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利用基于密度泛函理论的第一性原理对不同P掺杂形式(P替位Ti, P替位O, 间隙P)的锐钛矿相TiO2的晶格常数、电荷布居、能带结构、分态密度和吸收光谱进行了计算. 结果表明, P替位Ti时, TiO2体积减小, P替位O和间隙P的存在使TiO2的体积膨胀; 替位Ti的P和间隙P均有不同程度的氧化, 而替位O的P带有负电荷. 三种P掺杂形式均导致锐钛矿相TiO2禁带宽度的增大, 并在TiO2禁带之内引入了掺杂局域能级. P掺杂导致TiO2禁带宽度增大的程度依次为: 间隙P>P替位Ti>P替位O. 吸收光谱的计算结果表明, P替位Ti并不能增强TiO2的可见光吸收能力, 但间隙P的存在大幅提高了TiO2的可见光光吸收能力, 间隙P有可能是造成实验上P掺杂增强锐钛矿相TiO2光催化活性的重要原因.The lattice parameters, charge populations, band structures, density of states and absorption spectra of P-doped anatase TiO2 are calculated using the first-principles based on the density functional theory. The results indicate that when the Ti atom is substituted for P atom, the volume of TiO2 decreases. When P atom substitutes for O atom or exists as interstitial atom, the volume of TiO2 increases. The substitutional P at Ti site and interstitial P are oxidized to different degrees, and the substitutional P at O site is reduced a little. The different three sites of P doping result in the increase of anatase TiO2 forbidden gap width and the introduction of local doping energy levels. The band gap increasing of P-doped anatase TiO2 is in the following sequence: interstitial P>substitutional P at Ti site>substitutional P at O site. The absorption spectra indicate that the substitutional P at Ti site cannot enhance the visible light absorption ability of the anatase TiO2, whereas the interstitial P strongly enhances the visible light absorption ability of the anatase TiO2. The interstitial P is probably an important reason for the experimental enhancement of the photocatalytic activity of P-doped anatase TiO2.
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Keywords:
- P doping /
- anatase TiO2 /
- first-principles
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[1] Zhang Y, Tang C Q, Dai J 2005 Acta Phys. Sin. 54 323 (in Chinese) [张勇, 唐超群, 戴君 2005 54 323]
[2] Peng L P, Xia Z C, Yang C Q 2012 Acta Phys. Sin. 61 127104 (in Chinese) [彭丽萍, 夏正才, 杨昌权 2012 61 127104]
[3] Wu G H, Zheng S K, Liu L, Jia C J 2012 Acta Phys. Sin. 61 223101 (in Chinese) [吴国浩, 郑树凯, 刘磊, 贾长江 2012 61 223101]
[4] Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y 2001 Science 293 269
[5] Hamadanian M, Reisi-Vanani A, Behpour M, Esmaeily A S 2011 Desalination 281 319
[6] Hamadanian M, Reisi-Vanani A, Majedi A 2010 Appl. Surf. Sci. 256 1837
[7] Wang X K, Wang C, Jiang W J, Guo W L, Wang J G 2012 Chem. Eng. J. 189-190 288
[8] Parayil S K, Kibombo H S, Wu C M, Peng R, Baltrusaitis J, Koodali R T 2012 Inter. J. Hydrogen Energy 37 8257
[9] Lin L, Lin W, Xie J L, Zhu Y X, Zhao B Y, Xie Y C 2007 Appl. Catal. B: Environ. 75 52
[10] Lv Y Y, Yu L S, Zhang X L, Yao J Y, Zou R Y, Dai Z 2011 Appl. Surf. Sci. 257 5715
[11] Jin C, Qiu S C, Zhu Y X, Xie Y C 2011 Chin. J. Catal. 32 1173
[12] Asapu R, Palla V M, Wang B, Guo Z H, Sadu R, Chen D H 2011 J. Photochem. Photobio. A: Chem. 225 81
[13] Shi Q, Yang D, Jiang Z Y, Li J 2006 J. Mol. Catal. B: Enzym. 43 44
[14] Zheng R Y, Lin L, Xie J L, Zhu Y X, Xie Y C 2008 J. Phys. Chem. C 112 15502
[15] Yu H F 2007 J. Phys. Chem. Solids 68 600
[16] Xu L, Tang C Q, Qian J, Huang Z B 2010 Appl. Surf. Sci. 256 2668
[17] Sato J, Kobayashi H, Inoue Y 2003 J. Phys. Chem. B 107 7970
[18] Peng Y H, He J F, Liu Q H, Sun Z H, Yan W S, Pan Z Y, Wu Y F, Liang S Z, Chen W R, Wei S Q 2011 J. Phys. Chem. C 115 8184
[19] Lin L, Lin W, Zhu Y X, Zhao B Y, Xie Y C 2005 Chem. Lett. 34 284
[20] Nakahira A, Konishi K, Yokota K, Honma T, Aritani H, Tanaka K 2006 J. Ceram. Soc. Jpn. 114 46
[21] Baunack S, Oswald S, Scharnweber D 1998 Surf. Interface Anal. 26 471
[22] Körsi L, Dékány I 2006 Colloid Surf. A: Physicochem. Eng. Asp. 280 146
[23] Xiong S Y, Wang L, Dong Q M, Liang P 2012 Sci. China: Phys. Mech. Astron. 42 6 (in Chinese) [熊斯雨, 王乐, 董前民, 梁培 2012 中国科学: 物理学 力学 天文学 42 6]
[24] Zhang Y Y, Fu W Y, Yang H B, Liu S K, Sun P, Yuan M X, Ma D, Zhao W Y, Sui Y M, Li M H, Li Y X 2009 Thin Solid Films 518 99
[25] Lv Y Y, Yu L S, Huang H Y, Liu H L, Feng Y Y 2009 J. Alloys Compd. 488 314
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