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Nano-size effects on CuO/TiO2 catalysts for highly

Cite this: Chem. Commun., 2013,
efficient H2 production under solar light irradiation†
49, 9443
Dharani Praveen Kumar,a Muthukonda V. Shankar,*a Murikinati Mamatha Kumari,a
Received 24th June 2013,
Accepted 15th August 2013
Gullapelli Sadanandam,b Basavaraju Srinivasb and Valluri Durgakumari*b

DOI: 10.1039/c3cc44742a

www.rsc.org/chemcomm

Solar light induced interfacial charge transfer of electrons from TiO2 to in photoconversion efficiency and promote electron–hole
1 1
CuO in a water–glycerol mixture produced 99 823 lmol h g catalyst separation via an interfacial charge transfer process. Copper
of hydrogen gas. The dispersed CuO/TiO2 photocatalyst in solution oxides have several benefits, such as narrow band-gap, stability,
exhibited uni-directional electron flow and capture at the Schottky affordability, and they are abundantly available in nature.
barrier facilitating charge separation and electron transfer resulting in Nanostructured photocatalysts exhibited improved performance
enhanced H2 production performance. compared to nanoparticles in the water splitting process.2a,c
Particularly, the 1-D TiO2 nanostructure with a tubular structure and
Hydrogen (H2) generation from solar photocatalytic water splitting hollow inside (porous) is of great potential in photocatalysis.7a–d Such
is a clean process, performed under ambient conditions. Hydrogen catalysts showed a large surface area, extended energy band potential
reacts with oxygen in fuel cells, produces electricity and serves and electrons delocalized along the uni-directional axis. Enhance-
the societal demand.1 For commercial H2 production researchers ment in the H2 production rate with TiO2 nanostructures modified
are working on the development of efficient photocatalysts and with dopants,8a,b sensitizers,8c co-catalysts8d and scavengers8e
reactors with a targeted 10% quantum yield under visible was reported. Our group’s success in enhancement of photo-
light.2 Among the important criteria identified for efficient catalytic H2 production (Table 1 entries 4–6) using Cu2O/TiO2
photocatalytic water splitting are: (i) energy band configuration photocatalyst encouraged us to the present approach on TiO2
and (ii) surface properties. They greatly influence the band edge nanotube material. The scope of the present work is execution
potential, visible light absorption, charge carrier separation, of the heterojunction concept on nanotube and quantum dot
surface reactions, chemical stability and corrosion resistance.2 composites. Here we report the synthesis of CuO deposition
Significant progress has been made for efficient overall water over TiO2 nanotubes and optimization of parameters for highly
splitting into H2 and O2 using novel active photocatalysts under efficient H2 production. In the bio-diesel production process
solar light irradiation.3 Among the systems reported, TiO2 has the glycerol by-product generated is chosen as the scavenger for
been the most attractive due to its appropriate energy band H2 production as it provides a sustainable way to utilize the
potential, stability, non-toxicity, low-cost and easy availability. industrial by-product.
However, poor visible light absorption and fast charge carrier TiO2 nanotubes were synthesized using micrometer sized
(electron–hole) recombination limit its application potential. It TiO2 particles as the precursor with some modifications in the
is known that the use of heterojunction based semiconductor reported procedure.9a The wet-impregnation method was
composites is an effective route to overcome the above barriers adopted for preparation of CuO–TiO2 nanocomposites using
and improve the catalytic efficiency. Copper (Cu0, Cu2+, CuO, copper nitrate solution.6b The activity measurements were
Cu2O) based TiO2 heterojunction catalysts showed efficient H2
generation, superior even to those of several noble-metal Table 1 Comparison of H2 production rates
loaded TiO2 systems.4,5,6b They possess significant advantages
Light H2 production
Sl No. Photocatalyst Scavenger source mmol h 1 g 1cat Ref.
a
Nano Catalysis Research Lab, Department of Materials Science & Nanotechnology,
Yogi Vemana University, Kadapa 516003, India. E-mail: [email protected];
1 NiO/NaTaO3:La Methanol Hg 38 400 9b
2 Pt/TiO2 Methanol Hg 21 350 9c
Fax: +91-8562225419; Tel: +91-9966845899
b
3 CuO/TiO2NT Methanol Hg 71 600 9d
Inorganic and Physical Chemistry Division, Indian Institute of Chemical 4 Ag2O/TiO2 Methanol Solar 3350 6a
Technology (IICT), Hyderabad 500607, India. E-mail: [email protected]; 5 Cu2O/TiO2 Glycerol Solar 20 060 6b
Fax: +91-40-27160921; Tel: +91-40-27193165 6 CoO/TiO2 Glycerol Solar 11 021 6c
† Electronic supplementary information (ESI) available: Experimental, materials 7 CuO/TiO2NT Glycerol Solar 99 823 Present
characterization, results and Fig. S1–S6. See DOI: 10.1039/c3cc44742a report

This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 9443--9445 9443
Communication ChemComm

carried out in a quartz reactor under ambient conditions and

solar light irradiation. The photocatalysts used for H2 generation
experiments are given below:

Photocatalysts
TiO2 Degussa-P25 TNP
Calcined TiO2 nanotube TNT
0.1 wt% Cu-loaded TNT CuTNT-1
0.5 wt% Cu-loaded TNT CuTNT-2
1.0 wt% Cu-loaded TNT CuTNT-3
1.5 wt% Cu-loaded TNT CuTNT-4
2.0 wt% Cu-loaded TNT CuTNT-5
Fig. 1 TNT photocatalyst optimization for efficient H2 production.

The X-ray diffraction patterns (Fig. S1, ESI†) of TNP, TNT and
CuTNT-4 materials reveal that the anatase–rutile mixed phase sufficient for efficient H2 production rates under solar light
exists in TiO2 with characteristic diffraction peaks (101) and irradiation. This is the best active photocatalyst system for hydro-
(110) observed at 2y = 25.4 and 27.5 respectively. The CuTNT-4 gen production rate ever obtained using the smallest amount of
photocatalyst showed intense peaks due to improved crystal- photocatalyst. Similarly, an earlier report demonstrates that the
linity and no characteristic peak exists for copper species due to quantum yield doubled upon decreasing the amount of a highly
fine dispersion of quantum sized particles. The TEM image efficient photocatalyst from 0.5 to 0.05 g (Table 1, entry 1). Thus
(Fig. S2a (ESI†)) of TNT showed tubular shapes, hollow in our results indicate that our catalyst is well-dispersed at the
nature and open-ended on both sides. The tube lengths and optimal catalyst amount resulting in effective light utilization
diameters were 300 to 400 nm and 8–12 nm respectively. The for oxidation–reduction reactions.
TEM image (Fig. S2b, ESI†) of CuTNT-4 showed clear evidence Optimization of copper with TNT catalysts for efficient H2
for CuO quantum dots (o10 nm) deposited on the surface of generation was performed and results are displayed in Fig. S5
nanotubes without damaging the tubular structure. (ESI†). It is observed that increase in copper loading results in
The diffuse reflectance UV-Vis spectrum (Fig. S3, ESI†) of higher H2 production upto 1.5 wt%, beyond which the opposite
photocatalysts reveals that TNT absorption is slightly blue effect was observed. Above the monolayer dispersion, agglomeration
shifted compared with TNP due to quantum size effects. This of copper species on the nanotube surface may produce large
has pushed the band edges and increased the effective band size CuO nanoparticles having a low band potential, which is
gap to 3.2 eV. The CuTNT-4 catalyst appears pale yellow-blue in inefficient for H2 production besides the light screening effect.
colour and showed extended absorption towards the visible At optimized conditions the H2 production rate was found to be
region, Eg = 3.05 eV due to the CuO content. The observed shift 99 823 mmol h 1 g 1cat.
is likely due to nanoheterojunction formed between CuO and Fig. 2 displays a comparison of different photocatalysts for
TNT interface. Given potential energy level of CuTNT-4, it is H2 generation under solar irradiation. The efficiency of photo-
clear that CuO acts only as co-catalyst and not acts as inorganic catalytic H2 generation is in the following order CuTNT-4 > TNT >
visible light absorption sensitizer. TNP. In the TNP photocatalyst, the majority of the generated
The specific surface areas of the photocatalysts are 220, 157 charge carriers undergo fast recombination and only a fraction is
and 48 m2 g 1 for TNT, CuTNT-4 and TNP respectively. The utilized for H2 generation. The observed significant improvement
chemical composition of the CuTNT-4 photocatalysts and in H2 evolution is likely due to delocalization of electrons along
chemical status of copper was analysed using XPS spectroscopy
(Fig. S4, ESI†). The data for CuTNT-4 indicate that Ti, O, Cu and
C elements are observed and their respective photoelectron
peaks appear at binding energies of 459.4 (Ti2p), 530.6 (O1s),
933.7 (Cu2p) and 284.6 eV (C1s). The atomic ratio of Ti to O is
about 1:2, which is in good agreement with the nominal atomic
composition of TiO2. These binding energies indicate that the
oxidation state of copper present on the surface of TiO2 is +2.
The copper peak comes from CuO. This is also in agreement
with previous reports.6b
To begin with, optimization of catalyst loading was studied
from 1 to 100 mg with TNT as the photocatalyst. Fig. 1 displays the
increase in the volume of H2 generated with irradiation time and
the best results were observed with 5 mg catalyst and the rate of
H2 production was 4625 mmol h 1 g 1cat. The present results Fig. 2 Evaluation of photocatalytic activity for H2 generation under solar
reveal that approx. 10% of the catalyst amount i.e. 0.1 g L 1 is irradiation. Inset: CuTNT-4 sustainability.

9444 Chem. Commun., 2013, 49, 9443--9445 This journal is c The Royal Society of Chemistry 2013
ChemComm Communication

the axis of nanotube.9b CuTNT-4 exhibited largest H2 produc- Financial support from Ministry of New and Renewable
tion as a cumulative effect of photogenerated electrons and Energy (MNRE), New Delhi, India (No. 103/163/2009/NT), is
efficient transfer of electrons to CuO sites followed by proton gratefully acknowledged. Dr Shankar is indebted to Dr M.
reduction. CuTNT-4 has the best photocatalytic hydrogen Subrahmanyam, Emeritus Scientist of IICT, for providing valuable
evolution rate ever obtained for Ti-based catalysts which is insights during scientific discussion. Further, he acknowledges the
about five times larger than the best reported values so far using unstinted support extended by Prof. A. Ramachandra Reddy,
glycerol as the sacrificial agent. This has favourable band-edges former vice-chancellor, Prof. K. Krishna Reddy, Dean of Physical
that straddle the redox potential of water photoelectrolysis and Sciences, and Prof. M. Ramakrishna Reddy, Registrar of Yogi
also exhibit stability and recyclability in the literature compared Vemana University, for this research work.
with similar materials (Table 1). To evaluate the sustainability of
the photocatalysts, tests were also conducted by evacuating the
produced gases at regular intervals (4 h); a continuous and stable
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This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 9443--9445 9445