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Journal of Electroanalytical Chemistry 785 (2017) 33–39

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Flake-like Cu2O on TiO2 nanotubes array as an efficient nonenzymatic


H2O2 biosensor
Xin Wen a, Mei Long b,c, Aidong Tang a,⁎
a
School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, PR China
b
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, PR China
c
Key Laboratory for Mineral Materials and Application of Hunan Province, Central South University, Changsha 410083, PR China

a r t i c l e i n f o a b s t r a c t

Article history: This work provides a new method for fabrication of the flake-like Cu2O/TiO2 nanotubes array (TNA) electrode as a
Received 7 September 2016 H2O2 sensor. The flake-like Cu2O/TNA electrode was successfully constructed by potentiostatic electrodeposition
Received in revised form 10 December 2016 combining subsequent cyclic voltammetry (CV) technology in NaOH solution. The catalytic performance of the
Accepted 11 December 2016
sensor was studied in 0.1 M phosphate buffer (PBS, pH = 7.4). It was found that the flake-like Cu2O/TNA electrode
Available online 13 December 2016
displayed a good catalytic performance towards the reduction of H2O2 with a response time of 4 s, a wide linear
Keywords:
dependence on a concentration of H2O2 from 0.5 mM to 8 mM, a good sensitivity of 412.11 μA cm−2 mM−1 and
Nonenzymatic sensor a detection limit of 90.5 μM at a working voltage −0.40 V (vs. Hg/Hg2Cl2). The electrocatalytic mechanism of the
Flake-like morphology flake-like Cu2O/TNA electrodes was also proposed.
Cu2O © 2016 Elsevier B.V. All rights reserved.
TiO2 nanotubes array
Electrocatalysis

1. Introduction [23], nanowire [24], cube [25], octahedron [26], etc. However, two-di-
mensional nanosheets cuprous oxide still remains a challenge. On one
Two-dimensional (2D) nanostructured composite materials have hand, in comparison with other morphologies, the flake-like structure
been applied in various fields due to their unique performances in pla- has larger effective area, high electron transfer efficiency, and the fea-
nar topography, ultrathin thickness and 2D morphological feature [1– ture of two-dimensional crystal structures. Moreover, metal oxide par-
3]. In particular, the application of 2D nanostructured composite mate- ticles with flake-like shape have been confirmed to be beneficial to
rials in catalysis and sensors areas has attracted increasing attention. the catalytic reaction [27]. Therefore, the flake-like structures of cuprous
Amperometric enzyme biosensor is a representative. It was widely ap- oxide has the potential to be an appropriated electrochemical sensor.
plied because of its outstanding selectivity, high sensitivity, fast detec- On the other hand, advanced composites based on functional matrix
tion and low cost. In contrast, the enzyme electrodes presented some or silicate mineral had presented some unique performances due to
limits, such as poor stability, complex preparation procedure and easily 2D morphological feature [28]. For instance, Cu2O/sepiolite composite,
affected by the environment [4,5]. As a result, researchers turned their which helps to promote the catalytic properties compared with the uni-
focus to non-enzymatic biosensors. For instance, non-enzymatic sen- tary component Cu2O, has been synthesized in our previous work [29].
sors made by metal (Au, Ni, Pd) [6–8], metal oxide (CuO, Cu2O, MnO2) The SnO2@rGO nanostructures and Fe2O3@WO3 nanocomposites with
[9–11], and alloy (Pt-Pd) [12], which have been widely applied in superhigh surface areas successfully enhanced the gas-sensing and
electrocatalysis. Among them, cuprous oxide (Cu2O), a p-type oxide electroactive property [30,31]. Therefore, choosing appropriate mate-
semiconductor, demonstrates good potential applications in various rials as support is a good way to improve electrocatalytic performance
fields owing to its remarkable physicochemical properties [13]. Espe- of the Cu2O composite materials. Titanium dioxide, an n-type semicon-
cially, Cu2O nanocrystals have a good response towards the reduction ductor material, with steady chemical properties, high thermal stability,
of H2O2 [14–16]. The catalytic properties of nanomaterial are often asso- wide band gap and high catalytic activity becomes an excellent choice
ciated with the structure, morphologies and size of materials. Currently, [32–35]. Therefore, a flake-like Cu2O/TiO2 nanomaterial is expected to
nano-sized Cu2O particles were obtained by reduction of cupric salts present an excellent performance, although it is difficult to be prepared.
[17,18], electrodeposition [19], hydrothermal [20] or solvothermal Electrochemical deposition method with its facile operation be-
[21] method. Various nanostructures of Cu2O have been synthesized comes a promising means as well as gradually the best choice for
in experiments, such as nanoparticles [22], nanometer microsphere preparation of electrode materials. For example, our team adopted
electrodeposition modification route to fabricate Sb2Se3/TiO2 com-
⁎ Corresponding author. posites which successfully applied to catalytic reduction of nitro-
E-mail address: tangaidong@126.com (A. Tang). phenol [36,37]. Although a helical TiO 2 nanotube array modified

http://dx.doi.org/10.1016/j.jelechem.2016.12.018
1572-6657/© 2016 Elsevier B.V. All rights reserved.
34 X. Wen et al. / Journal of Electroanalytical Chemistry 785 (2017) 33–39

Fig. 3. Cyclic voltammogram of the four different Cu2O/TNA electrodes (a-d) and the TNA
electrode (e) in 0.1 M PBS (pH = 7.4) containing 1.0 mM H2O2 at scan rate of 100 mVs−1.
Fig. 1. XRD patterns of the Cu2O nanostructures prepared with (a, b) CV 100 cycles; (c, d) Note: (a, b) CV 100 cycles, CV was carried out in 0.1 M NaOH at scan rate of 100 mV s−1
calcination at 500 °C for 1 h. Note: CV was carried out in 0.1 M NaOH at scan rate of with voltage range of −0.6–0.6 V; (c, d) calcined at 500 °C for 1 h.
100 mV s−1 with voltage range of −0.6–0.6 V.

Fig. 2. SEM images of the Cu2O nanostructures prepared with (a, b) CV 100 cycles; (c, d) calcination at 500 °C for 1 h; (e,f) TNA electrode. Note: CV was carried out in 0.1 M NaOH at scan
rate of 100 mV s−1 with voltage range of −0.6–0.6 V.
X. Wen et al. / Journal of Electroanalytical Chemistry 785 (2017) 33–39 35

2. Experimental

2.1. Reagent and materials

High purity titanium (99.6%) were purchased from Bjyilite in-


dustry and trade co., Baoji, China (http://bjyilite.cn.china.cn/).
CuSO 4 ·5H 2 O was obtained from Xilong chemical co., Shantou,
China (http://www.xlhg.com/). NaH2PO4 ·2H2O, Na 2HPO4 ·12H2O,
NH 4 F, HNO 3 , NaOH, NaCl, glycerol, H 2 O 2 (30 wt%), nancic acid,
ascorbic acid, glucose, uric acid and dopamine were obtained
from ChangSha Chemical Crop., China and used as received. All
other chemical materials were of analytical grade and used without
any purification. In the whole experiment, double-distilled water
was used.

Fig. 4. Cyclic voltammograms of the Cu2O/TNA electrode prepared with different NaOH
2.2. Preparation of the Cu2O/TNA electrode
concentrations of (a)0.1 M, (b)0.5 M, (c)1.0 M in presence of 1.0 mM H2O2 at scan rate
of 100 mV s−1. TiO2 nanotubes array (TNA) was fabricated by reference to literature
[48] and calcinated at 500 °C for 3 h to transform completely into ana-
tase nanotubes array structure.
with Cu 2 O electrode was firstly fabricated and used for nonenzy- To obtain Cu2O modified electrode, 1 mol L− 1 CuSO4 in 3 mol L− 1
matic glucose detection in our previous work, the morphologies of lactic acid solution to form a copper lactate complex, and pH was ad-
the as-prepared Cu 2 O are octahedron or microsphere. We found justed to 12 using NaOH solution. The electrolyte was stirred and
that a flake-like Cu2O/TiO2 electrode is really difficult to be obtained kept at a constant temperature of 30 °C. Two electrodes prepared
by electrochemical deposition method. by potentiostatic method at − 1.4 V and − 1.6 V respectively. After
Determination of H 2 O2 is of great significance since it is a very the electrolysis finished, four electrodes cleaned by deionized
important intermediate and byproduct in many fields, such as bio- water, and dry naturally in the air. Then, the two electrodes prepared
chemistry, clinical diagnosis [38,39], food [40], environmental at − 1.4 V and − 1.6 V were separately put into 0.1 M NaOH solution,
analysis [41], energy [42,43] and pharmaceutical application [44– and were carried out cyclic voltammetry for 100 cycles at voltage
46] in recent years. Many analytical techniques have been used range of 0.6 V to − 0.6 V at a scan rate of 100 mV·s − 1 and finally
for detection of H2 O 2 , such as titrimetry, spectrophotometry, and achieve sample a and b. For comparison, in order to improve the
chemiluminescence [47]. However, these methods are time con- crystallinity of Cu 2O, the other two electrodes prepared by
suming and have a complicated process of operation. In contrast, potentiostatic method at − 1.4 V, − 1.6 V were calcinated at 500 °C
electroanalytical technique has become a considerably interesting for 1 h in the muffle furnace to achieve sample c and d.
subject since they can provide rapid response time on the basis of
direct reduction of H 2 O 2 . In this work, the novel flake-like Cu 2 O/
TiO2 electrodes have been successfully fabricated by potentiostatic 2.3. Characterization
electrodeposition combining cyclic voltammetry technology. The
electrochemical properties were investigated by cyclic voltamme- X-ray diffraction (XRD) patterns of the samples were deter-
try (CV) and amperometric experiments. The results indicated mined on a DX-2700 X-ray diffractometer at a scan rate of 0.05°
that a good electrochemical performance was provided by the s − 1 with 20° to 80°, using high-intensity Cu Kα radiation (λ =
two-dimensional structure. The electrocatalytic mechanism of 0.15418 nm). The surface morphology of electrode materials was
H 2 O 2 on the novel flake-like Cu 2 O/TNA electrodes was also analyzed by the scanning electron microscope (SEM) FEI Nova
proposed. NanoSEM 230.

Fig. 5. (A) Amperometric response of Cu2O/TNA electrode with successive addition of 0.5 mM H2O2 to 0.1 M PBS (pH 7.4) at −0.4 V;(B) is the calibration curve of the current response vs.
H2O2 concentration.
36 X. Wen et al. / Journal of Electroanalytical Chemistry 785 (2017) 33–39

Fig. 8. Amperometric responses of Cu2O/TNA electrode to successive addition of 1.0 mM


Fig. 6. Cyclic voltammograms of the Cu2O/TNA electrode prepared in 0.1 M NaOH solution H2O2, 1.0 mM glucose, 1.0 mM fructose, 1.0 mM AA in 0.10 M PBS(pH = 7.4) solution at
in presence of 1.0 mM H2O2 in 0.1 M PBS (pH 7.4). −0.4 V.

2.4. Electrochemical measurements The X-ray diffraction patterns of four samples are shown in Fig. 1
where all the diffraction peaks of the as-prepared products match well
All electrochemical measurements were carried out on a CHI660a with the standard PDF cards. The peaks at 2θ value of 25.3° in Fig. 1(a)
electrochemical workstation (Chenhua Instruments Co. Ltd., Shanghai, can be indexed to the diffraction peaks of anatase TiO2 (JCPD file: 21-
China) with a conventional three-electrode system containing a plati- 1272). Besides, two other weak reflection peaks at approximately
num wire as the auxiliary electrode, the Cu2O/TNA electrode as the 29.6° and 36.5° can be found, which was assigned to (110) and (111)
working electrode and a Hg/Hg2Cl2 (SCE) electrode (saturated KCl) as crystal planes of the Cu2O (JCPDS file: 65-3288). Aside from the diffrac-
the reference electrode. The test solution were 0.1 M phosphate-buff- tion peaks of Ti substrate and TiO2 nanotubes, no other peaks were ob-
ered solution (PBS, pH = 7.4), which contained NaH2PO4, Na2HPO4 served on the surface of the as-synthesized samples. From the
and NaCl. The cyclic voltammetric measurements (CV) were recorded microcosmic mechanism, the surface compositions and structural pa-
in a mixture solution containing 1.0 mM H2O2 and 0.1 M PBS in the po- rameter optimized on Cu2O nanocrystal follow the order of
tential window ranging −0.4 to 0.8 V versus SCE. The measurements of Cu2O(111) N Cu2O(110) ≫ Cu2O(100) [49]. In Shang's early report, the
amperometric curves required operation of the electrode under opti- (110) facet should be more positively charged than the (111) facet,
mized potential of − 0.4 V versus SCE under 25 °C. Once the current and the surface energies of Cu2O are in the following order: γ
reached a steady state signal in the absence of H2O2, a certain amount (100) b γ (111) b γ (110) [50]. Thereby, the (111) and (110) facets of
of H2O2 was successive injected into continuous stirred buffer solution. Cu2O crystals may have better catalytic performance. The obvious differ-
ence of the diffraction peaks among the samples a-d is that the diffrac-
3. Results and discussion tion peaks of (111) plane appear in the sample c and d while the
diffraction peaks of (110) appear in the sample a and b as shown in
3.1. Characterizations Fig. 1. Therefore, it is expected that the samples a-d will provide good
catalytic performance.
The structural features of chemical compounds and nanoparticles of The morphologies of as-synthesized Cu2O nanostructures and TNA
the samples obtained with cyclic voltammetry for 100 cycles and with electrode were observed by SEM with different magnification and are
calcination in a muffle furnace at 500 °C for 1 h displays in Fig.1(a)–(d). shown in Fig. 2. It can be clearly observed that the Cu2O nanostucture

Fig. 7. (A) CVs of Cu2O/TNA electrode in presence of 1.0 mM H2O2 in 0.10 M PBS (pH 7.4) at different scan rates (inner to outer): 50, 80, 100, 120, 150, 180 and 200 mV s−1; (B) the
dependence of the reduction peak current density at −0.4 V on the scan rate.
X. Wen et al. / Journal of Electroanalytical Chemistry 785 (2017) 33–39 37

Table 1
Sensing characteristics of Cu, CuxO based on H2O2 sensors.

Electrode Sensitivity Linear range Detection limit Detection potential


(μA·cm−2·mM−1) (mM) (μM) (V vs.SCE)

Au/Cu2O NPs 292.89 mA 0.025–11.2 1.05 0.36/SHE [25]


Cu2O/N-graphene 26.67 0.005–3.57 0.8 −0.6/GCE [22]
CQDs/octahedral Cu2O good 0.005–5.3 2.8 −0.2Ag/AgCl [26]
Cu2OMS–RGO none 0.005–2.775 10.8 −0.24 Ag/AgCl [56]
Cu2O–rGO 19.5 0.03–12.8 21.7 Hg/Hg2Cl2 [57]
Cu2O/H2O2 52.3 mA 0.05–0.1 0.0039 0.5 vs. Ag/AgCl [23]
Cu2O/Cu NC 870.4 0.0004–10 -0.2 −0.2vs. Ag/AgCl [40]
CuO 5030 0.01–0.96 2.1 −0.2vs. Ag/AgCl [58]
Cu-NPs high 0.0002–2.32 0.1 −0.2 vs. Ag/AgCl [59]
Cu2O/TiO2/Ti 412.11 0.5–8 90.5 −0.4 vs. SCE[This work]

presents a loose flake-like morphology on the surface of TiO2 nanotubes sample b in Fig. 3(b) also presents strong reduction reaction similar to
array in Fig. 2(a) and (b). The irregular lamellar structure of Cu2O results sample a, but the peak potential of reduction is more negative than
from repeatedly cyclic voltammetry in alkaline solution, which attribute that of sample a, which demonstrates that the reduction reaction of
to Cu2O particles constantly dissolve in alkaline solution and constantly H2O2 on the sample b is more difficult than on the sample a. Further-
regenerate under the electrical field. The overall reaction involved in the more, there is hardly no redox peaks appear in Fig. 3(c) and (d) for
growth of Cu2O crystals can be expressed as follows [51–54]: the samples c and d. Therefore, it can be conclude that the flake-like
Cu2O on the surface of electrode play an important role on the
2Cu2þ þ 2e− →2Cuþ ð1Þ electrocatalytical reduction reaction of H2O2 in 0.1 M PBS.
The effect of the Cu2O/TNA electrode prepared at different alkali con-
centration on H2O2 electrochemical property has been explored. Fig. 4
shows the cyclic voltammograms (CVs) curves of the Cu2O/TNA elec-
2Cuþ þ 2OH− →2CuOH ð2Þ trodes prepared at different NaOH concentrations. Compared with the
reduction peaks in Fig. 4, stronger reduction peaks were obtained for
the Cu2O/TNA electrodes prepared in (a) 0.1 M and (b) 0.5 M NaOH so-
lution. However, when NaOH concentration increase to 1.0 M, the re-
duction peak obtained could be found to decrease significantly. It
2CuOH þ OH− →Cu2 O þ 2H2 O ð3Þ
indicated that the content of Cu2O decreased when the concentration
A nanocube morphology along with a few flake-like structure of of alkali solution is up to 1.0 M, indicating that the low NaOH concentra-
Cu2O nanopartices was observed in Fig. 2(c). Moreover, there are tion is beneficial to form flake Cu2O structure. As a consequence, we se-
some nanorods and few flakes on the electrodes surface of sample (d) lected 0.1 M NaOH solution for preparation of the Cu2O modified
from Fig. 2(d). The big difference is that the samples (a) and (b) present electrode.
more flake-like morphologies while the calcination samples (c) and (d)
present mainly rod morphologies and a small amount of flake-like mor-
phologies. In conclusion, the flake-like Cu2O could be successfully 3.3. Selectivity, reproducibility and long-term stability of the Cu2O/TNA
achieved by cyclic voltammetry for 100 cycles at scan rate of electrode
100 mV s−1 in alkaline solution.
The responses of the electrode with different contents of hydrogen
3.2. Electrochemical properties of the Cu2O/TNA electrode peroxide were used to further verify the catalytic performance of the
Cu2O/TNA electrode. The amperometric measurement of the Cu2O/
The cyclic voltammograms (CVs) of the four Cu2O/TNA electrodes in TNA electrode under well experimental conditions upon successive ad-
the presence of 1.0 mM H2O2 in 0.1 M PBS (pH = 7.4) at scan rate of ditions of H2O2 into stirred PBS solution at −0.4 V versus SCE are shown
100 mV s−1 are displayed in Fig.3. Firstly, there is no distinct current re- in Fig. 5(A). The response time for detecting H2O2 to reach a steady-state
sponse of H2O2 observed at the TNA electrode in Fig.3 (e) at the studied current was about 4 s. The calibration curve in Fig. 5 (B) shows a high
potential. However, Fig.3(a) shows a strong redox peaks in the one of linear relationship (R2 = 0.999) between the current and concentration
the modified electrodes which is prepared by CV 100 cycles in 0.1 M of H2O2 in a broad range from 0.5 mM to 8.0 mM, and a detection sen-
NaOH at scan rate of 100 mV s−1 with voltage range of − 0.6–0.6 V. sitivity of a 412.11 μA cm−2 mM−1. We calculated that the detection
The cathodic and anodic peak currents can be attributed to electro- limit was 90.5 μM (S/N = 3). The modified electrode with a flake struc-
chemical reaction of Cu2O, including the reduction of CuO/Cu2O redox ture demonstrated fast amperometric response, wide linear range, high
couple and reactions of the produced CuO layer [55]. In other words, sensitivity and low detection limit, indicating that it is an excellent non-
the cathodic reduction of CuO occurs with the reduction of Cu2O. The enzyme sensor for electro catalytic reduction of hydrogen peroxide.

Fig. 9. Schematic illustration of the preparation of Cu2O/TNA electrode and the electro catalytic reduction of H2O2 on the Cu2O/TNA interface.
38 X. Wen et al. / Journal of Electroanalytical Chemistry 785 (2017) 33–39

In order to investigate the reproducibility of the non-enzyme sensor, dependencies can be described by the Randles-Sevcik equation under
the seven CVs of the same Cu2O/TNT electrode prepared in 0.1 M NaOH 25 °C:
solution in presence of 1.0 mM H2O2 in 0.1 M PBS (pH 7.4) at scan rate of
 
100 mV s−1 as shown in Fig.6. The standard deviation of 1.62% was cal- Ip ¼ 2:69  105 n3=2 AD0 1=2 v1=2 C 0 ð1Þ
culated. In addition, the Cu2O/TNA electrode was set in 6 days at room
temperature to examine the stability. The result with no obvious differ-
ence indicated that the sensor has a relatively stable electrochemical At the same scanning rates, reactants and concentration of reactants
performance. in Eq. (1), the current of peaks depends on the number of electron trans-
To further discuss the electrode kinetic process, the cyclic volt- fer and effective area. Therefore, for the same electrode, the redox peak
ammograms of the Cu2O/TNA electrode recorded in 0.1 M PBS solu- current is directly affected by the number of electron transfer in oxida-
tion at different scan rates with 1.0 mM H 2 O 2 in the range of 50– tion-reduction reaction. Comprehensively, a schematic illustration of
200 mV s − 1 are shown in Fig. 7(A). The dependence of reductive the preparation of Cu2O/TNA electrode and the electro catalytic reduc-
peak current i (the corresponding potential is − 0.4 V) on scan tion of H2O2 on the Cu2O/TNA interface was presented in Fig. 9. Prepara-
rate ν described in Fig. 7(B). A good linearity between peak current tion of heterostructures with narrow band gap semiconductors, e.g. CdS,
and scan rate is achieved, Ip (μA cm − 2 ) = 1108.6 + 22.5 ν CdSe or Cu2O can alleviate the charge carrier recombination, and then
(mV s− 1), with a correlation coefficient (R2 = 0.99). The results il- the formed p-n heterojunctions (e.g. Cu2O/TNA) could delivery elec-
lustrated that the hydrogen peroxide reduction reaction is under a trons from the semiconductor (Cu2O) conduction band transfer to the
diffusion-controlled process. TNA conduction band [61]. On the other hand, the reduction of CuII
The effect of common interfering species was tested by adding into CuI species, the reduction of H2O2 into OH– all need to obtain elec-
1.0 mM H2O2, followed with 1.0 mM glucose, fructose and ascorbic trons transfer [23], and meanwhile, the flake-like structure accelerated
acid (AA) in 0.1 M PBS. The amperometric responses shown in Fig. 8. electron transfer kinetics in the electroactive surface field and also
However, the subsequent substances of glucose, fructose and AA do lead to increase the response signals for H2O2. Thus, the flakiness Cu2O
not show any obvious additional response illustrating good selectivity deposited on the titanium dioxide nanotube arrays with large specific
of the Cu2O/TNA electrode. surface enhanced the catalytic activity of Cu2O/TNA composite for the
The linear range, the limits of detection and sensitivities of the detection of hydrogen peroxide.
different morphologies of copper-based materials towards H2O2 re-
duction have summarized in Table 1. It is found that as-prepared 4. Conclusions
flake Cu 2 O modified TNA electrode exhibited higher sensitivity
and comparatively linear range comparing to Cu 2 O/GO and other In this work, we have successfully synthesized the flake-like Cu2O/
H2 O2 sensor previous reported, indicating that as-prepared flake- TNA electrodes by potentiostatic electrodeposition combining cyclic
like Cu 2 O/TNA electrode could provide a potential application for voltammetry technology. The flake-like Cu2O nanoparticles was pro-
the fast detection of H2O2. duced by using cyclic voltammograms in alkaline solution. The great
catalytic performance of sensor might have benefited from the loose
two-dimensional structure, low weight, large specific surface area, spe-
3.4. Electrocatalysis mechanism of Cu2O/TNA electrode for hydrogen
peroxide cific crystal faces and abundant active sites. On the other hand, the TiO2
nanotube arrays with large surface area strengthen the electron transfer
From Fig.3, we can see that there is no distinct current response ability, which shows great catalytic properties. These properties are be-
to addition of H2O2 on the TNA electrode, however, a strong reduc- lieved to be very helpful for developing novel non-enzyme sensors for
tion peaks at about − 0.4 V was obtained on the flake-like Cu 2 O/ the detection of hydrogen peroxide. This research results will provide
TNA electrode, indicating the H 2 O 2 reduction reaction was en- a strategy for preparation of emerging composite to fabricate the H2O2
hanced by the flake-like Cu 2 O. The electrode reactions were ex- sensor.
plained as follow. The anodic and cathodic reactions of Cu2 O/TNA
electrode can be ascribed to the oxidation of Cu 2 O to CuO as Eq. Acknowledgements
(4), the reduction of CuO to Cu 2 O as Eq. (5) and the reduction of
This work was supported by the National Natural Science Founda-
H 2 O 2 to OH − as Eq. (6) [15,40,60]. The reaction equation can be
expressed as follow: tion of China (No. 51374250 and 51674293), the Hunan Provincial
Natural Science Foundation for Innovative Research Groups (No.
Cu2 O þ 2OH− −2e− →2CuO þ H2 O ð4Þ 2013-2) and the Fundamental Research Funds for the Central Universities
of Central South University (No. 502210011).

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