Citation: SU Ya-Ling, LI Yi, DU Ying-Xun, LEI Le-Cheng. Visible-Light-Driven Catalytic Properties and First-Principles Study of Fluorine-Doped TiO₂ Nanotubes[J]. Acta Physico-Chimica Sinica, ;2011, 27(04): 939-945. doi: 10.3866/PKU.WHXB20110401 shu

Visible-Light-Driven Catalytic Properties and First-Principles Study of Fluorine-Doped TiO₂ Nanotubes

SU Ya-Ling ^1,2, ,
LI Yi ³ ,
DU Ying-Xun ¹ ,
LEI Le-Cheng ^2,

1.
1. Nanjing Institute of Geography & Limnology, State Key Laboratory of Lake Science and Environment, Chinese Academy of Sciences, Nanjing 210008, P. R. China;
2. Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310028, P. R. China;
3. State Key Laboratory of Hydrology-Water Resources and Hydraulic Engineering, College of Environmental Science and Engineering, Hohai University, Nanjing 210098, P. R. China

Received Date: 1 November 2010
Available Online: 24 February 2011
Fund Project: 河海大学水文水资源与水利工程科学国家重点实验室开放研究基金(2009490911)与国家自然科学青年基金(20906097)资助项目 (2009490911)与国家自然科学青年基金(20906097)

Improving the photocatalytic activity and the utilization of visible light of TiO₂ is the most important research topics in the photocatalytic field. To improve the photocatalytic activity of TiO₂, we used chemical vapor deposition (CVD) to dope TiO₂ nanotubes with fluorine. Scanning electron microscopy (SEM) images showed that the annealing temperature significantly affected the morphological integrity of TiO₂ nanotubes. Upon annealing at 550 and 700 °C, the structure of F-doped TiO₂ nanotubes suffered from an observable disintegration of morphological integrity. X-ray diffraction (XRD) results indicated that the F impurity retarded the anatase-rutile phase transition. Fluorine was successfully doped into TiO₂ by CVD, as indicated by the X-ray photoelectron spectroscopy (XPS) results. F-doped TiO₂ nanotubes showed higher photocatalytic activity. First-principles calculations suggested that the F 2p states were located in the lower-energy range of valence band (VB) and less mixed with O 2p states. It thus contributed little to the reduction of the optical band gap. This is consistent with the finding that the band gap of F-doped TiO₂ is very close to that of undoped TiO₂. Therefore, the higher catalytic activity of F-doped TiO₂ should be attributed to the creation of surface oxygen vacancies upon F-doping, which enhances surface acidity and increases the amount of Ti³⁺ ions.
- TiO₂ nanotubes,
- Fluorine-doping,
- Visible-light,
- Catalytic property,
- Electronic structure
1. [1]
  
  (1) Fujishima, A.; Rao, T. N.; Tryk, D. A. J. Photochem. Photobiol. C: Photochem. 2000, 1, 1.
2. [2]
  (2) Linsebigler, A. L.; Lu, G. Q.; Yates, T., Jr. Chem. Rev. 1995, 95, 735.
3. [3]
  (3) Asahi, R.; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y. Science 2001, 293, 269.
4. [4]
  (4) Mokawa, T.; Asahi, R.; Ohwaki, T.; Aoki, K.; Taga, Y. Jpn. J. Appl. Phys. 2001, 40, 561.
5. [5]
  (5) Irie, H.; Watanabe, Y.; Hashimoto, K. J. Phys. Chem. B 2003, 107, 5483.
6. [6]
  (6) Khan, S. U. M.; Al-shahry, M.; Ingler, W. B., Jr. Science 2002, 297, 2243.
7. [7]
  (7) Irie, H.; Watanabe, Y.; Hashimoto, K. Chem. Lett. 1998, 32, 772.
8. [8]
  (8) Umebayashi, T.; Yamaki, T.; Tanaka, S.; Asai, K. Chem. Lett. 2003, 32, 330.
9. [9]
  (9) Ohno, T.; Mitsui, T.; Matsumura, M. Chem. Lett. 2003, 32, 364.
10. [10]
  (10) Hong, X. T.; Wang, Z. P.; Cai, W. M.; Lu, F.; Zhang, J.; Yang, Y. Z.; Ma, N.; Liu, Y. J. Chem. Mater. 2005, 17, 1548.
11. [11]
  (11) Song, S.; Tu, J. J.; Xu, L. J.; Xu, X.; He, Z. Q.; Qiu, J. P.; Ni, J. G.; Chen, J. M. Chemosphere 2008, 73, 1401.
12. [12]
  (12) Yu, J. C.; Yu, J. G.; Ho, W. K.; Jiang, Z. T.; Zhang, L. Z. Chem. Mater. 2002, 14, 3808.
13. [13]
  (13) Li, D.; Haneda, H.; Hishita, S.; Kolodiazhnyi T.; Haneda, H. J. Solid State Chem. 2005, 178, 3293.
14. [14]
  (14) Li, D.; Haneda, H.; Hishita, S.; Ohashi,N.; Labhsetwar, N. K. J. Fluorine Chem. 2005, 126, 69.
15. [15]
  (15) Huang, D. G.; Liao, S. J.; Liu, J. M.; Dang, Z.; Patrik, L. J. Photochem. Photobiol. A 2006, 184, 282.
16. [16]
  (16) Tang, J.; Quan, H.; Ye, J. Chem. Mater. 2007, 19, 116.
17. [17]
  (17) Varghese, O. K.; ng, D.; Paulose, M.; Grimes, C. A.; Dickey, E. C. J. Mater. Res. 2003, 18, 156.
18. [18]
  (18) Quan, X.; Yang, S. G.; Ruan, X. L.; Zhao, H. M. Environ. Sci. Technol. 2005, 39, 3770.
19. [19]
  (19) Hahn, R.; Macak, J. M.; Schmuki, P. Electrochem. Commun. 2007, 9, 947.
20. [20]
  (20) Macak, J. M.; Tsuchiya, H.; Schmuki, P. Angew Chem. Int. Edit. 2005, 44, 2100.
21. [21]
  (21) Ghicov, A.; Tsuchiya, H.; Macak, J. M.; Schmuki, P. Electrochem. Commun. 2005, 7, 505.
22. [22]
  (22) Taveira, L. V.; Macak, J. M.; Tsuchiya, H.; Dick, L. P.; Schmuki, P. J. Electrochem. Soc. 2005, 152, B405.
23. [23]
  (23) Macak, J. M.; Sirotna, K.; Schmuki, P. Electrochim. Acta 2005, 50, 3679.
24. [24]
  (24) Cai, Q. Y.; Paulose, M.; Varghese, O. K.; Grimes, C. A. J Mater. Res. 2005, 20, 230.
25. [25]
  (25) Macak, J. M.; Tsuchiya, H.; Taveira, L.; Aldabergerova S.; Schmuki, P. Angew Chem. Int. Edit. 2005, 44, 7463.
26. [26]
  (26) Vitiello, R. P.; Macak, J. M.; Ghicov, A.; Tsuchiya, H.; Dick L. F. P.; Schmuki, P. Electrochem. Commun. 2006, 8, 544.
27. [27]
  (27) Zlamal, M.; Macak, J. M.; Schmuki, P.; Krysa, J. Electrochem. Commun. 2007, 9, 2822.
28. [28]
  (28) Zhuang, H. F.; Lin, C. J.; Lai, Y. K.; Sun, L.; Li, J. Environ. Sci. Technol. 2007, 41, 4735.
29. [29]
  (29) Ghicov, A.; Macak, J. M.; Tsuchiya, H.; Kunze, J.; Haeublein, V.; Kleber, S.; Schmuki, P. Chem. Phys. Lett. 2006, 419, 426.
30. [30]
  (30) Ghicov, A.; Macak, J. M.; Tsuchiya, H.; Kunze, J.; Haeublein, V.; Frey, L.; Schmuki, P. Nano. Lett. 2006, 6, 1080.
31. [31]
  (31) Giovanni, A.; Battiston, G. A.; Gerbasi, R.; Porchia, M.; Man , A. Thin Solid Films 1994, 239, 186.
32. [32]
  (32) Yu, J. C.; Ho, W. K.; Yu, J. G.; Hark, S. K.; Iu, K. Langmuir 2003, 19, 3889.
33. [33]
  (33) Segall, M. D.; Lindan, P. J. D.; Probert, M. J.; Pickard, C. J.; Hasnip, P. J.; Clark, S. J.; Payne, M. C. J. Phys. Condens. Mat. 2002, 14, 2717.
34. [34]
  (34) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.
35. [35]
  (35) Lin, J.; Yu, J. C. J. Photochem. Photobiol. A: Chem. 1998, 116, 63.
36. [36]
  (36) Minero, C.; Mariella, G.; Maurino, V.; Vione, D.; Pelizzetti, E. Langmuir 2000, 16, 8964.
37. [37]
  (37) Minero, C.; Mariella, G.; Maurino, V.; Pelizzetti, E. Langmuir 2000, 16, 2632.
38. [38]
  (38) Lei, Y.; Zhang, L. D.; Meng, G. W.; Li, G. H.; Zhang, X. Y.; Liang, C. H.; Chen, W.; Wang, S. X. Appl. Phys. Lett. 2001, 78, 1125.
39. [39]
  (39) Sanjinés, R.; Tang, H.; Berger, H.; zzo, F.; Margaritondo, G.; Lévy, F. J. Appl. Phys. 1994, 75, 2945.
40. [40]
  (40) Bendavid, A.; Martin, P. J.; Jamting, A.; Takikawa, H. Thin Solid Films 1999, 355-356, 6.
41. [41]
  (41) Chang, H. J.; Kong, K. J.; Choi, Y. S.; In, E. J.; Choi, Y. M.; Baeg, J. O.; Moon, S. J. Chem. Phys. Lett. 2004, 398, 449.
42. [42]
  (42) Zhao, J. X.; Dai, B. Q. Mater. Chem. Phys. 2004, 88, 244.
43. [43]
  (43) Yang, K. S.; Dai, Y.; Huang, B. B., Whangbo, M. H. Chem. Mater. 2008, 20, 6528.
44. [44]
  (44) Argaman, N.; Mako, G. Am. J. Phys. 2000, 68, 69.
1. [1]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
2. [2]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
3. [3]
  Xinzhe HUANG , Lihui XU , Yue YANG , Liming WANG , Zhangyong LIU , Zhongjian WANG . Preparation and visible light responsive photocatalytic properties of BiSbO₄/BiOBr. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 284-292. doi: 10.11862/CJIC.20240212
4. [4]
  Qin Li , Huihui Zhang , Huajun Gu , Yuanyuan Cui , Ruihua Gao , Wei-Lin Dai . In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2025, 41(4): 100031-. doi: 10.3866/PKU.WHXB202402016
5. [5]
  Junqing WEN , Ruoqi WANG , Jianmin ZHANG . Regulation of photocatalytic hydrogen production performance in GaN/ZnO heterojunction through doping with Li and Au. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 923-938. doi: 10.11862/CJIC.20240243
6. [6]
  Yurong Tang , Yunren Shi , Yi Xu , Bo Qin , Yanqin Xu , Yunfei Cai . Innovative Experiment and Course Transformation Practice of Visible-Light-Mediated Photocatalytic Synthesis of Isoquinolinone. University Chemistry, 2024, 39(5): 296-306. doi: 10.3866/PKU.DXHX202311087
7. [7]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
8. [8]
  Hailang JIA , Hongcheng LI , Pengcheng JI , Yang TENG , Mingyun GUAN . Preparation and performance of N-doped carbon nanotubes composite Co₃O₄ as oxygen reduction reaction electrocatalysts. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 693-700. doi: 10.11862/CJIC.20230402
9. [9]
  Xueqi Yang , Juntao Zhao , Jiawei Ye , Desen Zhou , Tingmin Di , Jun Zhang . Modulating the d-band center of NNU-55(Fe) for enhanced CO₂ adsorption and photocatalytic activity. Acta Physico-Chimica Sinica, 2025, 41(7): 100074-. doi: 10.1016/j.actphy.2025.100074
10. [10]
  Xiufang Wang , Donglin Zhao , Kehua Zhang , Xiaojie Song . “Preparation of Carbon Nanotube/SnS₂ Photoanode Materials”: A Comprehensive University Chemistry Experiment. University Chemistry, 2024, 39(4): 157-162. doi: 10.3866/PKU.DXHX202308025
11. [11]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
12. [12]
  Jie Li , Huida Qian , Deyang Pan , Wenjing Wang , Daliang Zhu , Zhongxue Fang . Efficient Synthesis of Anethaldehyde Induced by Visible Light. University Chemistry, 2024, 39(4): 343-350. doi: 10.3866/PKU.DXHX202310076
13. [13]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015
14. [14]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
15. [15]
  Zhenming Xu , Mingbo Zheng , Zhenhui Liu , Duo Chen , Qingsheng Liu . Experimental Design of Project-Driven Teaching in Computational Materials Science: First-Principles Calculations of the LiFePO₄ Cathode Material for Lithium-Ion Batteries. University Chemistry, 2024, 39(4): 140-148. doi: 10.3866/PKU.DXHX202307022
16. [16]
  Shenhao QIU , Qingquan XIAO , Huazhu TANG , Quan XIE . First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2250-2258. doi: 10.11862/CJIC.20240104
17. [17]
  Zhihao HE , Jiafu DING , Yunjie WANG , Xin SU . First-principles study on the structure-property relationship of AlX and InX (X=N, P, As, Sb). Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1007-1019. doi: 10.11862/CJIC.20240390
18. [18]
  Yu Wang , Haiyang Shi , Zihan Chen , Feng Chen , Ping Wang , Xuefei Wang . Hollow AgPt@Pt core-shell cocatalyst with electron-rich Pt^δ^- shell for boosting selectivity of photocatalytic H₂O₂ production for faceted BiVO₄. Acta Physico-Chimica Sinica, 2025, 41(7): 100081-. doi: 10.1016/j.actphy.2025.100081
19. [19]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
20. [20]
  Xinyu Miao , Hao Yang , Jie He , Jing Wang , Zhiliang Jin . Adjusting the electronic structure of Keggin-type polyoxometalates to construct S-scheme heterojunction for photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(6): 100051-. doi: 10.1016/j.actphy.2025.100051

Get Citation

PDF

XML

Metrics

PDF Downloads(1740)
Abstract views(3071)
HTML views(4)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Visible-Light-Driven Catalytic Properties and First-Principles Study of Fluorine-Doped TiO2 Nanotubes

Metrics

通讯作者: 陈斌, bchen63@163.com

Visible-Light-Driven Catalytic Properties and First-Principles Study of Fluorine-Doped TiO₂ Nanotubes