La-Ce-Codoping Nano-Titania Photocatalyst: Preparation Via Microwave-Assisted Sol Process, Spectroscopy Characterization and Photocatalytic Activity
GUO Li1, WANG Dan-jun1, LI Dong-sheng1*, FU Feng1, PU Yong1, YAN Hong-tao2
1. College of Chemistry & Chemical Engineering, Yan’an University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan’an 716000, China 2. Department of Chemistry, Northwest University, Xi’an 710069, China
Abstract：La-Ce codoping nano-TiO2 catalyst was prepared by microwave-assisted sol process with TBT and distilled water as forerunner body, ethanol as solvent and glacial acetic acid as inhibitor. The prepared samples were characterized by using XRD, XPS and UV-Vis techniques. Results of structural characterization indicated that the prepared samples were all pure anatase phase nano-TiO2 and their diffraction peak broadened obviously after La and Ce doping. Results of XPS analysis revealed that La—O bond existed in the samples and many oxygen vacancies were produced on the surface of TiO2 nanoparticles after La and Ce codoping. UV-Vis absorption spectra demonstrated that the prepared samples had strong and wide absorption band between 200 and 400 nm and the absorption intensity increased after La and Ce doping because of La(Ⅲ)—O charge-transfer transition, Ce(Ⅳ) f→d transition and Ce(Ⅳ)—O charge-transfer transition. Photocatalytic experiment results showed that the titanium dioxide’s photocatalytic activity increased obviously after La and Ce codoping. The optimal parameters for the preparation were obtained by adjusting the mole ratio of La and Ce in photocatalysts. When the doping amount of La and Ce was 2% and 0.04% respectively, the prepared sample exhibited high photocatalytic activity, the decoloration ratio of methyl orange solution was above 90%, and COD removal of cigarette factory wastewater was 86.11%.
Key words：Nano-titanium dioxide;La-Ce-codoping;Microwave-assisted sol process;Photocatalytic activity
[1] Fujihira M, Satoh Y, Osa T. Bull. Chem. Soc. of Japan, 1982, 55: 666. [2] Jonathan R, Stromberg, Joshua D, et al. Nano Lett., 2006, 6: 1284. [3] Gouvea C A K, Wypych F, Moraes S G, et al. Chemosphere, 2000, 40: 433. [4] Byrne J A, Eggins B R, Brown N M D. et al. Appl. Catal. B: Environ., 1998, 17(1-2): 25. [5] Chen J, Ollis D F, Rulkens W H, et al. Water Res., 1999, 33: 669. [6] Linkous C A, Carter G, Locuson D B, et al. Environ. Sci. & Technol., 2000, 34: 4754. [7] Konstantinou I K, Sakellarides T M, Sakkas V A, et al. Environ. Sci. & Technol., 2001, 35: 398. [8] Weng C C, Chen C P, Ting C H, et al. J. Chem. Mater., 2005, 17: 3328. [9] ZHONG Chao-yang, PAN Hai-bo, GUO Long-fa, et al(钟超阳，潘海波，郭龙发，等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2007, 27(11): 2329. [10] ZHENG Huai-li, ZHANG Jun-hua, LI Hong, et al(郑怀礼, 张峻华, 李 宏, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2005, 25(12): 2065. [11] Premkumar J. Chem. Mater., 2004, 16: 3980. [12] Zhao Wei, Ma Wanhong, Chen Chuncheng, et al. J. Am. Chem. Soc., 2004, 126: 4782. [13] HE Chao, YU Yun, Andre LARBOT, et al(何 超, 于 云，Andre LARBOT, 等). Journal of Inorganic Materials(无机材料学报), 2003, 18(2): 457. [14] ZHANG Jun-ping, WANG Yan, QI Hui-xin(张俊平, 王 艳, 戚慧心). Journal of Chinese Rare Earth Society(中国稀土学报), 2002, 20(5): 478. [15] Lin J, Yu J C. J. Photochem. & Photobiol. A: Chem., 1998, 116: 63. [16] Galema S A. Chem. Rev., 1997, 97: 233. [17] Cao H L, Gong Q, Qian X F, et al. Crystal Growth & Design, 2007, 7: 425. [18] Zhang X H, Xie S Y, Jiang Z Y, et al. J. Phys. Chem. B, 2003, 107: 10114. [19] LIU Xin, LIU Fu-tian, ZHANG Ning, et al(刘 鑫, 刘福田, 张 宁, 等). Journal of Ceramics(陶瓷学报), 2007, 28(2): 104. [20] XI Dan-li, SUN Yu-sheng, LIU Xiu-ying(奚旦立, 孙裕生, 刘秀英). Environmental Monitoring(环境监测, 修订版). Beijing: Higher Education Press(北京: 高等教育出版社), 1995. [21] Zachariasen W H. Theory of X-ray Diffraction in Crystals. New York: John Wiley & Sons Ins, 1945. [22] Li F B, Li X Z, Hou M F, et al. Appl. Cata. A, 2005, 285: 181. [23] Wagner C, Muilnberg G. Handbook of X-Ray Photoelectron Spectroscopy. Eden Prairie: Perkin-Elmer Corporation, 1979, 68. [24] Signorelli A J, Hayes R G. Phys. Rev. B, 1973, 8: 81. [25] Dai H X, Ng C F, Au C T. J. Catal., 2001, 199: 177. [26] Jason F W, Car B H. J. Phys. Chem., 1994, 98: 8519. [27] Hammond J S, Garenstroom S W, Winograd N. Anal. Chem., 1975, 42: 2193. [28] Bukhtiyarow V I, Kaichev V V, Prosvirin I P. J. Chem. Phys., 1999, 111: 2169. [29] Natile M M, Glisenti A. Chem. Mater., 2003, 15: 2502. [30] Ding Z，Zhu H Y, Greenfiele P F, et al. Journal of Colloid & Interface Science, 2001, 238: 267. [31] Hua Z L, Shi J L, Zhang W H, et al. Mater. Lett., 2002, 53(4-5): 299. [32] Jing H, Guo Z Y, Ma H, et al. Journal of Catalysis, 2002, 212: 22. [33] Claude B, Ahmed B, Claude L J. J. Phys. Chem., 1994, 98: 6392. [34] CHEN En-wei, YIN Dong-hong, SONG Hui-juan, et al(陈恩伟, 银董红, 宋慧娟, 等). Chinese Journal of Catalysis(催化学报), 2006, 27(4): 344. [35] WU Yu-cheng, CHEN Ting-song, XIE Ting, et al(吴玉程, 陈挺松, 解 挺, 等). Journal of Functional Materials(功能材料), 2005, 36(1): 124. [36] Litter M I. Appl. Catal. B, 1999, 23(2-3): 89.
