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Acta Phys. -Chim. Sin.  2011, Vol. 27 Issue (05): 1149-1156    DOI: 10.3866/PKU.WHXB20110520
Preparation of F-Modified Nanosized TiO2 and Its Methyl Orange Photodegradation Mechanism
JIANG Jing-Jing, LONG Ming-Ce, WU De-Yong, CAI Wei-Min
School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China
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Fluorine-modified nanosized TiO2 (F-TiO2) was prepared by a facile precipitation-fluorination- reflux method. Characterizations of transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectroscopy (DRS) were carried out to investigate various properties of the as-prepared F-TiO2 powder. We found that the F-TiO2 particles were small (5-8 nm) and ellipsoidal in shape. The presence of fluorine not only suppressed the formation of a brookite phase, but also improved the crystallinity of the anatase phase. The fluorine atoms were mainly distributed on the surface of TiO2, and existed in both forms of chemical-adsorption and interstitial-doping. Compared to pure titania, the fluorine-modified TiO2 powder showed a much higher methyl orange (MO) degradation efficiency under UV light and under visible light. Through the experiments of alkaline washing and heat treatment, we found that the increased MO degradation rate under visible light irradiation was caused by the enhanced self- degradation of the dye over the surface-modified TiO2.

Key wordsFluorine-modification      Titanium dioxide      Reflux      Visible-light activity      Dye sensitization     
Received: 20 October 2010      Published: 08 April 2011
MSC2000:  O643  

The project was supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (20090073120042).

Corresponding Authors: LONG Ming-Ce     E-mail:
Cite this article:

JIANG Jing-Jing, LONG Ming-Ce, WU De-Yong, CAI Wei-Min. Preparation of F-Modified Nanosized TiO2 and Its Methyl Orange Photodegradation Mechanism. Acta Phys. -Chim. Sin., 2011, 27(05): 1149-1156.

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(1) Hoffmann, M. R.; Martin, S. T.; Choi, W.; Bahnemann, D. W. Chem. Rev. 1995, 95, 69.
(2) Xu, J. J.; Ao, Y. H.; Fu, D. G.; Yuan, C. W. Appl. Surf. Sci. 2008, 254, 3033.
(3) Tang, J. W.; Quan, H. D.; Ye, J. H. Chem. Mater. 2007, 19, 116.
(4) Li, J. Y.; Ma, J. H.; Bai, T. Y.; Suyou, L. M. Acta Phys.-Chim. Sin. 2007, 23, 1213.
[李静谊, 马俊华, 白图雅, 苏优乐玛. 物理化学学报, 2007, 23, 1213.]
(5) Li, D.; Ohashi, N.; Hishita, S.; Kolodiazhnyi, T.; Haneda, H. J. Solid State Chem. 2005, 178, 3293.
(6) Li, D.; Haneda, H.; Labhsetwar, N. K.; Hishita, S.; Ohashi, N. Chem. Phys. Lett. 2005, 401, 579.
(7) Ho, W.; Yu, J. C.; Lee, S. Chem. Commun. 2006, 1115.
(8) Ren, G.; Gao, Y.; Liu, X. ; Xing, A.; Liu, H.; Yin, J. Reac. Kinet. Mech. Cat. 2010, 100, 487.
(9) Wang, Q.; Chen, C.; Zhao, D.; Ma, W.; Zhao, J. Langmuir 2008, 24, 7338.
(10) Huang, D. G.; Liao, S. J.; Dang, Z. Acta Chim. Sin. 2006, 64, 1805.
[黄冬根, 廖世军, 党 志. 化学学报, 2006, 64, 1805.]
(11) Ren, D. S.; Cui, X. L.; Zhang, Q.; Yang, X. L.; Zhang, Z. J. Vac. Sci. Technol. (China) 2002, 22, 421.
[任达森, 崔晓莉, 张 群, 杨锡良, 章壮健. 真空科学与技术, 2002, 22, 421.]
(12) Park, H.; Choi, W. J. Phys. Chem. B, 2004, 108, 4086.
(13) Zhu, S. Y.; Huo, M. X.; Zhang, L. L.; Yu, Q.; Wang, T. Z. Science and Technology Review 2010, 28, 112.
[朱遂一, 霍明昕, 张蕾蕾, 于 琪, 王天竹. 科技导报, 2010, 28, 112.]
(14) Bezrodna, T.; Puchkovska, G.; Shimanovska, V.; Chashechnikova, I.; Khalyavka, T.; Baran, J. Appl. Surf. Sci. 2003, 214, 222.
(15) Hung, W. C.; Fu, S. H.; Tseng, J. J.; Chu, H.; Ko, T. H. Chemosphere 2007, 66, 2142.
(16) Su, H. D. Preparation and Photocatalytic Activity of Titanium Dioxide Photocatalyst. Ph. D. Dissertation, Northeastern University, Liaoning, 2005.
[苏会东. 二氧化钛光催化剂的制备及其性能研究
[D]. 辽宁: 东北大学, 2005.]
(17) Chen, Y. M.; Zhong, J.; Chen, F.; Zhang, J. L. Chin. J. Catal. 2010, 31, 120.
[陈艳敏, 钟 晶, 陈 锋, 张金龙. 催化学报, 2010, 31, 120.]
(18) Czoska, A. M.; Livraghi, S.; Chiesa, M.; Giamello, E.; Agnoli, S.; Granozzi, G.; Finazzi, E.; Di Valentin, C.; Pacchioni, G. J. Phys. Chem. C 2008, 112, 8951.
(19) Zhu, M. H. Instrumental Analysis, 3rd ed.; Higher Education Press: Beijing, 2000; p 275.
[朱明华. 仪器分析(第三版); 北京: 高等教育出版社, 2000: 275.]
(20) Yu, J. C.; Yu, J. G.; Ho, W.; Jiang, Z.; Zhang, L. Chem. Mater. 2002, 14, 3808.
(21) Liu, G.; Wu, T.; Zhao, J.; Hidaka, H.; Surpone, N. Environ. Sci. Technol. 1999, 33, 2081.
(22) Chen, C.; Zhao, W.; Li, J.; Zhao, J. C.; Hidaka, H.; Surpone, N. Environ. Sci. Technol. 2002, 36, 3604.
(23) Christine, M. D.; Joseph, R.; Jacques, J. V. Inorg. Chem. 1987, 26, 1212.
(24) Arichi, J.; Louis, B. Cryst. Growth Des. 2008, 8, 3999.
(25) Louis, B.; Lioubov K.-M. Microporous Mesoporous Mat. 2004, 74, 171.
(26) Minero, C.; Mariella, G.; Maurino, V.; Pelizzetti, E. Langmuir 2000, 16, 2632.
(27) Vohra, M.; Kim, S.; Choi, W. J. Photochem. Photobiol. A 2003, 160, 55.
(28) Morrison, S. R. Electrochemistry at Semiconductor and Oxidized Metal Electrodes; Plenum Press: New York, 1980; p 154.
(29) You, X. F.; Chen, F.; Zhang, J. L.; Huang, J. Z.; Zhang, L. Z. Chin. J. Catal. 2006, 27, 270.
[尤先锋, 陈 锋, 张金龙, 黄家桢, 张利中. 催化学报, 2006, 27, 270.]

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