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One-step synthesis of CdSTiO2chemically reduced graphene oxide composites via microwave-assisted reaction for visible-light photocatalytic degradation of methyl orangew
Downloaded on 16 August 2012 Published on 09 December 2011 on http://pubs.rsc.org | doi:10.1039/C2CY00452F

Tian Lv,a Likun Pan,*a Xinjuan Liu,a Ting Lu,a Guang Zhu,a Zhuo Suna and Chang Q. Sunb
Received 10th November 2011, Accepted 8th December 2011 DOI: 10.1039/c2cy00452f One-step synthesis of CdSTiO2chemically reduced graphene oxide (RGO) composites was carried out using microwave-assisted reduction of graphite oxide in CdS precursor solution with TiO2 suspension. The photocatalytic performance of CdSTiO2RGO composites in degradation of methyl orange was examined. Results show that the RGO addition could enhance the photocatalytic performance of CdSTiO2 composites with maximum degradation eciency of 99.5% under visible light irradiation as compared with the pure TiO2 (43%) and CdSTiO2 (79.9%) composites due to the increase of specic surface area for more adsorbed MO and the reduction of electronhole pair recombination with the introduction of RGO.

1. Introduction
Currently considerable attention has been paid to semiconductor oxide photocatalysis for water treatment due to its good ability to destroy pollutants and broad compound applicability.14 Among the various semiconductor oxides, TiO2 has been proven to be the promising photocatalyst for widespread environmental applications due to its intriguing optical and electrical properties, low cost, stability, nontoxicity, and abundance.5,6 However, the wide band gap of TiO2 (3.2 eV) limits its photocatalytic property in the UV region which only occupies 35% of the total solar spectrum. To improve the sunlight photocatalytic eciency, many promising studies are reported to couple TiO2 with a narrow band gap semiconductor material, typically CdS (2.4 eV), to extend the absorption to the visible light range.710 In the meantime, the photoexcited electrons in CdS can be eciently injected into TiO2 because the conduction band position of CdS is higher than that of TiO2.11,12 Unfortunately, the quick recombination of photo-generated charge carriers still exists in the CdSTiO2 composite and the recombination signicantly decreases its photocatalytic performance. Therefore, conductive nanomaterials with a
a

Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, China. E-mail: lkpan@phy.ecnu.edu.cn; Fax: +86 21 62234321; Tel: +86 21 62234132 b School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798, Singapore w Electronic supplementary information (ESI) available. See DOI: 10.1039/c2cy00452f

work function lower than the conduction band of TiO2, such as carbon nanotubes (CNTs)13,14 and Pt,1517 have been incorporated into the CdSTiO2 composite to form hybrid materials to solve this problem. In the photocatalysis process, these nanomaterials can act as an excellent electron-acceptor/ transport material to eectively facilitate the migration of photo-induced electrons and hinder the charge recombination in electron-transfer processes due to the electronic interaction between the CdSTiO2 composite and them, which enhances the photocatalytic performance. Recently, graphene, a rising star in the carbon family, has generated increasing interest both in fundamental science and potential applications due to its good conductivity, high electron mobility, superior chemical stability and large surface-to-volume ratio.1824 Similar to CNTs, graphene can also act as an excellent electron-acceptor/transport material.25 Eorts have been made to combine TiO2 and graphene to obtain hybrid materials with superior photocatalytic performance.2631 Li et al.32 reported the incorporation of chemically reduced graphene oxide (RGO) in TiO2 to form TiO2graphene composites by visible-light photocatalytic reduction of graphite oxide (GO). However, the study on the incorporation of RGO into CdSTiO2 composites for photocatalysis has not yet been reported. Thus, the exploration of the CdSTiO2RGO hybrid is necessary to gain the understanding of the individual contribution from RGO, CdS and TiO2 to form the basis for photocatalysis design and application. In this work, we report the one-step synthesis of CdSTiO2 RGO composites using microwave-assisted reduction of GO in CdS precursor solution with TiO2 suspension. Microwave irradiation heats the reactant to a high temperature in a short
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time by transferring energy selectively to microwave absorbing polar solvents. Thus it can facilitate mass production in a short time span with little energy consumption33,34 and form an intimate contact between the components.3537 Such a microwave-assisted reaction is hardly employed to synthesize CdSTiO2RGO composites though it has been used successfully to fabricate RGO,3640 CdS4143 or CdSTiO2,44 respectively. The photocatalytic eciency of the as-synthesized CdSTiO2RGO composite in degradation of methyl orange (MO) under visible light irradiation is much improved compared with the pure TiO2 and CdSTiO2.
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2. Experimental
Commercial graphite powder (Sianpharm Chemical Reagent Co, Ltd.) was used as the starting reagent for the synthesis of GO via a modied Hummers method.21,22,31,45 1.8 mg ml1 GO suspension, 7 ml 0.45 mM CdCl2 solution and 3 ml 0.64 mM Na2S solution were added into 10 ml 0.6 mM TiO2 (Degussa P25) suspension and then the solution was sonicated for 30 min to produce uniform dispersion. The pH value of solution was adjusted to 1011 by adding NaOH. It was observed that the color of suspension had changed into yellow, indicating the possibility of spontaneous CdS formation. The solution was then put into an automated focused microwave system (Explorer-48, CEM Co.) and irradiated at 150 1C under the power of 100 W for 10 min. It was observed that the color of suspension had changed into grayish-black, indicating the chemical reduction of the GO sheets.46 The obtained RGO consists of four to ve atom layers.36 The as-synthesized CdSTiO2RGO samples with 0, 0.72, 1.43, 2.13, 2.82, and 3.50 wt.% RGO, named as CTG-0, CTG-1, CTG-2, CTG-3, CTG-4 and CTG-5, were isolated by ltration. They were washed several times using distilled water, and nally dried in a vacuum oven at 60 1C for 24 h. TiO2RGO samples with 0.72, 1.43 and 2.13 wt% RGO, named as TG-1, TG-2 and TG-3, and CdSRGO samples with 0.72, 1.43 and 2.13 wt% RGO, named as CG-1, CG-2 and CG-3, were also synthesized by direct microwave assisted reaction in aqueous solution for comparison. Microwave-assisted synthesis of CdSTiO2RGO composites is a one-step process. RGO is synthesized by direct microwave assisted reduction of GO suspension. Due to the distribution of carboxylic acid groups on GO, TiO2 nanoparticles dispersed on the carbon support are found to accumulate along the wrinkles and edge of RGO.26 Meanwhile, positively charged Cd2+ ions form complexes with TiO2 nanoparticles and S2 from Na2S can move quickly to react with Cd2+ producing uniform CdS nuclei under microwave irradiation. The CdS nuclei grow, crystallize, and stabilize on TiO2 under the microwave irradiation, leading to a good contact between CdS and TiO2.37,47 The surface morphology, structure and composition of the samples were characterized by eld-emission scanning electron microscopy (FESEM, Hitachi S-4800), high-resolution transmission electron microscopy (HRTEM, JEOL-2010), energy dispersive X-ray spectroscopy (EDS, JEM-2100) and X-ray diraction spectroscopy (XRD, Holland PANalytical PRO PW3040/60) with Cu Ka radiation (V = 30 kV, I = 25 mA), respectively. The BrunauerEmmettTeller (BET) specic
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surface areas of the samples were evaluated on the basis of nitrogen adsorption isotherms measured at 77 K using a BELSORP-max nitrogen adsorption apparatus (Japan Inc.). All the samples were degassed at 150 1C before nitrogen adsorption measurements. The BET surface area was determined using the adsorption data in the relative pressure (P/P0) range of 0.050.35. The UV-vis absorption spectra and diuse reectance spectra with BaSO4 as a standard were recorded using a Hitachi U-3900 UV-vis spectrophotometer. The photocatalytic performance of the as-prepared samples was evaluated through the experiment of photocatalytic degradation of MO under visible light irradiation. 150 mg CdSTiO2RGO powders were dispersed into 100 ml MO aqueous solution (10 mg l1). The mixed suspensions were continuously stirred for 0.5 h in the dark to reach an adsorption desorption equilibrium. Under the ambient conditions and stirring, the mixed suspensions were exposed to visible light irradiation produced by a 400 W metal halogen lamp with a cut o lter (l 4 400 nm). The irradiation intensity was approximately 8.7 mW cm2 measured using a chromameter (CS-100A). At certain time intervals, 2 ml of the mixed suspensions were extracted and centrifugated to remove the photocatalyst. The degradation process was monitored by measuring the absorption of MO in the ltrate at 463 nm using a UV-vis absorption spectrometer.

3. Results and discussion

Fig. 1(a) shows the FESEM images of as-synthesized RGO. The RGO nanosheets are curled and corrugated. Fig. 1(b) and (c) display the FESEM images of CTG-0 and CTG-4. As compared with CTG-0, it is observed that RGO sheets are decorated densely by CdSTiO2 in CTG-4, which displays a

Fig. 1 FESEM images of (a) RGO, (b) CTG-0 and (c) CTG-4; (d) low-magnication and (e) high-magnication HRTEM images of CTG-4; (f) EDS spectrum of CTG-4.

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good combination between them. From the low-magnication HRTEM image of CTG-4 in Fig. 1(d), it is seen that some nanoparticles are attached onto the surface of the RGO sheet. The RGO sheets act as bridges for the connection between dierent nanoparticles. Fig. 1(e) shows a high-magnication HRTEM image of CTG-4. The larger crystallite is identied as TiO2 nanoparticles. The lattice spacing measured for this crystalline plane is 0.352 nm, corresponding to the (101) plane of anatase TiO2 (JCPDS#211272). Around the edge of TiO2 crystallite, ne crystallites are observed. The crystallites connecting to the TiO2 have lattice fringes of 0.335 nm which are ascribed to the (111) plane of CdS (JCPDS#80-0019). The existence of CdS and TiO2 in the composite is conrmed by the presence of Cd, S, Ti and O peaks in the EDS prole (Fig. 1(f)). Furthermore, the BET specic surface areas of CTG-0, CTG-2, and CTG-4 are found to be 1.3, 4.6 and 8.3 m2 g1, respectively, indicating that the increase of RGO can supply more surface sites to accommodate more adsorbed MO, which is benecial to the photocatalytic degradation of MO.48 The XRD patterns of CdS, RGO, TiO2, CTG-0 and CTG-4 are shown in Fig. 2. The main peaks located at 26.61, 43.81, and 51.81 correspond to the (111), (220) and (311) planes of CdS (JCPDS#80-0019). RGO sheets exhibit a (002) diraction peak at 261 and a (100) peak at 44.51.49 Compared with the XRD pattern of pure TiO2 in which the peaks correspond to anatase and rutile phases of TiO2 (JCPDS#21-1272), three main peaks of CdS appear in the XRD proles of CTG-0 and CTG-4. This nding further conrms the existence of CdS on TiO2. The signals corresponding to CdS indicate that CdS crystallites are mainly present as a cubic structure. No typical diraction peaks of carbon species are observed, which may be due to the low amount and relatively low diraction intensity of RGO.50 Fig. 3 shows the UV-vis absorption spectra of TiO2, CTG-0, CTG-1, CTG-2, CTG-3, CTG-4 and CTG-5. It can be seen that the RGO shows an absorption peak at B240 nm, which is generally regarded as the excitation of p-plasmon of graphitic structure.51,52 The absorption peak near 350 nm is dominated by TiO2. The addition of CdS results in the appearance of an absorption peak near 500 nm. The increase of the absorbance with the increase of RGO content in the composite, also observed by others,2628 is suggested to be due to the absorption contribution from RGO, the increase of surface electric

Downloaded on 16 August 2012 Published on 09 December 2011 on http://pubs.rsc.org | doi:10.1039/C2CY00452F

Fig. 3 UV-vis absorption spectra of TiO2, CTG-0, CTG-1, CTG-2, CTG-3, CTG-4 and CTG-5.

Fig. 2 XRD spectra of CdS, RGO, TiO2, CTG-0 and CTG-4 with notations of aanatase TiO2, rrutile TiO2, ccubic CdS.

charge of the oxides and the modication of the fundamental process of electronhole pair formation during irradiation.53,54 Furthermore, the diuse reectance spectra were also used to approximate the optical absorbance precisely through the KubelkaMunk function:55 K/S = F(R) = (1 R)2/2R and the similar result as UV-vis absorption spectra was revealed (see Fig. S1, ESIw). The photocatalytic degradation of MO under visible light irradiation was conducted to evaluate the photocatalytic performance of TiO2, CTG-0, CTG-1, CTG-2, CTG-3, CTG-4 and CTG-5, as shown in Fig. 4a. It is observed that the concentration of MO is hardly reduced under visible light irradiation in the absence of the photocatalyst. The CdSTiO2 composite (CTG-0) exhibits much higher photocatalytic degradation eciency (79.9%) than the pure TiO2 (43%) because the incorporation of CdS extends the absorption to the visible light range. When the RGO is introduced into the composite, the degradation eciency is increased to 82.1%, 93.4%, and 98.5% for CTG-1, CTG-2 and CTG-3 and reaches the maximum value of 99.5% for CTG-4. The enhancement of the photocatalytic performance should be ascribed to the increase of the amount of adsorbed MO in the presence of RGO with giant two-dimensional planar structure in the composite,26 as indicated by BET measurement, and the stepwise structure of energy levels constructed in the dye CdSTiO2RGO composite,31 as shown in Fig. 5. Two photoinduced degradation paths, one initiated by CdS excitation and another from the self-sensitized destruction of the dyes,56,57 are at work simultaneously under visible light: (i) considering the potential of the conduction band of TiO2 (4.2 eV), CdS (3.98 eV) vs. vacuum and the work function of RGO (4.4 eV),5861 photo-induced electrons easily transfer from photoexcited dye (MO*) to RGO via the conduction bands of CdS and TiO2, which react with adsorbed oxidants, usually O2, to produce reactive oxygen radicals (O2). The increase of the amount of adsorbed MO can cause its more ecient self-sensitized degradation; (ii) the photoexcited electrons at the CdS conduction band also easily transfer to RGO via the TiO2 conduction band, which could eciently separate the photo-induced electrons and hinder the charge recombination in the processes of electron-transfer, thus enhance the photocatalytic performance. However, when the RGO content
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Fig. 5 Schematic diagram of energy levels of MO, CdS, TiO2 and RGO. CB, VB, and F are conduction band, valence band and work function.

work, and self-sensitized destruction of the dyes still exists if only using wide-band gap TiO2 under visible light irradiation,63 the photocatalytic activities of TiO2RGO in degradation of MO under visible light irradiation are investigated in order to discriminate the contribution of CdS from self-sensitized degradation of dyes. The degradation eciencies, as shown in Fig. 4b, for TG-1, TG-2 and TG-3 are 53%, 63% and 57%, respectively. Therefore, the large contribution of CdS can be obviously observed from the enhanced degradation eciencies of CdSTiO2RGO composites as compared with TiO2RGO composites. Fig. 4c shows the degradation results of MO under visible light irradiation in the presence of pure CdS and CdSRGO composites. The degradation eciencies for pure CdS, CG-1, CG-2 and CG-3 are 30%, 43%, 48% and 40%, respectively. Although CdS can absorb the visible-light radiant energy,64 CdS nanoparticles are easily aggregated in aqueous solution during the preparation process, which accordingly results in their rather lower eciency.65 As is expected, an enhanced photocatalysis of the CdSRGO composite is observed, which is attributed to migration of photo-induced electrons from the CdS conduction band to RGO. However, compared to CdS TiO2RGO composites, anity between CdSRGO and dye may decrease, thus aecting the photooxidation reaction rate.66

4. Conclusions
CdSTiO2RGO composites synthesized via microwaveassisted reduction of GO in CdS precursor solution with TiO2 suspension show much improved eciency for photocatalytic degradation of MO. In the composites, CdS extends the absorption of TiO2 from the UV region to visible light range while RGO increases the specic surface areas of the composites and facilitates the charge transportation and separation. The results of photocatalytic experiments indicate that (i) CdSTiO2RGO composites exhibit a better photocatalytic performance than the pure TiO2, CdSTiO2 composites and TiO2RGO composites; (ii) the photocatalytic performance of CdSTiO2RGO is dependent on the proportion of RGO in the composites and the composite with 2.82% RGO achieves a highest MO degradation eciency of 99.5%; (iii) the enhanced photocatalytic performance is ascribed to the increase
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Fig. 4 Photocatalytic degradation of MO by (a) TiO2, CTG-0, CTG-1, CTG-2, CTG-3, CTG-4 and CTG-5, (b) TiO2, TG-1, TG-2 and TG-3, (c) CdS, CG-1, CG-2 and CG-3 under visible light irradiation.

is further increased above its optimum value, the photocatalytic performance deteriorates. This deterioration should be due to the following possible reasons: (i) the excessive RGO can act as a kind of recombination center instead of providing an electron pathway;31,61,62 (ii) RGO simply lters light and decreases the number of charge carriers in the composite to be photogenerated. Because both CdS excitation and self-sensitized degradation of dyes contribute to the photocatalytic performance in this
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of specic surface area for more adsorbed MO and the reduction of photoelectronhole pair recombination with the introduction of RGO.

Acknowledgements
Financial support from Special Project for Nanotechnology of Shanghai (No. 1052nm02700) and the Key laboratory of new ceramics and ne processes at Tsinghua University is gratefully acknowledged.
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Notes and references

1 C. T. Chen, J. Q. Kao, C. Y. Liu and L. Y. Jiang, Catal. Sci. Technol., 2011, 1, 54. 2 R. Guttel, M. Paul and F. Schuth, Catal. Sci. Technol., 2011, 1, 65. 3 C. C. Ou, C. S. Yang and S. H. Lin, Catal. Sci. Technol., 2011, 1, 295. 4 M. Zarezade, S. Ghasemi and M. R. Gholami, Catal. Sci. Technol., 2011, 1, 279. 5 J. Shang, M. Chai and Y. F. Zhu, J. Solid State Chem., 2003, 174, 104. 6 J. Zhang, Y. P. Zhang, Y. K. Lei and C. X. Pan, Catal. Sci. Technol., 2011, 1, 273. 7 Y. Xie, G. Ali, S. H. Yoo and S. O. Cho, ACS Appl. Mater. Interfaces, 2010, 2, 2910. 8 J. Bai, J. Li, Y. Liu, B. Zhou and W. Cai, Appl. Catal., B, 2010, 95, 408. 9 S. C. Hayden, N. K. Allam and M. A. El-Sayed, J. Am. Chem. Soc., 2010, 132, 14406. 10 A. H. Zyoud, N. Zaatar, I. Saadeddin, C. Ali, D. Park, G. Campet and H. S. Hilal, J. Hazard. Mater., 2010, 173, 318. 11 G. Zhu, F. F. Su, T. Lv, L. K. Pan and Z. Sun, Nanoscale Res. Lett., 2010, 5, 1749. 12 W. Zhao, Z. Bai, A. Ren, B. Guo and C. Wu, Appl. Surf. Sci., 2010, 256, 3493. 13 B. Huang, Y. Yang, X. Chen and D. Ye, Catal. Commun., 2010, 11, 844. 14 W. Lee, J. Lee, S. Lee, W. Yi, S. H. Han and B. W. Cho, Appl. Phys. Lett., 2008, 92, 153510. 15 V. Daskalaki, M. Antoniadou, G. L. Puma, D. I. Kondarides and P. Lianos, Environ. Sci. Technol., 2010, 44, 7200. 16 H. Park, W. Choi and M. R. Homann, J. Mater. Chem., 2008, 18, 2379. 17 Q. Kang, Q. Z. Lu, S. H. Liu, L. X. Yang, L. F. Wen, S. L. Luo and Q. Y. Cai, Biomaterials, 2010, 31, 3317. 18 T. N. Lambert, C. A. Chavez, B. Hernandez-Sanchez, P. Lu, N. S. Bell, A. Ambrosini, T. Friedman, T. J. Boyle, D. R. Wheeler and D. L. Huber, J. Phys. Chem. C, 2009, 113, 19812. 19 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov, Science, 2004, 306, 666. 20 M. Pumera, Energy Environ. Sci., 2011, 4, 668. 21 T. Lu, Y. P. Zhang, H. B. Li, L. K. Pan, Y. L. Li and Z. Sun, Electrochim. Acta, 2010, 55, 4170. 22 H. B. Li, T. Lu, L. K. Pan, Y. P. Zhang and Z. Sun, J. Mater. Chem., 2009, 19, 6773. 23 W. T. Zheng and C. Q. Sun, Energy Environ. Sci., 2011, 4, 627. 24 W. T. Zheng, Y. M. Ho, H. W. Tian, M. Wen, J. L. Qi and Y. A. Li, J. Phys. Chem. C, 2009, 113, 9164. 25 P. Wang, Y. Zhai, D. Wang and S. Dong, Nanoscale, 2011, 3, 1640. 26 H. Zhang, X. Lv, Y. Li, Y. Wang and J. Li, ACS Nano, 2010, 4, 380. 27 Y. J. Wang, R. Shi, J. Lin and Y. F. Zhu, Appl. Catal., B, 2010, 100, 179.

28 K. Zhou, Y. Zhu, X. Yang, X. Jiang and C. Li, New J. Chem., 2011, 35, 353. 29 Y. Zhang and C. Pan, J. Mater. Sci., 2011, 46, 2622. 30 J. Liu, H. Bai, Y. Wang, Z. Liu, X. Zhang and D. D. Sun, Adv. Funct. Mater., 2010, 20, 4175. 31 G. Zhu, T. Xu, T. Lv, L. K. Pan, Q. Zhao and Z. Sun, J. Electroanal. Chem., 2011, 650, 248. 32 H. B. Li, W. Zhang, L. Zou, L. K. Pan and Z. Sun, J. Mater. Res., 2011, 26, 970. 33 S. Horikoshi, H. Abe, K. Torigoe, M. Abe and N. Serpone, Nanoscale, 2010, 2, 1441. 34 X. J. Liu, L. K. Pan, T. Lv, T. Lu, G. Zhu, Z. Sun and C. Q. Sun, Catal. Sci. Technol., 2011, 1, 1189. 35 G. Zhu, L. K. Pan, T. Xu, Q. Zhao, B. Lu and Z. Sun, Nanoscale, 2011, 3, 2188. 36 T. Lu, L. K. Pan, H. B. Li, G. Zhu, T. Lv, X. J. Liu, Z. Sun, T. Chen and D. H. C. Chua, J. Alloys Compd., 2011, 509, 5488. 37 G. Zhu, L. K. Pan, T. Xu and Z. Sun, ACS Appl. Mater. Interfaces, 2011, 3, 1472. 38 W. Chen, L. Yan and P. R. Bangal, Carbon, 2010, 48, 1146. 39 A. V. Murugan, T. Muraliganth and A. Manthiram, Chem. Mater., 2009, 21, 5004. 40 B. G. Choi, H. Park, M. H. Yang, Y. M. Jung, S. Y. Lee, W. H. Hong and T. J. Park, Nanoscale, 2010, 2, 2692. 41 R. M. Nirmal, K. Pandian and K. Sivakumar, Appl. Surf. Sci., 2011, 257, 2745. 42 Y. Liu, T. Tan, B. Wang, R. Zhai, X. Song, E. Li, H. Wang and H. Yan, J. Colloid Interface Sci., 2008, 320, 540. 43 A. L. Wangshington and G. F. Strouse, Chem. Mater., 2009, 21, 3586. 44 S. M. Wang, L. Qing, B. Xie, J. Wu and Y. T. Qian, Mater. Chem. Phys., 2002, 78, 288. 45 H. B. Li, L. K. Pan, T. Lu, Y. K. Zhan, C. Y. Nie and Z. Sun, J. Electroanal. Chem., 2011, 653, 40. 46 H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao and Y. Chen, ACS Nano, 2008, 2, 463. 47 S. Kundu, H. Lee and H. Liang, Inorg. Chem., 2009, 48, 121. 48 Y. P. Zhang and C. X. Pan, J. Mater. Sci., 2011, 46, 2622. 49 L. Tang, Y. Wang, Y. Li, H. Feng, J. Lu and J. Li, Adv. Funct. Mater., 2009, 19, 2782. 50 Y. L. Chen, Z. A. Hu, Y. Q. Chang, H. W. Wang, Z. Y. Zhang, Y. Y. Yang and H. Y. Wu, J. Phys. Chem. C, 2011, 115, 2563. 51 J. L. Wu, X. P. Shen, L. Jiang, K. Wang and K. M. Chen, Appl. Surf. Sci., 2010, 256, 2826. 52 X. Wang, L. J. Zhi, N. Tsao, J. L. Tomovic and K. Mullen, Angew. Chem., Int. Ed., 2008, 47, 2990. 53 T. G. Xu, L. W. Zhang, H. Y. Cheng and Y. F. Zhu, Chem. Rev., 2010, 101, 382. 54 Y. Miyake and H. Tada, J. Chem. Eng. Jpn., 2004, 37, 630. 55 Y. P. Zhang and C. X. Pan, J. Mater. Sci., 2011, 46, 2622. 56 D. Zhao, C. Chen, Y. Wang, W. Ma, J. Zhao, T. Rajh and L. Zang, Environ. Sci. Technol., 2008, 42, 308. 57 H. Park and W. Choi, J. Phys. Chem. B, 2004, 108, 4086. 58 M. Gra tzel, Nature, 2001, 414, 338. 59 Y. L. Lee and Y. S. Lo, Adv. Funct. Mater., 2009, 19, 604. 60 R. Czerw, B. Foley, D. Tekleab, A. Rubio, P. M. Ajayan and D. L. Carroll, Phys. Rev. B: Condens. Matter, 2002, 66, 033408. 61 N. Yang, J. Zhai, D. Wang, Y. S. Chen and L. Jiang, ACS Nano, 2010, 4, 887. 62 X. Y. Zhang, H. P. Li, X. L. Cui and Y. Lin, J. Mater. Chem., 2010, 20, 2801. 63 B. J. Li and H. Q. Cao, J. Mater. Chem., 2011, 21, 3346. 64 J. Y. Wang, Z. H. Liu, Q. Zheng, Z. K. He and R. X. Cai, Nanotechnology, 2006, 17, 4561. 65 H. Y. Zhu, R. Jianga, L. Xiao, Y. H. Chang, Y. J. Guan, X. D. Li and G. M. Zeng, J. Hazard. Mater., 2009, 169, 933. 66 J. C. Tristao, F. Magalhaes, P. Corio and M. C. Sansiviero, J. Photochem. Photobiol., A, 2006, 181, 152.

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