View Article Online / Journal Homepage / Table of Contents for this issue

Nanoscale Dynamic Article Links < C

Cite this: Nanoscale, 2012, 4, 3875

www.rsc.org/nanoscale COMMUNICATION
A cuprous oxide–reduced graphene oxide (Cu2O–rGO) composite
photocatalyst for hydrogen generation: employing rGO as an electron
acceptor to enhance the photocatalytic activity and stability of Cu2O†
Published on 03 May 2012. Downloaded by Tulane University on 1/22/2019 3:19:49 AM.

Phong D. Tran,*a Sudip K. Batabyal,a Stevin S. Pramana,b James Barber,bcd Lydia H. Wong*b
and Say Chye Joachim Loo*b
Received 13th April 2012, Accepted 1st May 2012
DOI: 10.1039/c2nr30881a

Photocorrosion, that causes rapid deactivation of Cu2O photo-
catalysts, was addressed by incorporating this oxide in a composite
with reduced graphene oxide which acts as an electron acceptor to
extract photogenerated electrons from Cu2O. Cu2O–rGO
composite engineering also allows enhancing significantly photo-
catalytic activities of Cu2O for H2 generation.
The exploitation of renewable, carbon-free energy sources is one of
the greatest challenges confronting us to address the increasing energy
demand of our society and environmental issues associated with the
use of fossil energy. Solar energy is the largest source available to us
and can be converted into electricity through the photoelectric effect
for direct use or stored in batteries.1 Alternatively, it can be converted
into chemical energy stored within chemical bonds of reduced
compounds such as hydrogen, methanol, methane, etc., i.e. solar
fuels, ideally by employing a photo-electrochemical cell.2 In principle,
a photo-electrochemical cell consists of a photoanode to capture solar
energy and convert it into oxidative potential that is subsequently
used for extracting electrons from water via water oxidation reaction
eqn (1), and a cathode or photocathode to employ these energised
electrons for hydrogen generation via proton reduction eqn (2):
2H2O / O2 + 4H+ + 4e (1)
2H+ + 2e / H2 (2)
(2.17 eV) p-type semiconductor, appears as an attractive metal oxide
photocathode material. It can also be easily used for large-scale
applications as it is non-toxic, widely abundant and relatively cheap.
Theoretical calculation estimated a maximal photocurrent of
14.7 mA cm
2 and an optimal solar-to-hydrogen efficiency of up to
18% based on the AM1.5 spectrum.3 Even though Cu2O has been
reported as a visible light photocatalyst for H2 generation3–6 it suffers
from the photo-corrosion phenomenon since the potentials of its
reduction and oxidation into copper metallic and CuO lie within the
band gap. As a photocathode, the photogenerated hole in Cu2O can
be efficiently suppressed by electrons driven from photoanode or
from a sacrificial electron donor. The limiting factor for the photo-
stability of Cu2O is how fast the photogenerated electrons can be
extracted from this material and used for driving hydrogen produc-
tion to prevent or mitigate the self-reduction reaction. Combining
Cu2O with an appropriate n-type semiconductor such as TiO2, ZnO,
etc., which has more positive conduction bands, in an n–p junction
allows efficient transport of photogenerated electrons from Cu2O to
the n-type semiconductor conduction band that results in improving
photostability of Cu2O.3,7–9
Herein we report the utilization of a reduced graphene oxide (rGO)
layer to improve the photocatalytic activities as well as photostability
of Cu2O nanoparticles. The schematic of composite photocatalyst
engineering and its function is presented in Fig. 1. In this Cu2O–rGO
composite, rGO acts as the electron acceptor to extract

To efficiently exploit the solar spectrum, visible light absorption

materials are preferred. Cuprous oxide (Cu2O), a direct band gap

a
Energy Research Institute@NTU, Research TechnoPlaza, 5th Storey, 50
Nanyang Drive, Singapore 637553. E-mail: dptran@ntu.edu.sg; Fax: +65
6790 6748; Tel: +65 6790 4626
b
Solar Fuel Laboratory, School of Materials Science and Engineering,
Nanyang Technological University, 50 Nanyang Avenue, Singapore
639798. E-mail: LydiaWong@ntu.edu.sg; JoachimLoo@ntu.edu.sg; Fax:
+65 6790 9081; Tel: +65 6790 4603
c
Division of Molecular Biosciences, Imperial College London, London SW7
2AZ, UK
d
Department of Material Sciences and Chemical Engineering, Polytechnic Fig. 1 Schematic presentation of Cu2O–rGO composite engineering and
of Torino, Corso Duca degli Abruzzi, 24, 10129 Torino, Italy its function. The rGO electron acceptor extracts the photogenerated
† Electronic supplementary information (ESI) available: Experimental electron from Cu2O resulting in enhancement of photocatalytic activity
details and supporting data. See DOI: 10.1039/c2nr30881a and photostability of Cu2O.

This journal is ª The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 3875–3878 | 3875

photogenerated electrons from Cu2O, thus resulting in an increased
charge separation efficiency within this oxide semiconductor, while
limiting its self-photoreduction process. With this, hydrogen photo-
generation activities and stability of the Cu2O–rGO composite in
neutral aqueous solution were found to be significantly higher than
those found for pristine Cu2O.
Carbon nanomaterials (graphene, carbon nanotubes (CNTs), and
C60) are being largely exploited as a smart support for engineering
advanced materials for solar-to-energy conversion applications,
thanks to their outstanding thermal and chemical stability, high
specific surface area, etc. When composited with semiconductor,
Published on 03 May 2012. Downloaded by Tulane University on 1/22/2019 3:19:49 AM.
these carbon nanostructured supports act as good electron acceptors
that help enhance charge separation within the semiconductor. As
a result, enhancing photocatalytic activities were reported for semi-
conductor–CNT composites compared with the corresponding pris-
tine semiconductor.10–13 Similar positive effects were achieved for
semiconductor–rGO composites including TiO2–rGO,14,15 ZnO–
rGO,16 CdS–rGO,15,17–19 mpg–CNx–rGO,20 and BiVO4–rGO.21 Since
the Cu2O conduction band lies at a more negative potential than
those of ZnO and TiO2 and at the same level to that of CdS,22 it is
reasonable to expect similar electron accepting properties for the
Cu2O–rGO composite.
To synthesize the Cu2O–rGO composite, copper(II) acetate
(Cu(Ac)2) precursor was first loaded onto graphene oxide sheets
(GO) dispersed in an aqueous solution. A similar strategy was
employed by Kim and Park for loading the Cu(Ac)2 precursor onto
the oxidized-CNTs surface.12 Both GO and oxidized-CNTs contain
–COOH, –CHO, etc. functional groups that act as anchoring sites for
the copper precursor. Treatment of the resulted GO–Cu(Ac)2 with
NaOH solution resulted in precipitation of Cu(OH)2 on the GO
surface which was subsequently reduced into Cu2O by using glucose
solution at 100  C. The Cu2O–rGO weight ratio was varied by
varying the amount of Cu(Ac)2 and GO precursors assuming that the
Cu(Ac)2 to Cu2O and GO to rGO conversion yields are unity. Pris-
tine Cu2O was prepared by a similar procedure without using the GO
support. To accelerate the hydrogen photo-generation process, we
employed a platinum nanoparticles co-catalyst in this study. Plat-
inum loading on Cu2O–rGO was kept at 1 wt%. To achieve this,
a pre-calculated quantity of K2PtCl6 precursor was added into
Cu(OH)2–GO suspension with glucose, which reduced this precursor
into Pt nanoparticles at high temperatures. For simplicity in our
discussion, we denote our composite as Cu2O–rGO(x) where x is the
Cu2O–GO weight ratio.
We first investigated the morphology, chemical composition, and
absorption properties of our composites by TEM, XRD, EDX and
UV-vis absorption spectroscopy. Fig. 2A shows TEM and HRTEM
images of the Cu2O–rGO(15) composite, which reveal homogeneous
distribution of Cu2O nanoparticles (grain size of 10 nm) on rGO
sheets. It was found that agglomeration of Cu2O particles occurred
when the Cu2O content was increased. Larger size Cu2O particles
(10–30 nm) were found on graphene sheets in the Cu2O–rGO(25)
composite (Fig. 2B and S1†). XRD analysis clearly confirmed that
the obtained deposits were Cu2O crystals (Fig. 2C). Platinum was not
observed in either TEM or XRD analyses due to its low content in
the Cu2O–rGO materials. Platinum signals were however found in
EDX analysis (Fig. S2†). The control experiment clearly confirmed
that black Pt nanoparticles were produced from the K2PtCl6
precursor in aqueous glucose solution at 100  C. Fig. 2D shows UV-
vis absorption spectra of pristine Cu2O and Cu2O–rGO composites.
3876 | Nanoscale, 2012, 4, 3875–3878
View Article Online
Fig. 2 Characterisation of Cu2O–rGO composites and pristine Cu2O
nanoparticles: TEM images of Cu2O–rGO(15) (A) and Cu2O–rGO(25)
(B) composites, X-ray diffraction of these two composites (C), and UV-
vis absorption spectra of these two composites in comparison with that of
pristine Cu2O (D).
As expected, Cu2O–rGO composites showed higher absorption
intensity in visible light compared with pristine Cu2O nanoparticles
due to the additional absorption by rGO. Absorption intensity
increased with increasing rGO content. Absorption of the rGO
support does however compete with that of Cu2O. To achieve the
highest activity for light-to-hydrogen conversion, the content of rGO
within the composite was optimised. We found that Cu2O–rGO(x)
composites with 15 # x # 25 were the best to fulfil two critical
requirements: (i) having sufficient rGO support material to ensure
high dispersion of Cu2O nanoparticles, and (ii) ensuring that rGO
absorption does not reduce the light absorption of Cu2O.
We have investigated the photoelectrochemical properties of
Cu2O–rGO composites as a photocathode for photo-assisted
reduction of protons to hydrogen. For this propose, the Cu2O–
rGO(15) composite was deposited as a thin film onto Fluorine-doped
Tin Oxide (FTO) by spin coating a suspension of this composite in
ethanol. After drying overnight in a vacuum oven, a homogeneous
film was obtained (Fig. S3†). A 0.1 M potassium phosphate buffer at
pH7 was used as electrolyte solution, which represented the best
compromise between activity and stability of the composites. Under
visible light irradiation (150 W xenon lamp with a 400 nm cut-off
filter as a visible light source; power density on the FTO electrode was
100 mW cm
2), a photocurrent of 0.12 mA cm
2 was obtained at an
applied bias of
0.4 V vs. Ag/AgCl (0.23 V vs. RHE), which is four
(4) times higher than that achieved for the pristine Cu2O/FTO elec-
trode (0.03 mA cm
2) (Fig. 3A). This photocurrent enhancement
clearly indicated that rGO acts as an electron acceptor that helps
enhance charge separation within the Cu2O semiconductor.
When we investigated the photostability of our Cu2O based
photocathodes it was found that both pristine Cu2O and Cu2O–
rGO(15) composite photoelectrodes showed stable photocurrent for
This journal is ª The Royal Society of Chemistry 2012

Published on 03 May 2012. Downloaded by Tulane University on 1/22/2019 3:19:49 AM.
Fig. 3 Photocatalytic activities characterisation of Cu2O–rGO
composite. (A) Transient photocurrent at bias
0.4 V vs. Ag/AgCl
(0.23 V vs. RHE) for the Cu2O/FTO electrode (square dots) and the
Cu2O/rGO(15)/FTO electrode (bulk) using pH7 0.1 M potassium phos-
phate buffer electrolyte solution, 100 mW cm
2 visible light irradiation.
(B) Hydrogen photogeneration from methanol–H2O solution (v/v, 2/8)
using Cu2O nanoparticles (i), mixture of Cu2O nanoparticles and rGO
(25/1, w/w) (ii), and Cu2O–rGO(x) composite photocatalysts (x ¼ 50 (iii),
15 (iv), 25 (v)).
at least 1 h under light irradiation in on–off mode (5 min irradiation
and 5 min under dark condition per cycle). However, given that both
catalytic reduction of protons into H2 and self-photoreduction of
Cu2O into Cu can contribute to the photocurrent observed, we
determined photo-to-hydrogen efficiency to assay photostability of
Cu2O based photocathodes. At an applied bias of
0.4 V vs. Ag/
AgCl, the Cu2O/rGO/FTO electrode generated 0.41 Coulomb
photoelectrons after 1 h of irradiation and 1.4 mmol H2 was produced
giving a faradic yield of 65% (Fig. S4†). This photocurrent-to-
hydrogen yield is far from unity suggesting that part of the photo-
current (ca. 35%) was used in self-reduction of Cu2O into Cu. This
was further confirmed by XRD analysis which showed the appear-
ance of new Cu peaks at 2q 43.5 and 50.6 (Fig. S5†). The self-
photoreduction is more significant for Cu2O/FTO without graphene
support. Only 70 nmol H2 was found after a 0.13 Coulomb photo-
electron was generated (faradic yield of 10%).
In the above experiments, we applied a bias (0.23 V vs. RHE) to
suppress photogenerated holes and drive photogenerated electrons to
reduce protons to H2. Alternatively hole suppression can be achieved
by using a sacrificial electron donor, such as methanol, Na2S/
Na2SO3, etc. We chose to use methanol–H2O solution (2/8, v/v) and
investigate the photocatalytic activities of the Cu2O–rGO composite
for hydrogen evolution. In so doing we used a closed 50 mL Schlenk
tube as the reaction vessel and adjusted the visible light source (150 W
xenon lamp with a 400 nm cut-off filter) to 100 mW cm
2 at the
reactor surface. Gas produced during irradiation was sampled and
analyzed by gas chromatography. Fig. 3B shows hydrogen evolution
for Pt decorated-Cu2O nanoparticles without graphene support
(curve (i)) and different Pt decorated-Cu2O–rGO(x) composites
(curves (iii)–(v)). A control experiment employing pristine Cu2O
nanoparticles without Pt nanoparticles decoration produced only
trace of hydrogen. It was found that H2 generation reached a plateau
after 5 h of irradiation using a Pt decorated-Cu2O nanoparticles
photocatalyst indicating the complete deactivation of the Cu2O
photocatalyst due to the self-photoreduction of this oxide into Cu0.
Photoinstability of a Pt-decorated Cu2O thin film was also reported.3
We note that platinum is the best electrocatalyst for hydrogen
This journal is ª The Royal Society of Chemistry 2012
View Article Online
evolution reaction. Therefore, the deactivation of Pt-decorated Cu2O
nanoparticles is likely due to less efficient interfacial interaction
between Pt and Cu2O nanoparticles which could not allow an effi-
cient electron injection from excited Cu2O to Pt catalyst. rGO has
high specific surface area that allows enhancing interface with Cu2O
nanoparticles. As a consequence, we observed longer lifetimes for all
Cu2O–rGO composite photocatalysts compared with that of Cu2O
nanoparticles, consistent with higher current-to-hydrogen efficiencies
measured for composites. There was a linear evolution of H2 up to
15 h before achieving a plateau using a composite photocatalyst while
the Cu2O nanoparticles photocatalyst without rGO support was
completely deactivated after 5 h. We also performed a control
experiment by employing a mixture of pristine Cu2O nanoparticles
and rGO as a photocatalyst (Cu2O–rGO weight ratio was 25/1). This
mixture showed comparable catalytic H2 photogeneration efficiency
to that obtained for Cu2O nanoparticles without graphene support
and it is significantly lower than those achieved for Cu2O–rGO
hybrids (Fig. 3B, curve (ii)). This result indicates that physical mixing
of Cu2O nanoparticles and rGO sheets does not result in an efficient
charge transport at the Cu2O–rGO junction. Agglomeration of Cu2O
into few hundred nm nanoparticles can be the reason for its poor
interaction with rGO. In contrast, when Cu2O was grown in situ on
graphene sheets, the latter acts as a stabilizer to ensure effective
dispersion of small Cu2O nanoparticles (few ten nm particles) that
resulted in a good electron transport between Cu2O and the rGO
electron acceptor.
Along with enhancing photostability, employing a graphene elec-
tron acceptor resulted in a significant enhancement of photocatalytic
activities of Cu2O nanoparticles (Fig. 3B, S6 and S7†) that consists
with the increasing of photocurrent (Fig. 3A). However, it was found
that employing an electrocatalyst for H2 evolution as a co-catalyst is
still required. The control Cu2O–rGO(25) sample without Pt nano-
particles co-catalyst loading produced only trace of hydrogen. With
1 wt% Pt nanoparticles co-catalyst, highest H2 generation efficiency
was achieved for the Cu2O–rGO(25) composite with an average H2
production rate of 264.5 mmol H2 gcat
1 h
1 that represents a factor of
3.5 higher efficiency compared with Cu2O nanoparticles without
graphene. This catalytic enhancement is comparable to those repor-
ted for CdS–GO composites.15,17 It was found that H2 generation
efficiency slightly depended on rGO and Cu2O content in the
composites. Both higher rGO and lower rGO content have less
efficiency. Increasing rGO content resulted in light absorption
competition for Cu2O, whereas decreasing rGO content caused
agglomeration of Cu2O nanoparticles. Both phenomena caused
a decrease in the light harvesting efficiency of Cu2O that translated
into lower catalytic efficiencies.
To conclude, we have shown that by utilizing graphene sheets as an
electron acceptor the photocatalytic activity for hydrogen production
using visible light and photostability of Cu2O are significantly
enhanced due to the formation of a p–n Cu2O–rGO junction. It was
found that in situ growth and stabilization of Cu2O nanoparticles
onto graphene sheets are required to achieve a good p–n Cu2O–rGO
junction.
Acknowledgements
The authors acknowledge Nanyang Technological University
(NTU), Center of Artificial Photosynthesis (CAPS) for the funding
support.
Nanoscale, 2012, 4, 3875–3878 | 3877

Notes and references
1 A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo and H. Pettersson, Dye-
sensitized solar cells, Chem. Rev., 2010, 110(11), 6595–6663.
2 M. G. Walter, E. L. Warren, J. R. McKone, S. W. Boettcher, Q. Mi,
E. A. Santori and N. S. Lewis, Solar water splitting cells, Chem. Rev.,
2010, 110(11), 6446–6473.
3 A. Paracchino, V. Laporte, K. Sivula, M. Gr€atzel and E. Thimsen,
Highly active oxide photocathode for photoelectrochemical water
reduction, Nat. Mater., 2011, 10(6), 456–461.
4 S. Somasundaram, C. Raman Nair Chenthamarakshan, N. R. de
Tacconi and K. Rajeshwar, Photocatalytic production of hydrogen
from electrodeposited film and sacrificial electron donors, Int. J.
Hydrogen Energy, 2007, 32(18), 4661–4669.
Published on 03 May 2012. Downloaded by Tulane University on 1/22/2019 3:19:49 AM.
5 D. Barreca, P. Fornasiero, A. Gasparotto, V. Gombac, C. Maccato,
T. Montini and E. Tondello, The potential of supported Cu2O and
CuO nanosystems in photocatalytic H2 production, ChemSusChem,
2009, 2(3), 230–233.
6 J.-N. Nian, C.-C. Hu and H. Teng, Electrodeposited p-type Cu2O for
H2 evolution from photoelectrolysis of water under visible light
illumination, Int. J. Hydrogen Energy, 2008, 33(12), 2897–2903.
7 W. Siripala, A. Ivanovskaya, T. F. Jaramillo, S.-H. Baeck and
E. W. McFarland, A Cu2O/TiO2 heterojunction thin film cathode
for photoelectrocatalysis, Sol. Energy Mater. Sol. Cells, 2003, 77(3),
229–237.
8 J. Cui and U. J. Gibson, A simple two-step electrodeposition of Cu2O/
ZnO nanopillar solar cells, J. Phys. Chem. C, 2010, 114(14), 6408–
6412.
9 S. Zhang, S. Zhang, F. Peng, H. Zhang, H. Liu and H. Zhao,
Electrodeposition of polyhedral Cu2O on TiO2 nanotube arrays for
enhancing visible light photocatalytic performance, Electrochem.
Commun., 2011, 13(8), 861–864.
10 L. Sheeney-Haj-Ichia, B. Basnar and I. Willner, Efficient generation
of photocurrents by using CdS/Carbon nanotube assemblies on
electrodes, Angew. Chem., Int. Ed., 2005, 44(1), 78–83.
11 I. Robel, B. A. Bunker and P. V. Kamat, Single-walled carbon
nanotube–CdS nanocomposites as light-harvesting assemblies:
photoinduced charge-transfer interactions, Adv. Mater., 2005,
17(20), 2458–2463.
3878 | Nanoscale, 2012, 4, 3875–3878
View Article Online
12 Y. K. Kim and H. Park, Light-harvesting multi-walled carbon
nanotubes and CdS hybrids: application to photocatalytic hydrogen
production from water, Energy Environ. Sci., 2011, 4(3), 685–
694.
13 K. Woan, G. Pyrgiotakis and W. Sigmund, Photocatalytic carbon-
nanotube–TiO2 composites, Adv. Mater., 2009, 21(21), 2233–2239.
14 N. J. Bell, Y. H. Ng, A. Du, H. Coster, S. C. Smith and R. Amal,
Understanding the enhancement in photoelectrochemical properties
of photocatalytically prepared TiO2-reduced graphene oxide
composite, J. Phys. Chem. C, 2011, 115(13), 6004–6009.
15 X.-J. Lv, W.-F. Fu, H.-X. Chang, H. Zhang, J.-S. Cheng,
G.-J. Zhang, Y. Song, C.-Y. Hu and J.-H. Li, Hydrogen evolution
from water using semiconductor nanoparticle/graphene composite
photocatalysts without noble metals, J. Mater. Chem., 2012, 22(4),
1539–1546.
16 G. Williams and P. V. Kamat, Graphene
semiconductor
nanocomposites: excited-state interactions between ZnO
nanoparticles and graphene oxide, Langmuir, 2009, 25(24), 13869–
13873.
17 Q. Li, B. Guo, J. Yu, J. Ran, B. Zhang, H. Yan and J. R. Gong,
Highly efficient visible-light-driven photocatalytic hydrogen
production of CdS-cluster-decorated graphene nanosheets, J. Am.
Chem. Soc., 2011, 133(28), 10878–10884.
18 P. V. Kamat, Graphene-based nanoassemblies for energy conversion,
J. Phys. Chem. Lett., 2011, 2(3), 242–251.
19 P. Gao, J. Liu, S. Lee, T. Zhang and D. D. Sun, High quality
graphene oxide-CdS-Pt nanocomposites for efficient photocatalytic
hydrogen evolution, J. Mater. Chem., 2012, 22(5), 2292–2298.
20 Y. Zhang, T. Mori, L. Niu and J. Ye, Non-covalent doping of
graphitic carbon nitride polymer with graphene: controlled
electronic structure and enhanced optoelectronic conversion, Energy
Environ. Sci., 2011, 4(11), 4517–4521.
21 A. Iwase, Y. H. Ng, Y. Ishiguro, A. Kudo and R. Amal, Reduced
graphene oxide as a solid-state electron mediator in Z-scheme
photocatalytic water splitting under visible light, J. Am. Chem. Soc.,
2011, 133(29), 11054–11057.
22 R. van de Krol, Y. Liang and J. Schoonman, Solar hydrogen
production with nanostructured metal oxides, J. Mater. Chem.,
2008, 18(20), 2311–2320.
This journal is ª The Royal Society of Chemistry 2012