Electrochemistry Communications 13 (2011) 861–864

Contents lists available at ScienceDirect

Electrochemistry Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e l e c o m

Electrodeposition of polyhedral Cu2O on TiO2 nanotube arrays for enhancing visible

light photocatalytic performance
Shengsen Zhang a, b, Shanqing Zhang b, Feng Peng a,⁎, Haimin Zhang b, Hongwei Liu b, Huijun Zhao b
a
The School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China
b
Centre for Clean Environment and Energy and Griffith School of Environment, Griffith University, Gold Coast, QLD 4222, Australia

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

Article history: Nano-sized polyhedral crystalline Cu2O was evenly loaded throughout the structure of TiO2 nanotube arrays
Received 26 April 2011 (TNTs) using an electrodeposition method, which resulted in a nanocomposite namely Cu2O/TNTs. The
Received in revised form 16 May 2011 content of Cu2O loaded on the arrays was controlled by varying the electrodeposition charges. Under visible
Accepted 16 May 2011
light, the photocurrent for water splitting and photocatalytic decolorization efficiency of dye Acid orange
Available online 23 May 2011
II (AO-II) of the Cu2O/TNTs obtained with the deposition charges of 500 mC were about 35 and 18 times that
Keywords:
of TNTs, respectively. The polyhedral Cu2O/TNTs would be a promising material for solar energy conversion
Electrodeposition and organic pollutant degradation.
TiO2 nanotube arrays © 2011 Elsevier B.V. All rights reserved.
Cu2O
Photocatalysis
Photoelectrocatalysis

1. Introduction
Highly ordered TiO2 nanotube arrays (TNTs), have attracted much
attention in the past few years, owing to their high regulation, large
surface areas, excellent controllability and superior electron transport
rate [1, 2]. Among all synthesis methods, anodization represents one
of the most promising approaches, allowing the synthesis of the TNTs
with tunable shapes and sizes [3]. These well aligned TNTs have been
successfully applied in making solar cells and photocatalysts [4].
However, the TiO2 material absorbs only UV light due to its wide band
gap [5], which severely limits the applicability of TNTs under visible
light. Sensitization of the TiO2 nanotube arrays with narrow bandgap
semiconductors has shown promising potential in utilizing visible
light [6].
Significant efforts have been devoted to the fabrication of Cu2O/TNTs
composites as an efficient photocatalyst. Hou [7, 8] and Yang [9] et al.
recently assembled Cu2O nanoparticles on the top surface of the TNTs by
photochemical and electrochemical approaches, respectively. These
composites showed a higher photocatalytic activity than the pure TNTs
under solar light. However, these Cu2O nanoparticles were supported
mainly on the top surface of the TNTs, leading to insufficiently effective
electron pathways between the Cu2O and TiO2. Our previous study [6]
demonstrated that octahedral Cu2O particles-TNTs with exposed (111)
crystal surfaces have better photocatalytic activities (46%) than that of
Cu2O nanoparticles without specific crystal facets deposited on TNTs
⁎ Corresponding author. Fax: + 86 20 87114916.
E-mail address: cefpeng@scut.edu.cn (F. Peng).
(12%). However, this reported octahedral Cu2O particles had relatively
large sizes (i.e., 300–400 nm) [6]. These particles couldn't be deposited
into the inner and external walls of the nanotubes. Therefore, the large
surface area of the 3-D TNTs frameworks could not be fully utilized.
Consequently, the photocatalytic activity of the Cu2O/TNTs composite is
still not satisfactory under visible light.
In this work, we successfully fabricated high efficient Cu2O/TNTs
composites by incorporating the nano-sized polyhedral Cu2O with
exposed (111) crystalline surfaces into the entire TNTs frameworks
using an electrodeposition method [10]. The photocatalytic and
photoelectrocatalytic performance of the as-prepared Cu2O/TNTs
were evaluated under visible light.
2. Experimental
2.1. Preparation of TNTs and Cu2O/TNTs
The TNTs were prepared by an electrochemical anodization
process according to our previous report [11]. The TNTs were
annealed in a tubular furnace at 450 °C for 4 h in air for subsequent
electrodeposition experiments. The Cu2O/TNTs composites were
obtained by electrochemical deposition of Cu2O in a three-electrode
cell(Autolab PGSTAT30) , using the TNTs, Ag/AgCl and Pt mesh as the
working, reference, and counter electrodes, respectively. The electro-
lyte was prepared by dissolving 0.4 M CuSO4 in a 3 mol L −1 lactic
acid solution, and was further adjusted to pH = 11.0 with 5.0 M NaOH
solution. The electrolyte was stirred and kept at a constant temper-
ature of 25 °C and a potential of − 0.8 V vs. Ag/AgCl was used during
the deposition process. Four types of samples are obtained by varying

1388-2481/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2011.05.022
862 S. Zhang et al. / Electrochemistry Communications 13 (2011) 861–864
electrodeposition charges i.e., 50 mC, 250 mC, 500 mC and 750 mC,
and denoted as Cu2O/TNTs-50, Cu2O/TNTs-250, Cu2O/TNTs-500 and
Cu2O/TNTs-750, respectively. The obtained samples were dried at
50 °C for 24 h in vacuum.
2.2. Characterization of Cu2O/TNTs
X-ray diffraction (XRD) analysis was carried out with an X-ray
diffractometer (D/max-IIIA, Japan) using Cu Kα radiation source. The
chemical nature of Cu was studied using X-ray photoelectron spec-
troscopy (XPS) in Krato Axis Ultra DLD spectrometer with Al Kα
X-ray (hv = 1486.6 eV) at 15 kV and 150 W. The binding energy was
referenced to C 1s line at 284.6 eV for calibration. The surface morphol-
ogy was examined by scanning electron microscope (HRTEM) analysis
were carried out using a microscope JEM-2200FS with field emission
gun (FEG) under 200 KV accelerating voltage. UV–vis diffuse reflectance
spectroscopy (DRS) was recorded by a UV-1601 spec-trophotometer
(Shimazu, Japan).
Photocurrent measurements were carried out in a standard
electrochemical workstation (CV-27, BAS) coupled with a Xe lamp
(PLS-SXE300UV, TrustTech, China). The wavelengths of the incident
light were greater than 400 nm through a UV-400 filter. The intensity
of the incident light was 150 mW/cm 2. A 0.05 M Na2SO4 solution was
used as supporting electrolyte. The photocatalytic activity was
evaluated through photocatalytic decolorization of dye Acid orange
II (AO-II) under visible light after the samples reached adsorption
equilibriums according to our previous report [11].
3. Results and discussions
Fig. 1A shows the average inner diameter of TNTs is ca. 100 nm
while the length is ca. 900 nm. The SEM image indicates that the
nanotubes were well-aligned and vertically oriented on the titanium
substrate. The growth evolution of the Cu2O/TNTs can be demon-
strated from Fig. 1B to F. The original TNTs have a relatively smooth
surface (Fig. 1A) and become “rough” with 50 mC deposition charge
(Fig. 1B) and “rougher” with 250 mC deposition charge (Fig. 1C) due
to the increasing Cu2O deposition. This suggests that the Cu2O
particles were formed on the surface of the TNTs presumably due to
the satisfactory conductivity of the TNTs. The uniform polyhedral
A B
D E
Fig. 1. SEM images of the Cu2O/TNTs with different electrodeposition charges, (A) 0 mC, (B) 50 mC, (C) 250 mC, (D, E) 500 mC and (F) 750 mC. The circle indicates the Cu2O particles
inside the nanotubes.
Cu2O can be observed with electrodeposition charges of 500 mC (Fig.
1D and E). These as-prepared Cu2O particles have a polyhedral shape
with average side length of ca. 80 nm. The cross-section image in
Fig. 1E shows that the polyhedral Cu2O particles are embedded into
the entire TNTs structure, including the surface, the external and
internal walls of the TNTs. With the increase of electrodeposition
charge to 750 mC (Fig. 1F), the average side length of the polyhedral
Cu2O grows to ca. 100 nm. This results in a dense Cu2O particles layer
that almost covers all the nanotube pores.
Fig. 2A confirms that the inner diameter of nanotube is about
100 nm, and the wall thickness is about 20 nm. In order to confirm the
crystalline phase of the nanoparticles, HRTEM, flourier fast transition
(FFT) image and inverse fast flourier transformation (IFFT) image were
obtained (Fig. 2B to D). Fig. 2B provides lattice fringes of a singular Cu2O
nanoparticle. The corresponding FFT image could be indexed as [011]
using the Cu2O crystal parameter. Fig. 2D shows the IFFT image derived
from Fig. 2C gives two mutual perpendicular lattice fringes of (111) and
(211). Lattice fringes with interplanar spacings, i.e., d(111) = 0.24 nm
and d(211) = 0.17 nm, are clearly imaged and are consistent with the d
value of lattice spacing of the Cu2O (JCPDS 05-667). Overall, Fig. 2B
confirms polyhedral Cu2O nanoparticles with (111) crystal surface were
successfully grown into the frameworks of TNTs.
Fig. 3A shows the TNTs sample consists of anatase predominantly
and a small amount of rutile. The characteristic peaks of Cu and CuO
were not observed for all the samples, which suggests that no metal
copper or CuO formed in the electrodeposition processes. There are
four peaks with 2θ values of 36.52, 42.44, 61.54 and 73.69, corre-
sponding to (111), (200), (220), and (311) crystal planes of pure
Cu2O, respectively [9]. The (111) reflection of the samples obtained is
comparatively strong, which is probably due to the exposed
orientation of the nanocrystalline Cu2O. Fig. 3A also displays the
intensities of the Cu2O characteristic peaks increase with the increase
in deposition charges, suggesting the increased size and amount of the
nanocrystalline Cu2O. The characteristic peaks of Cu2O for the Cu2O/
TNTs-50 were not observed probably due to the Cu2O with insufficient
amount and size. The typical XPS peaks of the Cu(2p) at 952.9 and
932.7 eV [12] for Cu2O/TNTs-500 demonstrate the existence of Cu +, as
shown in Fig. 3B. Furthermore, the characteristic peak for Cu 2+ at
942 eV (2p3/2) was not observed [13]. This result confirms that the
sample contains Cu + rather than Cu 2+.
C
F
 S. Zhang et al. / Electrochemistry Communications 13 (2011) 861–864 863

1.8
A B A d a: 0 mC
1.6 b: 50 mC
e c: 250 mC

Absorbance (a.u.)
d: 500 mC
1.4 e: 750 mC
c

1.2
b
1.0
a
0.8

C D 300 400 500

Wavelength (nm)
600 700

1.2
B Light Light Light a: 0 mC
1.0 d b: 50 mC
c: 250 mC
0.8 d: 500 mC

Iph (mA/cm2)
e e: 750 mC
0.6 c
Fig. 2. TEM and HRTEM analysis of the sample Cu2O/TNTs-500: (A) TEM image;
(B) HRTEM image of the selected B section in image A; (C) FFT image of the selected C 0.4 b
section in image B; (D) IFFT image derived from image C.

0.2
Fig. 4A shows the visible light absorption of the Cu2O/TNTs Dark Dark a Dark Dark
increases dramatically with the electrodeposition charge from 50 to 0
500 mC due to the increased Cu2O amount. However, the absorption 0 20 40 60 80 100 120 140 160
decreases when the electrodeposition charge is 750 mC. This can be Time(s)
explained by the observation on Fig. 1F. The polyhedral Cu2O particles 100
are larger and packed in a much compact way, which leads to the C
enhancement of the light reflection and the reduction of the light Adsorption
80
Visible light irradiation
Efficiency (%)

60
A A : Anatase
R : Rutile
a: 0mC
b: 50mC T
T : Tisubstrate c: 250mC 40
C : Cu2O d: 500mC
Intensity (a.u)

T e: 750mC
20

A C
0
R TC A CT CT 0 mC 50 mC 250 mC 500 mC 750 mC
e R
d
c
b Fig. 4. (A) UV–vis DR spectra of the Cu2O/TNTs samples; (B) photocurrent density
a profiles (Iph) of the Cu2O/TNTs at a bias potential of 0.0 V (vs. Ag/AgCl) under visible
light; (C) the comparison of adsorption and visible light photocatalytic degradation
20 30 40 50 60 70 80
efficiencies of the Cu2O/TNTs to the dye AO-II.
θ,degree
2θ

diffusion. Consequently, the Cu2O/TNTs-750 has a weaker visible light

6.0 B Cu 2p 932.7 eV absorption than Cu2O/TNTs-500.
The photocurrent density was tested in the photoelectrocatalytic
Intensity (10000 cps)

5.0
water splitting process as shown in Fig. 4B. No significant current is
observed in the dark for all the samples. Under visible light, the
4.0
952.9 eV photocurrents spike and then reach a relatively steady state after ca.
20 s. The average steady photocurrent increases with the electrode-
3.0
position charge from 50 to 500 mC and then declines with the charge
2.0
of 750 mC. This coincides with the UV–vis DRS perfectly, suggesting
that the increases of the photocurrents are attributed to the enhance-
1.0 ment of the visible light adsorption of the samples. Fig. 4C shows the
TNTs have a decolorization percentage of 5.0% for AO-II under visible
960 955 950 945 940 935 930 925 light. In strong contrast, the photocatalytic activity of Cu2O/TNTs
Binding Energy (eV) increases significantly from 45.1% to 90.8% with the increase of the
electrodeposition charges from 50 to 500 mC, and then decreases with
Fig. 3. (A) XRD patterns of the Cu2O/TNTs samples; (B) XPS spectrum of Cu 2p of the the further increase of the charges, i.e., 67.1% for the Cu2O/TNTs-750.
sample Cu2O/TNTs-500. Fig. 4C also shows the adsorption amount of the AO-II for all samples is
864 S. Zhang et al. / Electrochemistry Communications 13 (2011) 861–864
very small in comparison with the photocatalytic decolorization
percentage, demonstrating adsorption plays an insignificant part on
the photocatalytic decolorization of the dye.
The Cu2O/TNTs samples show the same trend for photoelectroca-
talytic water splitting and photocatalytic decolorization of AO-II.
Under visible light irradiation, the photocurrent and photocatalytic
decolorization percentage of the Cu2O/TNTs-500 were about 35 and
18 times that of the pure TNTs, respectively. The mechanism respon-
sible for the increased efficiency can be explained as below. Firstly,
the photocatalytic efficiencies depend on not only the Cu2O loading,
but also the light-exposed Cu2O surface area. The Cu2O/TNTs-750
possesses lower photocatalytic efficiency than the Cu2O/TNTs-500
mainly because less amount of visible light is able to penetrate the
Cu2O layer and trigger valid illumination. Secondly, well-ordered
structure of the TNTs provides the large surface area and frameworks
and act as a directional charge transport channel [6]. If the Cu2O
particles can be distributed evenly and closely on the internal and
external walls of the TNTs, the photo-generated electrons can be
quickly transferred into TNTs frameworks and consequently reduce
the electron-hole recombination [14]. It is for these reasons that the
decolorization efficiency has been dramatically improved to 90.8% in
comparison with our previous work, where only 46% decolorization
percentage was achieved for the large size polyhedral [6].
In conclusion, the size, loading amount, distribution, and mor-
phology of the nanocrystalline Cu2O on the TNTs can be controlled by
the electrodeposition charges. The as-prepared Cu2O/TNTs-500 exhib-
ited excellent photoelectrochemical performance and photocatalytic
activity under visible light.
Acknowledgement
The authors thank the National Natural Science Foundation of
China (No. 20873044).
References
[1] I. Paramasivalm, J.M. Macak, P. Schmuki, Electrochem. Commun. 10 (2008) 71.
[2] J.M. Macak, M. Zlamal, J. Krysa, P. Schmuki, Small 3 (2007) 300.
[3] J.M. Macak, H. Tsuchiya, L. Taveira, S. Aldabergerova, P. Schmuki, Angew. Chem.
Int. Edit. 44 (2005) 7463.
[4] D.A. Wang, T.C. Hu, L.T. Hu, B. Yu, Y.Q. Xia, F. Zhou, W.M. Liu, Adv. Funct. Mater. 19
(2009) 1930.
[5] A. Bendavid, P.J. Martin, A. Jamting, H. Takikawa, Thin Solid Films 356 (1999) 6.
[6] L. Huang, S. Zhang, F. Peng, H. Wang, H. Yu, J. Yang, S. Zhang, H. Zhao, Scripta
Mater. 63 (2010) 159.
[7] Y. Hou, X.Y. Li, X.J. Zou, X. Quan, G.C. Chen, Environ. Sci. Technol. 43 (2009) 858.
[8] Y. Hou, X.Y. Li, Q.D. Zhao, X. Quan, G.H. Chen, Appl. Phys. Lett. 95 (2009) 093108.
[9] L.X. Yang, S.L. Luo, Y. Li, Y. Xiao, Q. Kang, Q.Y. Cai, Environ. Sci. Technol. 44 (2010)
7641.
[10] L.L. Wu, L.K. Tsui, N. Swami, G. Zangari, J. Phys. Chem. C 114 (2010) 11551.
[11] S.S. Zhang, F. Peng, H.J. Wang, H. Yu, S.Q. Zhang, J. Yang, H.J. Zhao, Catal. Commun.
12 (2011) 689.
[12] Z.Q. Yu, C.M. Wang, M.H. Engelhard, P. Nachimuthu, D.E. McCready, I.V.
Lyubinetsky, S. Thevuthasan, Nanotechnology 18 (2007) 115601.
[13] S.Y. Gao, S.X. Yang, J. Shu, S.X. Zhang, Z.D. Li, K. Jiang, J. Phys. Chem. C 112 (2008)
19324.
[14] Y. Bessekhouad, D. Robert, J.V. Weber, Catal. Today 101 (2005) 315.