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过渡金属(Fe,Co,Ni,Zn)掺杂金红石TiO2的电子结构和光学性质

张小超 赵丽军 樊彩梅 梁镇海 韩培德

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过渡金属(Fe,Co,Ni,Zn)掺杂金红石TiO2的电子结构和光学性质

张小超, 赵丽军, 樊彩梅, 梁镇海, 韩培德

Electronic structures and optical properties of transition metals (Fe, Co, Ni, Zn) doped rutile TiO2

Zhang Xiao-Chao, Zhao Li-Jun, Fan Cai-Mei, Liang Zhen-Hai, Han Pei-De
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  • 采用基于密度泛函理论的第一性原理方法对未掺杂以及不同浓度过渡金属Fe,Co,Ni,Zn掺杂金红石TiO2的超晶胞体系进行了几何优化,并讨论了其晶格常数,电子能带结构和光学性质.研究结果表明:掺杂前后的晶格参数与实验值偏差在3.6%以下;适量的过渡金属掺杂不但影响体系能带结构,拓宽光吸收范围,而且扮演着俘获电子的重要角色,有利于光生电子-空穴对的有效分离以及增强光吸收能力;Fe,Co,Ni,Zn最佳理论掺杂体系分别为Ti0.75Fe0.25O2,Ti0.75Co0.25O2,Ti0.75Ni0.25O2,Ti0.83Zn0.17O2;Fe,Co,Ni3d态分裂为t2g和eg态,分别贡献于价带高能级和导带低能级部分,促进了电子-空穴对的生成,从而可提高TiO2的光催化性能;Zn3d态电子成对填满轨道,不易被激发,故光催化活性无明显提高.
    The geometric structures of transition metals (Fe, Co, Ni and Zn) doped rutile TiO2 are studied using the first-principles method based on the density functional theory. The lattice parameters, the electronic energy band structure, and the optical properties are calculated and discussed. The results show that the errors between calculated and experimental values of lattice parameters are less than 3.6%. Appropriate dopants of transition metal ions not only influence the band structure of rutile TiO2 system and broaden the scope of light absorption, but also play an important role in trapping electrons, improving the effective separation of electronic-hole pair and enhancing light absorption ability. The optimum Fe, Co, Ni, Zn doped rutile TiO2 systems in theory are Ti0.75Fe0.25O2, Ti0.75Co0.25O2, Ti0.75Ni0.25O2, Ti0.17Zn0.17O2, respectively. The 3d orbits of Fe, Co, Ni split into two groups of energy bands, t2g and eg states contribute to the higher level of valence band and the lower level of conduction band, respectively, which is conducive to the generation of electronic-hole pair and the enhancement of photocatalytic performance of rutile TiO2. Zn 3d orbit is completely filled with electrons, and the electrons are hardly excited, so the photocatalytic activity of rutile TiO2 is not obviously improved.
    • 基金项目: 国家自然科学基金(批准号:20876104,20771080);山西省科技攻关项目(批准号:20090311082)资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 20876104, 20771080), and the Key Science and Technology Program of Shanxi Province, China (Grant No. 20090311082).
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    Wang X H, Li J G, Kamiyama H, Katada M, Ohashi N, Moriyoshi Y, Ishigaki T 2005 J. Am. Chem. Soc. 127 10982

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    Kim S, Gislason J J, Morton R W, Pan X Q, Sun H P, Laine R M 2004 Chem. Mater. 16 2336

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    Xu X G, Jiang Y, Yu G H, Liu Q L, Geng W T 2008 Phys. Lett. A372 2098

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    Geng W T, Kim K S 2003 Phys. Rev. B 68 125203

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    Chen Q L, Tang C Q 2006 J. Mater. Sci. Engin. 24 514 (in Chi-nese) [陈琦丽, 唐超群 2006 材料科学与工程学报 24 514]

  • [1]

    Fujishima A, Hond A K 1972 Nature 238 37

    [2]

    Khan S U M, Al-Shahry M, Ingler Jr W B 2002 Science 297 2243

    [3]

    Niishiro R, Kato H, Kuto A 2005 Phys. Chem. Chem. Phys. 7 2241

    [4]

    Wang J, Zhang G, Zhang Z H, Zhang X D, Zhao G, Wen F Y, Pan Z J, Li Y, Zhang P, Kang P L 2006 Water Res. 40 2143

    [5]

    Chen X B, Liu L, Yu P Y, Mao S S 2011 Science 331 746

    [6]

    Zhao J, Yang X 2003 Build. Environ. 38 645

    [7]

    O’Regan B, Grätzel M 1991 Nature 353 737

    [8]

    Bach U, Lupo D, Comte P, J. Moser E, Weissörtel F, Salbeck J, Spreitzer H, Grätzel M 1998 Nature 395 583

    [9]

    Burdett J K, Hughbanks T, Miller G J, Richardson Jr J W, Smith J V 1987 J. Am. Chem. Soc. 109 3639

    [10]

    Litter M I 1999 Appl. Catal. B: Environ. 23 89

    [11]

    Luan Y, Fu P F, Dai X G, Du Z W 2004 Prog. in Chem. 16 738(in Chinese) [栾勇, 傅平丰, 戴学刚, 杜竹玮 2004 化学进展 16 738]

    [12]

    Eslava S, McPartlin M, Thomson R I, Rawson J M, Wright D S 2010 Inorg. Chem. 49 11532

    [13]

    Melghit K, Al-Shukeili O S, Al-Amri I 2009 Ceram. Int. 35 433

    [14]

    Barakat M A, Schaeffer H, Hayes G, Ismat-Shah S 2004 Appl. Catal. B: Environ. 57 23

    [15]

    Uhm Y R, Woo S H, Kim W W, Kimb S J, Rhee C K 2006 J. Magn. Magn. Mater. 304 e781

    [16]

    Jing L Q, Xin B F, Yuan F L, Xue L P, Wang B Q, Fu H G 2006 J. Phys. Chem. B 110 17860

    [17]

    Liu G G, Zhang X Z, Xu Y J, Niu X S, Zheng L Q, Ding X J 2005 Chemosph. 59 1367

    [18]

    Choi W, Termin A, Hoffmann M R 1994 J. Phys. Chem. 98 13669

    [19]

    Gao G Y, Yao K L, Liu Z L 2006 Phys. Lett. A 359 523

    [20]

    Wendt S, Sprunger P T, Lira E, Madsen G K H, Li Z, Hansen J, Matthiesen J, Blekinge-Rasmussen A, L gsgaard E, Hammer B, Besenbacher F 2008 Science 320 1755

    [21]

    Zhang Z J, Meng D W, Wu X L, He K H, Fan X Y, Liu W P, Huang L W, Zheng J P 2011 Acta Phys. Sin. 60 037802 (in Chinese) [章正杰, 孟大维, 吴秀玲, 何开华, 樊孝玉, 刘卫平, 黄利武, 郑建平 2011 物理学报 60 037802]

    [22]

    Restori R, Schwarzenbach D, Schneider J R 1987 Acta Cryst. B 43 251

    [23]

    Hohenberg P, Kohn W 1964 Phys. Rev. 136 B864

    [24]

    Segall M D, Lindan P L D, Probert M J 2002 J. Phys. Condens. Matt. 14 2717

    [25]

    Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865

    [26]

    Monkhorst H J, Pack J D, Freeman D L 1979 Solid State Commun.29 723

    [27]

    Umebayashi T, Yamaki T, Itoh H, Asai K 2002 J. Phys. Chem. Solids 63 1909

    [28]

    Hossain F M, Murch G E, Sheppard L, Nowotny J 2007 Solid State Ionics 178 319

    [29]

    Bian L, Song M X, Zhou T L, Zhao X Y, Dai Q Q 2009 J. Rare Earths 27 461

    [30]

    Yu X H, Li C S, Tang A, Ling Y, Tang T A, Wu Q, Kong J J 2010 Comput. Mater. Sci. 49 430

    [31]

    Perdew J P 1983 Phys. Rev. Lett. 51 1884

    [32]

    Zhao X Y, Liu Q J, Zhang J, Zhu Z Q 2007 Acta Phys. Sin. 56 6592 (in Chinese) [赵宗彦, 柳清菊, 张瑾, 朱忠其 2007 物理学报 56 6592]

    [33]

    Baizaee S M, Mousavi N 2009 Physica B 404 2111

    [34]

    Karakitsou K E, Verykios X E 1993 Phys. Chem. 97 1184

    [35]

    Ding T, Liu Z F, Song K 2008 Prog. in Chem. 20 1283 (in Chi-nese) [丁涛, 刘占芳, 宋恺 2008 化学进展 20 1283]

    [36]

    Wantala K, Laokiat L, Khemthong P, Grisdanurak N, Fukaya K 2010 J. Taiwan Inst. Chem. Eng. 41 612

    [37]

    Wang X H, Li J G, Kamiyama H, Katada M, Ohashi N, Moriyoshi Y, Ishigaki T 2005 J. Am. Chem. Soc. 127 10982

    [38]

    Kim S, Gislason J J, Morton R W, Pan X Q, Sun H P, Laine R M 2004 Chem. Mater. 16 2336

    [39]

    Xu X G, Jiang Y, Yu G H, Liu Q L, Geng W T 2008 Phys. Lett. A372 2098

    [40]

    Geng W T, Kim K S 2003 Phys. Rev. B 68 125203

    [41]

    Chen Q L, Tang C Q 2006 J. Mater. Sci. Engin. 24 514 (in Chi-nese) [陈琦丽, 唐超群 2006 材料科学与工程学报 24 514]

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  • 收稿日期:  2011-05-12
  • 修回日期:  2012-04-05
  • 刊出日期:  2012-04-05

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