al
corresponding to Co2p1/2 and Co2p3/2, respectively. Two
‘shake-up’ satellites (donated as Sat.) at 803.9 and 788.2 eV
indicate the presence of Co3O4 [26, 30]. The ‘shake-up’
satellites at 941.8 eV and 962.1 eV in the Cu 2 p XPS spectrum
(figure 1(c)) confirm the presence of Cu2+ [31, 32]. Moreover,
the spin–orbit-coupled Cu 2p region fits perfectly with a set of
single peaks at 932.8 eV (2 p3/2) and 952.8 V (2 p1/2), indi-
cating the existence of Cu1+ [28, 33]. The XRD and XPS
results demonstrate the co-existence of Cu2O, CuO and Co3O4
in the composite. The O 1 s high-resolution spectrum
(figure 1(d)) has four distinct components, which are denoted
as O1, O2, O3 and O4, respectively. The O1 (529.5 eV) and O2
(530.6 eV) are ascribed to the metal–oxygen bonds and the
oxygen atoms in the hydroxyl groups, respectively [34, 35].
The O3 (531.5 eV) is assigned to a multiplicity of defect sites
[36]. The O4 (532.3 eV) is due to the large amount of absorbed
water within and near the surface of the sample [35].
The three-step formation of the hierarchical Cu2O/CuO/
Co3O4 NWs is illustrated in figure S1 (see supplementary
information). The Cu/CuO NWs with rough surfaces are
obtained by air-oxidizing (step I), which serve as the substrate
Nanotechnology 26 (2015) 304002
Figure 2. (a) SEM image of pure Cu nanowires; (b), (c) typical SEM images of the Cu2O/CuO/Co3O4 NWs at different magnifications; (d)
EDS elemental mapping images of (c) an individual Cu2O/CuO/Co3O4 NWs.
for the growth of Co-hydroxide-carbonate nanoflakes. The
XRD patterns of Cu-based NWs before and after the heat
treatment are shown in figure S2. The presence of both Cu
and CuO phases is observed after the heat treatment. The CuO
layer is deliberately introduced as an interfacial reactive layer
for the subsequent growth of the Co-hydroxide-carbonate
nanoflakes. With the increase of the reaction temperature, the
hydrolysis–precipitation process of ammonium fluoride and
urea with the presence of the Co precursor occurred. An
ultrathin layer of Co-hydroxide-carbonate nanoflakes is
formed on Cu-based NWs (step II). The rudiments of Co-
hydroxide-carbonate nanoflakes are grown and then the ske-
letons of Cu-based NWs are uniformly decorated with Co-
hydroxide-carbonate nanoflakes when the reaction time is
prolonged (figure S3). Meanwhile, the Cu/Cu2O/CuO core
was gradually formed by oxidation of Cu/CuO during the
hydrothermal procedure (figure S3). The final hierarchical
Cu2O/CuO/Co3O4 NWs with Co3O4 as the shell and Cu2O/
CuO as the core were obtained by further calcination at
300 °C for 2 h (step III). The morphology and microstructure
of the Cu NWs is shown in figure 2(a). It can be seen that the
Cu NWs are uniform, with diameters ranging from
100–200 nm and having smooth surfaces (figure 2(a)). After
being treated in air, the surface of the Cu NWs becomes rough
(figure S5). Figure 2(b) shows the SEM images of the sample
after coating with Co3O4. Co3O4 nanoflakes grow uniformly
on the Cu-based NWs. The morphology of the product after
calcination does not change much, maintaining the hier-
archical nanostructure (see figure S3). The Co3O4 nanoflakes
are ∼150 nm in lateral dimension and ∼20 nm in thickness,
interconnecting with each other to form a loose network with
ample open space (figure 2(c)). Such open structure is
advantageous for electrolyte infiltration. Figure 2(e) shows
the energy dispersive x-ray spectrometry (EDS) mapping of
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M Kuang et al
an individual Cu2O/CuO/Co3O4 NW (figure 2(d)). The
mapping results demonstrate the co-existence of Co, Cu and
O elements. In addition, the uniform distribution of the Co,
Cu and O elements implies uniform coating of Co3O4 nano-
flakes on Cu-based NWs. The effect of the CuO layer can be
better demonstrated by another two control experiments. We
synthesized the Co3O4 on pure Cu NWs (figure S6) and pure
Co3O4 without any substrate (figure S7), with all the other
experimental conditions remaining the same. It was clearly
seen that, without the presence of the CuO layer, Co3O4
nanobelts with a length of 500 nm were obtained on pure Cu
NWs (see figure S6). Without the use of Cu/CuO NWs,
irregular microflowers appeared (see figure S7). Hierarchical
tubular porous structure can only be obtained in the presence
of Cu/CuO NWs.
More structural and morphological information on the
Cu2O/CuO/Co3O4 NWs was obtained from TEM and selec-
ted area electron diffraction (SAED), as shown in figure 3. A
core–shell structure with Cu2O/CuO NWs as the core part and
Co3O4 nanoflakes (vertical dimension ∼120 nm) as the shell
layer can be seen in figure 3(a). Figures 3(b)–(d) show that the
calcined Co3O4 nanoflakes consist of interconnected nano-
particles with a diameter of 3–8 nm. The interplanar spacings
of 0.24 and 0.21 nm correspond to the (311) and (400) crystal
planes of the cubic spinel Co3O4, respectively (figures 3(e)
and (f)). The SAED pattern (figure 3(g)) of the Co3O4
nanoflakes indicates the polycrystalline structure of the
nanoflakes. The bright diffraction rings can be indexed to the
(220), (311), (400) and (440) crystal planes of Co3O4,
respectively, consistent with the cubic spinel structure of
Co3O4 (JPCDS: 43-1003) from XRD.
Figure 4 shows the nitrogen adsorption/
desorption analysis results of the Cu2O/CuO/Co3O4 NWs.
The isotherm (figure 4(a)) is of type IV, indicating that the
Nanotechnology 26 (2015) 304002 M Kuang et al

Figure 3. (a), (b) Low- and (c) high-magnification TEM images, (d)–(f) HRTEM image, and (d) the corresponding SAED pattern of the
Cu2O/CuO/Co3O4 NWs.

Figure 4. N2 adsorption and desorption isotherms (a) and corresponding pore size distribution (b) of the as-prepared Cu2O/CuO/Co3O4 NWs.

Cu2O/CuO/Co3O4 NWs contain mesopores [37, 38]. The
Barrett–Joyner–Halenda pore size distribution shows two
peaks centered at 0.36 and 7.5 nm, respectively (figure 4(b)).
The presence of mesopores will facilitate the electrolyte ion
transport within the electrode.
The electrochemical properties of the Cu2O/CuO/Co3O4
NWs were first evaluated using a three-electrode system in a
3 M KOH aqueous solution. Figure 5(a) shows the CV curves
of the Cu2O/CuO/Co3O4 electrode at different scan rates. The
existence of the redox peaks illustrates the typical pseudo-
capacitive behavior of the Cu2O/CuO/Co3O4 electrode.
The cathodic peak shifts to a lower potential with the increase
of the scan rate due to the polarization of the electrode [17].
The galvanostatic charge–discharge curves of the

5
Nanotechnology 26 (2015) 304002 M Kuang et al

Figure 5. (a) Cyclic voltammograms of the Cu2O/CuO/Co3O4 NWs at different scan rates; (b) charge-discharge of the Cu2O/CuO/Co3O4
NWs at various current densities; (c) current density dependence of the specific capacitance of the Cu2O/CuO/Co3O4 NWs; (d) variation of
capacitance with cycle number at 5 A g−1 (the inset shows the SEM image of c Cu2O/CuO/Co3O4 NWs after 3000 cycles); (e) schematic of
the charge storage merit of Cu2O/CuO/Co3O4 NWs; (f) Nyquist plots for Cu2O/CuO/Co3O4 NWs in the frequency range of
100 kHz ∼ 0.01 Hz, insert shows the equivalent circuit for the electrochemical impedance spectrum.

Cu2O/CuO/Co3O4 electrode at the current densities from 0.5 The specific capacitance of the Cu2O/CuO/Co3O4 electrode is
to 10 A g−1 are shown in figure 5(b). The curves show a fairly 318 F g−1 at a current density of 0.5 A g−1, which is higher
triangular shape with good symmetry, indicating the good than some of the CuO-based or Co3O4-based electrodes
capacitive and reversible characteristic of the electrode [39]. reported in the literature: (136 F g−1 at 40 mV s−1 for CuO-

6
Nanotechnology 26 (2015) 304002
Figure 6. (a) Schematic illustration of the fabricated Cu2O/CuO/Co3O4//AG asymmetric supercapacitor cell; CV curves (b), charge/discharge
behavior (c) and (d) Ragone plot of Cu2O/CuO/Co3O4//AG asymmetric supercapacitor.
PAA thin films [32]; 173 F g−1 at 1 A g−1 for the Cu2O/CuO/
RGO electrode [28]; and 263 F g−1 at 2.5 A g−1 for the Co3O4/
RGO electrode [40]). A comparison of the specific capaci-
tance between this work and previous reports is summarized
in table S1 (see supplementary information). In addition, the
Cu2O/CuO/Co3O4 electrode retained 73.6% of its original
specific capacitance value when the current density increased
from 0.5 to 10 A g−1, implying good ion diffusion and elec-
tron transport ability at a high current.
The stability of the Cu2O/CuO/Co3O4 electrode was
evaluated using a long-term galvanostatic charge–discharge
process at a constant current of 5 A g−1. A capacitance
retention of more than 78% was achieved after 3000 cycles,
demonstrating good stability of the Cu2O/CuO/Co3O4 elec-
trode. Such good cycling stability is mainly attributed to the
porous core–shell structure and the synergic effect between
the Co3O4 nanoflakes and copper oxide NW. Such a hybrid
porous structure, can not only provide sufficient contact area
for the electrolyte, but can also restrain the anodic dissolution
of the Co3O4 and consequently enhances the stability of the
Cu2O/CuO/Co3O4 electrode. More significantly, the Cu2O/
CuO NWs core provides a direct pathway for electron
7
M Kuang et al
transport while the partial connected ultrathin Co3O4 shell
provides more electronic transmission channels (as schemati-
cally illustrated in figure 5(e)). After 3000 cycles, the structure
of the Cu2O/CuO/Co3O4 electrode shows little damage, as
seen in the inset of figure 5(d). These results indicate that
Cu2O/CuO/Co3O4 NW is stable as an electrode material.
EIS was performed before and after 3000 cycles to fur-
ther investigate the cycling stability, as shown in figure 5(f)
(the inset is the electrical equivalent circuit). During the initial
cycling, the Cu2O/CuO/Co3O4 electrode shows that the
impedance plot increases sharply, and this incline becomes a
vertical line in the low-frequency region, demonstrating a
capacitive characteristic [6]. The main distinction is that a
bigger semicircle diameter appears at the impedance plot of
the Cu2O/CuO/Co3O4 electrode after 3000 cycles. These
results further indicate the good cycling stability of the Cu2O/
CuO/Co3O4 electrode.
An asymmetric supercapacitor cell was assembled by
using Cu2O/CuO/Co3O4 NWs as the positive electrode and
AG as the negative electrode (marked as Cu2O/CuO/Co3O4//
AG, figure 6(a)), respectively. Figure 6(b) shows the typical
CV curves of the Cu2O/CuO/Co3O4//AG asymmetric cell for
Nanotechnology 26 (2015) 304002
voltages up to 1.4 V with various scan rates. The asymmetric
cell revealed rectangle-like CV curves. There is no apparent
distortion of the CV curves at the scan rate up to 80 mV s−1,
demonstrating good charge propagation of the Cu2O/CuO/
Co3O4//AG asymmetric cell [41]. The galvanostatic charge–
discharge curves show a near triangular shape within a stable
potential window of 0–1.4 V at different current densities,
further indicating the good capacitive properties of the
asymmetric cell.
The Ragone plot showing the energy density and power
density of the Cu2O/CuO/Co3O4//AG asymmetric cell is
shown in figure 6(d). The asymmetric cell exhibits a maximum
energy density of 12 Wh kg−1 at a power density of 162 W kg−1
and a high retention of 6 Wh kg−1 at the maximum power
density of 11. kW kg−1. The energy density is comparable to or
higher than the asymmetric cells reported in the literature, such
as the MnFe2O4//LiMn2O4 asymmetric cell (5.5 Wh kg−1)
[42], NiCo2O4-MnO2//AG asymmetric cell (9.4 Wh kg−1)
[43], MnO2-SiO2//MnO2-SiO2 symmetric cell (3.75 Wh kg−1)
[44], TiO2/CNT//CNT asymmetric cell (4.47 Wh kg−1) [45]
and Ni-Co oxide//ac asymmetric cell (12 Wh kg−1) [46].
4. Conclusion
Cu2O/CuO/Co3O4 core–shell NWs were successfully syn-
thesized via a facile chemical deposition and thermal
annealing process. The Cu2O/CuO/Co3O4 electrode exhibited
good specific capacitance (318 F g−1 at 0.5 A g−1), high rate
capability and long cycle life due to the synergetic effects of
various pseudocapacitive oxides in the electrode. The asym-
metric supercapacitor cell based on Cu2O/CuO/Co3O4 NWs
as the positive electrode and AG as the negative electrode can
provide an energy density of 12 Wh kg−1 and a maximum
power density of 11 kW kg−1 with a stable operational voltage
of 1.4 V. This work affords a facile and efficient approach to
constructing unique electrode architectures based on pseu-
docapacitive oxides for energy storage devices.
Acknowledgments
The authors gratefully acknowledge the financial support
provided by the National Natural Science Foundation of
China (Grant no. 51104194), the National Key Laboratory of
Fundamental Science of Micro/Nano-device and System
Technology (2013MS06, Chongqing University), and the
State Education Ministry and Fundamental Research Funds
for the Central Universities (Project no. CDJZR14135501 and
CDJZR13130035, Chongqing University, P R China).
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