Please wait a minute...
Acta Phys. Chim. Sin.  2014, Vol. 30 Issue (7): 1318-1324    DOI: 10.3866/PKU.WHXB201404222
CATALYSIS AND SURFACE SCIENCE     
Performance, Deactivation and Regeneration of SnO2/TiO2 Nanotube Composite Photocatalysts
ZHAO Wei-Rong, SHI Qiao-Meng, LIU Ying
Department of Environmental Engineering, Zhejiang University, Hangzhou 310058, P. R. China
Download:   PDF(765KB) Export: BibTeX | EndNote (RIS)      

Abstract  

SnO2/TiO2 nanotube composite photocatalysts were synthesized by microwave-assisted hydrothermal and micro-emulsion methods. The photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy with energy-dispersive X-ray spectroscopy (TEM/EDX), and electrochemical techniques. Toluene was chosen as a model pollutant to evaluate the performance, deactivation, and regeneration behavior of the photocatalysts under ultraviolet (UV) and vacuum ultraviolet (VUV) irradiation. The results show that ternary heterojunctions of SnO2/TiO2 nanotube composite photocatalysts including anatase TiO2 (A-TiO2)/rutile TiO2 (R-TiO2), A-TiO2/SnO2, and R-TiO2/SnO2 were successfully created. They were able to separate photogenerated electron-hole pairs efficiently, and promote photocatalytic activity accordingly. SnO2/TiO2 showed the best photocatalytic performance. Under UV or VUV irradiation, the toluene degradation rate of SnO2/TiO2 was 100%, and the CO2 formation rate (k2) of SnO2/TiO2 was approximately 3 times higher than that of P25. Because of the low mineralization rate under UV irradiation, the refractory intermediates generated can occupy active photocatalytic sites on the photocatalyst surface, which hinders the photocatalytic oxidation rate. After 20 h of UV irradiation, the k2 of SnO2/TiO2 decreased from 138.5 to 76.1 mg·m-3·h-1, implying that the photocatalysts can be deactivated quickly. VUV irradiation was employed to regenerate the deactivated SnO2/SnO2/TiO2 nanotube composite photocatalysts were synthesized by microwave-assisted hydrothermal and micro-emulsion methods. The photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy with energy-dispersive X-ray spectroscopy (TEM/EDX), and electrochemical techniques. Toluene was chosen as a model pollutant to evaluate the performance, deactivation, and regeneration behavior of the photocatalysts under ultraviolet (UV) and vacuum ultraviolet (VUV) irradiation. The results show that ternary heterojunctions of SnO2/TiO2 nanotube composite photocatalysts including anatase TiO2 (A-TiO2)/rutile TiO2 (R-TiO2), A-TiO2/SnO2, and R-TiO2/SnO2 were successfully created. They were able to separate photogenerated electron-hole pairs efficiently, and promote photocatalytic activity accordingly. SnO2/TiO2 showed the best photocatalytic performance. Under UV or VUV irradiation, the toluene degradation rate of SnO2/TiO2 was 100%, and the CO2 formation rate (k2) of SnO2/TiO2 was approximately 3 times higher than that of P25. Because of the low mineralization rate under UV irradiation, the refractory intermediates generated can occupy active photocatalytic sites on the photocatalyst surface, which hinders the photocatalytic oxidation rate. After 20 h of UV irradiation, the k2 of SnO2/TiO2 decreased from 138.5 to 76.1 mg·m-3·h-1, implying that the photocatalysts can be deactivated quickly. VUV irradiation was employed to regenerate the deactivated SnO2/TiO2 because reactive species such as ·OH, O2, O(1D), O(3P), and O3 can be generated. These play an important role in the oxidation of refractory intermediates on the photocatalyst surface, and k2 increased to 143.6 mg·m-3·h-1 accordingly. Therefore, UV photodegradation combined with VUV regeneration could be a feasible photocatalytic process because of a synergistic effect between UV and VUV.



Key wordsHeterojunction      Vacuum ultraviolet      Toluene      Electron-hole pair      Photocatalytic activity     
Received: 26 January 2014      Published: 22 April 2014
MSC2000:  O643  
Fund:  

The project was supported by the National Natural Science Foundation of China (51178412, 51278456) and National Key Technologies R&D Program of China (2013BAC16B01).

Corresponding Authors: ZHAO Wei-Rong     E-mail: weirong@mail.hz.zj.cn
Cite this article:

ZHAO Wei-Rong, SHI Qiao-Meng, LIU Ying. Performance, Deactivation and Regeneration of SnO2/TiO2 Nanotube Composite Photocatalysts. Acta Phys. Chim. Sin., 2014, 30(7): 1318-1324.

URL:

http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/10.3866/PKU.WHXB201404222     OR     http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/Y2014/V30/I7/1318

(1) Wang, C. H.; Shao, C. L.; Zhang, X. T.; Liu, Y. C. Inorg. Chem. 2009, 48, 7261. doi: 10.1021/ic9005983
(2) Chang, S. Y.; Chen, S. F.; Huang, Y. C. J. Phys. Chem. C 2011, 115, 1600. doi: 10.1021/jp109103a
(3) Zhou, X. F.; Cao, J. L.; Xu, M. F.;Wang, Z. S.; Lu, J. Mater. Res. Bull. 2013, 48, 4942. doi: 10.1016/j.materresbull. 2013.07.031
(4) Wu, L.; Xing, J.; Hou, Y.; Xiao, F. Y.; Li, Z.; Yang, H. G. Chem. Eur. J. 2013, 19, 8688. doi: 10.1002/chem.201390096
(5) Smith,W.;Wolcott, A.; Fitzmorris, R. C.; Zhang, J. Z.; Zhao, Y. P. J. Mater. Chem. 2011, 21, 10792. doi: 10.1039/c1jm11629k
(6) Su, C. Y.; Shao, C. L.; Liu, Y. C. J. Colloid Interface Sci. 2010, 346, 324. doi: 10.1016/j.jcis.2010.02.027
(7) Wu, Z. Y.; Zhao, G. H.; Zhang, Y. N.; Tian, H. Y.; Li, D. M. J. Phys. Chem. C 2012, 116, 12829. doi: 10.1021/jp300374s
(8) Chaguetmi, S.; Mammeri, F.; Nowak, S.; Decorse, P.; Lecoq, H.; Gaceur, M.; Naceur, J. B.; Achour, S.; Chtourou, R.; Ammar, S. RSC Adv. 2013, 3, 2572. doi: 10.1039/c2ra21684a
(9) Jovi, F.; Tomaši, V.; Davidson, A.; Nogier, J. P.; Li,W.; Kosar, V. Chem. Biochem. Eng. Q. 2013, 27, 37.
(10) Mo, J. H.; Zhang, Y. P.; Xu, Q. J.; Lamson, J. J.; Zhao, R. Y. Atmos. Environ. 2009, 43, 2229. doi: 10.1016/j.atmosenv.2009.01.034
(11) Jeong, J. Y.; Sekiguchi, K.; Sakamoto, K. Chemosphere 2004, 57, 663. doi: 10.1016/j.chemosphere.2004.05.037
(12) Huang, H. B.; Leung, D. Y. C.; Li, G. S.; Leung, M. K. H.; Fu, X. L. Catal. Today 2011, 175, 310. doi: 10.1016/j.cattod.2011.04.015
(13) Zhao,W. R.; Yang, Y. N.; Dai, J. S.; Liu, F. F.;Wang, Y. Chemosphere 2013, 91, 1002. doi: 10.1016/j.chemosphere.2013.01.086
(14) Chen, S. H.; Xu, Y.; Lu, B. L.;Wu, D. Acta Phys. -Chim. Sin. 2011, 27, 2933. [陈淑海, 徐耀, 吕宝亮, 吴东. 物理化学学报, 2011, 27, 2933.]
(15) Ou, H. H.; Lo, S. L.; Liao, C. H. J. Phys. Chem. C 2011, 115, 4000. doi: 10.1021/jp1076005
(16) Zhang, H.; Li, G. R.; An, L. P.; Yan, T. Y.; Gao, X. P.; Zhu, H. Y. J. Phys. Chem. C 2007, 111, 6143. doi:10.1021/jp0702595
(17) Zhao,W. R.;Wang, Y.; Yang, Y. N.; Tang, J.; Yang, Y. Appl. Catal. B: Environ. 2012, 115, 90.
(18) Dong, L. F.; Gari, R. R. S.; Li, Z.; Craig, M. M.; Hou, S. F. Carbon 2010, 48, 781. doi: 10.1016/j.carbon.2009.10.027
(19) Tang, Z. R.; Li, F.; Zhang, Y. H.; Fu, X. Z.; Xu, Y. J. J. Phys. Chem. C 2011, 115, 7880. doi: 10.1021/jp1115838
(20) Debono, O.; Thevenet, F.; Gravejat, P.; Hequet, V.; Raillard, C.; Lecoq, L. Appl. Catal. B: Environ. 2011, 106, 600. doi: 10.1016/j.apcatb.2011.06.021
(21) Jankulovska, M.; Berger, T.; Lana-Villarreal, T.; Gómez, R. Electrochim. Acta 2012, 62, 172. doi: 10.1016/j.electacta.2011.12.016
(22) Komaguchi, K.; Nakano, H.; Araki, A.; Harima, Y. Chem. Phys. Lett. 2006, 428, 338. doi: 10.1016/j.cplett.2006.07.003
(23) Xing, M. Y.; Zhang, J. L.; Chen, F.; Tian, B. Z. Chem. Commun. 2011, 47, 4947. doi: 10.1039/c1cc10537j
(24) Zhao, L.; Ran, J. R.; Shu, Z.; Dai, G. T.; Zhai, P. C.;Wang, S. M. Int. J. Photoenergy 2012, 2012, 1. doi: 10.1155/2012/472958
(25) Huang, H. B.; Li,W. B. Appl. Catal. B: Environ. 2011, 102, 449. doi: 10.1016/j.apcatb.2010.12.025
(26) Zhao,W. R.; Dai, J. S.; Liu, F. F.; Bao, J. Z.;Wang, Y.; Yang, Y.; Yang, Y. N.; Zhao, D. Y. Sci. Total Environ. 2012, 438, 201. doi: 10.1016/j.scitotenv.2012.08.081

[1] ZHANG Chi, WU Zhi-Jiao, LIU Jian-Jun, PIAO Ling-Yu. Preparation of MoS2/TiO2 Composite Catalyst and Its Photocatalytic Hydrogen Production Activity under UV Irradiation[J]. Acta Phys. Chim. Sin., 2017, 33(7): 1492-1498.
[2] CHEN Xin, HU Shao-Zheng, LI Ping, LI Wei, MA Hong-Fei, LU Guang. Photocatalytic Production of Hydrogen Peroxide Using g-C3N4 Coated MgO-Al2O3-Fe2O3 Heterojunction Catalysts Prepared by a Novel Molten Salt-Assisted Microwave Process[J]. Acta Phys. Chim. Sin., 2017, 33(12): 2532-2541.
[3] BI Hui-Zi, DOU Rong-Fei, WANG Hao, PEI Yan, QIAO Ming-Hua, SUN Bin, ZONG Bao-Ning. Effect of the Support on Partial Hydrogenation of Toluene over Ru/Oxide Catalysts[J]. Acta Phys. Chim. Sin., 2016, 32(7): 1765-1774.
[4] LIU Zhao-Xin, LI Wei-Bin. Catalytic Activity and Deactivation of Toluene Combustion on Rod-Like Copper-Manganese Mixed Oxides[J]. Acta Phys. Chim. Sin., 2016, 32(7): 1795-1800.
[5] TANG Wei, WANG Jing. Enhanced Gas Sensing Mechanisms of Metal Oxide Heterojunction Gas Sensors[J]. Acta Phys. Chim. Sin., 2016, 32(5): 1087-1104.
[6] WANG Yan-Juan, SUN Jia-Yao, FENG Rui-Jiang, ZHANG Jian. Preparation of Ternary Metal Sulfide/g-C3N4 Heterojunction Catalysts and Their Photocatalytic Activity under Visible Light[J]. Acta Phys. Chim. Sin., 2016, 32(3): 728-736.
[7] QIAO Zhi, XIE Xin-Jian, XUE Jun-Ming, LIU Hui, LIANG Li-Min, HAO Qiu-Yan, LIU Cai-Chi. Optimization of Intrinsic Silicon Passivation Layers in nc-Si:H/c-Si Silicon Heterojunction Solar Cells[J]. Acta Phys. Chim. Sin., 2015, 31(6): 1207-1214.
[8] LI Xian-Hua, ZHANG Lei-Gang, WANG Xue-Xue, YU Qing-Bo. PANI/g-C3N4 Composites Synthesized by Interfacial Polymerization and Their Thermal Stability and Photocatalytic Activity[J]. Acta Phys. Chim. Sin., 2015, 31(4): 764-770.
[9] YU Jian-Hua, FAN Min-Guang, LI Bin, DONG Li-Hui, ZHANG Fei-Yue. Preparation and Photocatalytic Activity of Mixed Phase TiO2-Graphene Composites[J]. Acta Phys. Chim. Sin., 2015, 31(3): 519-526.
[10] YU Chang-Lin, WEI Long-Fu, LI Jia-De, HE Hong-Bo, FANG Wen, ZHOU Wan-Qin. Preparation and Characterization of GO/Ag3PO4 Composite Photocatalyst and Its Visible Light Photocatalytic Performance[J]. Acta Phys. Chim. Sin., 2015, 31(10): 1932-1938.
[11] LIN Cai-Fang, CHEN Xiao-Ping, CHEN Shu, SHANGGUAN Wen-Feng. Preparation of NiS-Modified Cd1-xZnxS by a Hydrothermal Method and Its Use for the Efficient Photocatalytic H2 Evolution[J]. Acta Phys. Chim. Sin., 2015, 31(1): 153-158.
[12] WANG Li-Guo, ZHANG Xiao-Dan, WANG Feng-You, WANG Ning, JIANG Yuan-Jian, HAO Qiu-Yan, XU Sheng-Zhi, WEI Chang-Chun, ZHAO Ying. Influence of Different Pyramidal Structural Morphologies of Crystalline Silicon Wafers for Surface Passivation and Heterojunction Solar Cells[J]. Acta Phys. Chim. Sin., 2014, 30(9): 1758-1763.
[13] ZHANG Jian-Fang, WANG Yan, SHEN Tian-Kuo, SHU Xia, CUI Jie-Wu, CHEN Zhong, WU Yu-Cheng. Visible Light Photocatalytic Performance of Cu2O/TiO2 Nanotube Heterojunction Composites Prepared by Pulse Deposition[J]. Acta Phys. Chim. Sin., 2014, 30(8): 1535-1542.
[14] LI Yan-Rong, PEI Yi-Qiang, QIN Jing, ZHANG Miao. A Reaction Mechanismof Polycyclic Aromatic Hydrocarbons for Gasoline Surrogate Fuels TRF[J]. Acta Phys. Chim. Sin., 2014, 30(6): 1017-1026.
[15] AO Ping, XU Xiang-Sheng, XU Xiao-Xiao, LI Jia-Heng, YAN Xin-Huan. Low-Temperature Total Oxidation of Toluene over Assembled Pt/TiO2 Catalyst[J]. Acta Phys. Chim. Sin., 2014, 30(5): 950-956.