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Electrochemistry Communications 36 (2013) 99–102

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Short communication

Electrochemical formation and reduction of copper oxide nanostructures


in alkaline media
Ye Wan a,b,c,⁎, Yundian Zhang b, Xianle Wang b, Qing Wang a
a
School of Materials Science and Engineering, Shenyang Jianzhu University, Shenyang 110168, China
b
School of Traffic and Mechanical Engineering, Shenyang Jianzhu University, Shenyang 110168, China
c
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

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

Article history: Formation and reduction of copper oxides in alkaline media were investigated via cyclic voltammetry combined
Received 25 August 2013 with scanning electron microscopy and focus ion beam. Cu2O nanoparticles were generated in the first oxidation
Received in revised form 16 September 2013 peak of cyclic voltammetry. A layer of CuO dendrite crystal, rooting on copper substrate, was transformed from
Accepted 25 September 2013
Cu2O nanoparticles in the preferred growth directions in the second oxidation peak. The nanobranches,
Available online 2 October 2013
composed of nanobelts, and the roots of CuO dendrite crystals were reduced to be Cu2O nanoparticles orig-
Keywords:
inating from the roots of CuO dendrite crystal in the first reduction peak during the reverse scan. The reduc-
Copper oxides tion of CuO was incomplete at the tail of the first reduction peak. Copper nanoparticles, reduced from Cu2O
Nanostructure nanoparticles and the residual CuO dendrite crystals during the second reduction peak, covered the whole
Dendrite crystal sample surface.
Cyclic voltammetry © 2013 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental

The electrochemical processes of copper in alkaline media have Copper samples (99.99% purity) with the size of 15 mm ×
attracted considerable interest because of its technological importance 15 mm × 2 mm were polished with SiC paper (successively 800
in many fields such as transistor system, chemical engineering, and nu- and 1000 grits), degreased with alcohol and rinsed with deionized
clear reactor [1–11]. Many of the papers involved voltammetry [1–10] (DI) water, dried prior to electrochemical experiments.
coupled with many surface techniques such as Raman spectroscopy CV curves were recorded at 25 °C in a three electrode cell with a
[4,6], scanning electron microscopy (SEM) [5,12], X-ray photoelectron LK3200A (Lanlike Co. Ltd., CN). The cell exposed a 1 cm2 portion of
spectroscopy (XPS) [2,4] and photoelectrochemical spectroscopy [6]. the samples to be work electrodes. A flat platinum mesh was served
Cyclic voltammetry (CV) of copper illustrated that two principal oxida- as a counter electrode. All potentials were measured against the sat-
tion peaks and two principal reduction peaks appeared in alkaline solu- urated calomel electrode (SCE, + 0.2415 V vs NHE) and quoted
tion [1,3–5,9]. Although many mechanisms, including dissolution and against this scale. The electrolyte was 1 mol·L− 1 sodium hydroxide
surface reaction mechanisms, mono-layer and double-layer mecha- (NaOH) solution and made from DI water and Sinopharm NaOH.
nisms, and Cu(II) and Cu(III) mechanisms, have been postulated for for- The onset potential of CV was − 1.6 V. It was delayed 20 s prior to
mation of CV peaks of copper in alkaline solution [1,3,4,9,12], there is running every CV curve.
still some dispute pertaining to the nature of the anodic and the cathod- The samples terminated at various potential regions were rinsed
ic processes involved in the formation and reduction of copper oxides in and dried prior to being performed the surface analysis via XPS, SEM
alkaline media for lack of direct proof. and FIB. No significant species changed after removal of the samples
The purpose of this communication is to present direct evidence and from the electrochemical cell. All XPS spectra were recorded using
explore the nature of formation of the CV peaks of copper in alkaline so- an ESCALAB250 (Thermo VG, USA) with a background pressure of
lution via XPS, SEM and FIB. 6.0 × 10−11 bar. The ion gun was with 3 kV beam and 2 μA sample cur-
rent. The surface morphologies of the samples were observed using a
SEM (Nova NanoSEM 430, FEI, Netherlands). A FIB system (Helios
Nanolab 650, FEI, Netherlands) used gallium ions to trench a region of in-
⁎ Corresponding author at: School of Materials Science and Engineering, Shenyang
terest with nanometer scale precision and examined the cross-section
Jianzhu University, Shenyang 110168, China. Tel.: +86 2424690313. image. Imaging was performed with an accelerating voltage of 15.0 kV
E-mail address: ywan@sjzu.edu.cn (Y. Wan). by SEM and 10.0 kV by FIB to produce high resolution images.

1388-2481/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.elecom.2013.09.026
100 Y. Wan et al. / Electrochemistry Communications 36 (2013) 99–102

Cu2p3/2 Cu2p1/2
3. Results and discussion pC2 Raw c
Cu2p3/2,sat
pC2 Sum
A typical CV curve of copper in 1 mol·L− 1 NaOH can be seen in
800.0k
the curve 5 of Fig. 1, and illustrated four significant anodic and ca- pA2 Raw b
thodic peaks. The two anodic peaks located at −0.481 V (labeled A1) pA2 Sum
and − 0.019 V (labeled A2). The two cathodic peaks, labeled C2
(− 0.607 V) and C1 (− 1.11 V), arose during the reverse scan.
600.0k

CPS
In order to investigate the surface species and images involved in the
four CV peaks, the CVs of copper were performed and terminated at dif-
ferent potentials, which should, in principle, allow one to distinguish
between the oxidation and/or reduction processes. For comparison pur- 400.0k
pose, five CV runs were terminated at potentials (1) shortly after the an-
odic peak A1 (curve 1, Fig. 1), (2) prior to the top of anodic peak A2
(curve 2, Fig. 1), (3) at the tail of the anodic peak A2 (curve 3, Fig. 1), a
(4) at the tail of the cathodic peak C2 (curve 4, Fig. 1), and (5) at the 200.0k pA1
tail of the cathodic peak C1 (curve 5, Fig. 1). In going from curve 1
through curve 5, the species and images responsible for different peaks 930 940 950
are addressed in the following sections. B.E.(eV)
Illustrated in Fig. 2 is a series of XPS spectra acquired from the as-
prepared samples, which were removed from the electrolytes at the po- Fig. 2. High resolution XPS spectra of Cu2p core level for the samples removed during CV
scan (fitting results of spectrum b and c were shown as the red solid lines). Removal po-
tentials shown in the CV curves 1, 3 and 4. There were two characteristic
tentials of the samples for the spectra a, b and c indicated by curves 1, 3 and 4 in Fig. 1.
peaks of Cu2p for the spectrum a. One was Cu2p3/2 component at a Spectra were offset to improve readability.
binding energy of 932.2 eV, which could be attributed to either Cu2O
or metallic copper [13–17]. However, one could identify the presence
of Cu2O from the binding energy of the Cu2p1/2 peak at 952 eV,
due to Cu2O [13–15]. The results revealed that the anodic peaks A1
corresponded to oxidation of Cu to Cu2O. Presenting the images of the samples, as in Fig. 3, provides new ob-
Using XPSPEAK 41 software, the Cu2p1/2 main bands of the XPS spec- vious evidence for the anodic and the cathodic processes. Fig. 3 shows
tra b and c were resolved, as shown in Fig. 2, into two main peaks. One the high magnified SEM images of copper during oxidation and reduc-
arose from CuO at 953.7 eV [13,18] and the other from Cu2O at 952 eV. tion processes in going from curve 1 to curve 5 of Fig. 1. Fig. 3(a) illus-
Similarly the Cu2p3/2 bands were resolved into two peaks corresponded trated the image of incorporated Cu2O nanoparticles, due to oxidation
to CuO at 933.6 eV [13,19] and Cu2O at 932.2 eV. The peak at approxi- of copper in the first anodic peaks, covered the surface completely. Den-
mately 943 ± 0.3 eV was due to the Cu2p3/2 satellite peak of CuO [20]. drite crystal, corresponded to the appearance of the second anodic peak
One can estimate the relative amounts of Cu2O and CuO from the resolv- A2 in the CVs, was observed on the surface of the sample removed at
ing results. The mole fraction of Cu2O is ca. 14.9% in the spectrum b and − 0.13 V (curve 2, Fig. 1), as shown in Fig. 3(b). Area A and area D in
approximately 31.3% in the spectrum c. The results indicated that the Fig. 3(b) show that dendrite crystals were mainly three-branched
incompletion of the oxidation of Cu2O to CuO at 0.176 V (curve 3, and four-branched and transformed from Cu2O nanoparticles and pre-
Fig. 1) and the reduction of CuO to Cu2O at the tail of the peak C2 ferred growth direction better than width and thickness. It should be
(curve 4, Fig. 1). Interestingly to note from the CV curve 3 that the mole noted that every dendrite branch was made of CuO nanobelts, for in-
fraction of Cu2O, responsible for the shoulder at −0.15 V, in the anodic stance in the areas B, C and E of Fig. 3(b). Nucleation and growth of
peak A2 (curve 3, Fig. 1) is ca. 17.0% (the fitting result is not shown). It the nanobelts continued until the surface was mainly covered (85.1%)
is close to and correlates well with the mole fraction from the XPS results. by CuO dendrite crystals, when the CV terminated at 0.176 V (curve 3,
Fig. 1), seen in Fig. 3(c). Dendrite branching growth enabled facile cov-
erage of copper substrate with CuO but avoided growth of a thicker CuO
layer. These highly crystalline CuO dendrite structures were not opaque
40 but transparent to electron beam. The length of the branch was up to
40 several micrometers and the width up to 300 nm.
40 A2 In order to explore the cross-section protocol of the oxidation layer
40 formed in the second anodic peak, a FIB system was used to trench
40
the desired surface of the species. Pt was deposited on the sample in
I(mA·cm-2)

A1 the sample chamber of FIB just before trenching to protect the surface
0 1 from ion beam. Fig. 3(f) is the 52°-tilted cross-section image of
0 2 the sample and illuminated a porous layer of dendrite crystal CuO
0 3 covered on the surface of copper substrate with the thickness ca.
0 4 975 nm (600 nm/cos52°). The root size of the dendrite crystal was ap-
0 5 proximately 340 nm (210 nm/cos52°) thick.
C2 Further evidence for the XPS spectrum c is presented in Fig. 3(d) and
illustrated that the species was composed of dendrite crystal CuO and
nanoparticle Cu2O. It is interesting to note that the Cu2O nanoparticles
C1
nucleated originally at the roots of the CuO dendrite crystals and grew
-1.6 -1.2 -0.8 -0.4 0.0 0.4 by the conversion of CuO crystals. The present results explored the re-
E(V) duction process of the peak C2 (Fig. 1) corresponded to transformation
of CuO to Cu2O. Coexistence of CuO and Cu2O in Fig. 3(d) indicated that
Fig. 1. Cyclic voltammograms of copper terminated at different potentials in 1 mol·L-1
NaOH at 40 mV/s scan rate; Curves 1, 3 and 4 correspond to the XPS spectra (a)–(c) in
the cathodic process responsible for the peak C2 of Fig. 1 was in-
Fig. 2. In addition, curves 1–5 correspond to the SEM micrographs (a)–(e) in Fig. 3 as well. complete. In going from curve 4 through curve 5 of Fig. 1, Cu2O
The layers were overlapped and the horizontal axes for curves 1–4 were omitted for clarity. nanoparticles and the residual CuO dendrite crystals were reduced
Y. Wan et al. / Electrochemistry Communications 36 (2013) 99–102 101

Fig. 3. (a)–(e) Surface images of the samples removed from the electrolytes (removal potentials indicated by curves 1–5 in Fig. 1). (f) Cross-section image of the same sample as (c). DCs
denote dendrite crystals.

into copper nanoparticles during the reduction peak C1 (curve 5, Cu2O and the residual CuO indicated incompletions of the oxidation of
Fig. 1), as seen in Fig. 3(e). This result explained the wider potential re- Cu2O to CuO at the tail of the peak A2 and the reduction of CuO to
gion in the reduction peak C1 than the other three peaks in Fig. 1. The re- Cu2O at the tail of the peak C2. The mixture was reduced to be copper
duced copper nanoparticles, denser than Cu2O nanoparticles in Fig. 3(a), nanoparticles in the reduction peak C1 of the CVs.
eventually covered the whole surface.
Acknowledgments
4. Conclusion
The authors gratefully appreciate the financial support from the Na-
The results of CV couples with XPS, SEM and FIB explored the forma- tional Natural Science Foundation of China (Grant Nos.: 51101106 and
tion and reduction processes of copper oxides in alkaline media. The 51131007) and Program for Innovative Research Talent by the Ministry
present results revealed that Cu2O nanoparticles were generated in of Liaoning Education (Grant No.: LR2012019).
the first oxidation peak of the CV scans. A layer (~975 nm thick) of
CuO dendrite crystals, made of the roots of dendrite crystals and their References
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