N, Co共掺杂锐钛矿相TiO2光催化剂的第一性原理研究

张学军; 张光富; 金辉霞; 朱良迪; 柳清菊

doi:10.7498/aps.62.017102

摘要

采用第一性原理平面波超软赝势方法研究了N, Co共掺杂锐钛矿相TiO2的微观结构和光学性质.结果表明: N, Co共掺杂后TiO2晶格中产生的偶极矩使光生电子-空穴对更有效地分离; 在TiO2导带和价带之间形成了新的杂质能级, 一方面使吸收带边红移到可见光区, 光吸收性能明显增强, 另一方面有利于光生电子-空穴对的分离, 提高TiO2的光量子效率; 与纯TiO2相比, N, Co共掺杂锐钛矿相TiO2带边的氧化还原势只有微小的变化, 共掺杂后TiO2的强氧化还原能力得以保持.

关键词:

Abstract

The microstructures and optical properties of N and Co-codoped anatase TiO2 are investigated by using the plane-wave ultrasoft pesudopotential method of first-principles. The calculated results show that the octahedral dipole moment of anatase TiO2 increases after N and Co codoping, which is favorable for effective separation of photogenerated electron-hole pairs. Some new impurity energy levels of codoped TiO2 appear between the conduction band and the valence band, which results in the red shift of the absorption wavelength toward visible-light region and an apparent increase in performance of light absorption. These impurity energy levels can promote the effective separation of photogenerated electron-hole pairs, which facilitates the improvement of the photocatalytic efficiency of codoped TiO2. The band edge redox potential of codoped TiO2 is only slightly changed compared with that of pure TiO2, which means that the strong redox capacity of codoping photocatalyst is still excellent.

Keywords:

作者及机构信息

1.
湖南城市学院通信与电子工程学院, 益阳 413000;

2.
云南大学云南省高校纳米材料与技术重点实验室, 昆明 650091

基金项目: 国家自然科学基金(批准号: 50862009, 51062017)和湖南省科技计划项目(批准号: 2011FJ3174)资助的课题.

Authors and contacts

1.
School of Communication and Electronic Engineering, Hunan City University, Yiyang 413000, China;

2.
Key Laboratory of Nanomaterials and Nanotechnology of Yunnan Province, Yunnan University, Kunming 650091, China

Funds: Project supported by the Nation Natural Science Foundation of China (Grant Nos. 50862009, 51062017) and Hunan Provincial Science and Technology Project, China (Grant No. 2011FJ3174).

参考文献

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施引文献

[1]	Arconada N, Castro Y, Durán A 2010 Appl. Catal. A: Gen. 385 101
[2]	Vougioukalakis G, Stergiopoulos T, Kantonis G, Kontos A, Papadopoulos K, Stublla A, Potvin P, Falaras P 2010 J. Photochem. Photobiol. A: Chem. 214 22
[3]	Zhang Y W, Yin C H, Zhao Q, Li F Q, Zhu S S, Liu H S 2012 Acta Phys. Sin. 61 027801 (in Chinese) [张永伟, 殷春浩, 赵强, 李富强, 朱姗姗, 刘海顺 2012 61 027801]
[4]	Yu J X, Fu M, Ji G F, Chen X R 2009 Chin. Phys. B 18 269
[5]	Lin F, Zheng F W, Ouyang F P 2009 Acta Phys. Sin. 58 193 (in Chinese) [林峰, 郑法伟, 欧阳方平2009 58 193]
[6]	Xu L, Tang C Q, Qian J 2010 Acta Phys. Sin. 59 2721 (in Chinese) [徐凌, 唐超群, 钱俊 2010 59 2721]
[7]	Zhu L, Xie J S, Cui X L, Shen J, Yang X L, Zhang Z J 2010 Vacuum 84 797
[8]	Zhang R S, Liu Y, Teng F, Song C L, Han G R 2012 Acta Phys. Sin. 61 017101 (in Chinese) [章瑞铄, 刘涌, 滕繁, 宋晨路, 韩高荣2012 61 017101]
[9]	Liu Y, Wang H Q, Wu Z B 2007 J. Environ. Sci. 19 1505
[10]	Sato S 1986 Chem. Phys. Lett. 123 126
[11]	Asahi R, Morikawa T, Ohwaki T, Aoki O K, Taga Y 2001 Science 293 269
[12]	Kang I C, Zhang Q W, Yin S, Sato T, Saito F 2008 Environ. Sci. Technol. 42 3622
[13]	Di Valentin C, Finazzi E, Pacchioni G, Selloni A, Livraghi S, Paganini M C, Giamello E 2007 Chem. Phys. 339 44
[14]	Zhang X, Hu Y, Gong Q, Wei C H 2010 Chem. Ind. Eng. Prog. 29 1071 (in Chinese) [张霞, 胡芸, 龚倩, 韦朝海 2010化工进展 29 1071]
[15]	Chen S F, Liu W, Zhang S J, Chen Y H 2010 J. Sol.-Gel. Sci. Technol. 54 258
[16]	Liu X H, He X B, Fu Y B 2008 Acta Chim. Sin. 66 1725 [刘秀华, 何小波, 傅依备 2008 化学学报 66 1725]
[17]	Sun Y B, Zhang X Q, Li G K, Yang H T, Cheng Z H 2012 Acta Phys. Sin. 61 027503 (in Chinese) [孙运斌, 张向群, 李国科, 杨海涛, 成昭华 2012 61 027503]
[18]	Yan S, Huang Q D, Liu J D, Yuan Y Z, Liao D W 2011 Acta Phys. Chim. Sin. 27 2406 (in Chinese) [闫石, 黄勤栋, 林敬东, 袁友珠, 廖代伟 2011 物理化学学报 27 2406]
[19]	Shi J Y, Leng W H, Cheng X F, Zhang Z, Zhang J Q, Cao C N 2007 Chin. J. Nonferrous Met. 171536 (in Chinese) [施晶莹, 冷文华, 程小芳, 张昭, 张鉴清, 曹楚南 2007 中国有色金属学报 17 1536]
[20]	Yu H L, Zhao X, Xia Z 2009 Petrochem. Tech. 38 1331 (in Chinese) [愈慧丽, 赵鑫, 夏志 2009 石油化工 38 1331]
[21]	Segall M D, Lindan P J D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phys. Cond. Matt. 14 2717
[22]	Ceperley D M, Alder B J 1980 Phys. Rev. Lett. 45 566
[23]	Perdew J P, Zunger A 1981 Phys. Rev. B 23 5048
[24]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[25]	Zhang X J, Gao P, Liu Q J 2010 Acta Phys. Sin. 59 4930 (in Chinese) [张学军, 高攀, 柳清菊2010 59 4930]
[26]	Zhang X J, Liu Q J, Deng S G, Chen J, Gao P 2010 Acta Phys. Sin. 60 087103 (in Chinese) [张学军, 柳清菊, 邓曙光, 陈娟, 高攀 2011 60 087103]
[27]	Gao P, Wu J, Liu Q J, Zhou W F 2010 Chin. Phys. B 19 087103
[28]	Sato J, Kobayashi H, Inoue Y 2003 J. Phys. Chem. B 107 7970
[29]	Zhang Z Y, Han P D, Zhang C L, Zhang X, Sun X L, Li Y P 2012 Acta Phys. Chim. Sin. 28 324 (in Chinese) [张治宇, 韩培德, 张彩丽, 张雪, 孙向雷, 李玉平 2012 物理化学学报 28 324]
[30]	Gai Y Q, Li J B, Li A S, Xia J B, Wei S H 2009 Phys. Rev. Lett. 102 036402
[31]	Long R, Niall J 2009 Appl. Phys. Lett. 94 132102
[32]	Ma X G, Jiang J J, Liang P 2008 Acta Phys. Sin. 57 3120 (in Chinese) [马新国, 江建军, 梁培2008 57 3120]
[33]	Ma X G, Miao L, Bie S W, Jiang J J 2010 Solid State Commun. 150 689
[34]	Tang J, Durrant J R, Klug D R 2008 J. Am. Chem. Soc. 130 1388
[35]	Yu H F, Zhang Z W, Hu F C 2008 J. Alloys Compd. 465 484
[36]	Tang J W, Ye J H 2005 Chem. Phys. Lett. 410 104

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