Modification of the photocatalytic properties of anatase TiO2 (101) surface by doping transition metals

Su Qiao-Zhi; Han Qing-Zhen; Gao Jin-Hua; Wen Hao; Jiang Zhao-Tan

doi:10.7498/aps.66.067101

Abstract

Exploring new types of photocatalysts and modifying the photocatalytic activity have attracted more and more extensive attention in many research fields. Anatase TiO2, a promising photocatalyst widely studied, can only absorb the ultraviolet light and thus only make little use of the power in visible light. Therefore, it is an urgent task to make theoretical and experimental investigations on the photocatalytic mechanism in anatase TiO2 and then improve its visible light response so as to utilize more visible light. Now, in the present paper, we carry out a systematic theoretical investigation on modifying the photocatalytic properties of the anatase TiO2 (101) surface via doping transition metal neutral atoms such as Fe, Ni, Pd, Pt, Cu, Ag, and Au by using the plane wave ultrasoft pseudopotential method of the density functional theory. The dependence of the macroscopic catalytic activity on electronic structure and optoelectronic property is uncovered by making a comparative analysis of the geometric structures, the electronic structures, and the optical properties of the undoped and doped anatase TiO2 (101) surfaces. Our numerical results show that doping certain transition metals can suppress the band gap or induce extra impurity energy levels, which is beneficial to improving the visible light response of the TiO2 (101) surface in different ways. In most cases, the new impurity energy levels will appear in the original band gap, which comes from the contribution of the d electronic states in the transition metal atoms. Moreover, the photocatalytic activity of the TiO2 (101) surface can be changed differently by doping different transition metal atoms, which is closely dependent on the bandgap width, Fermi energy, the impurity energy level, and the electron configuration of the outermost shell of the dopants. This research should be an instructive reference for designing TiO2 (101) photocatalyst and improving its capability, and also helpful for understanding doping transition metal atoms in other materials.

Keywords:

Authors and contacts

1.
School of Physics, Beijing Institute of Technology, Beijing 100081, China;
2.
State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Han Qing-Zhen, qzhan@ipe.ac.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11504374, 11274040) and the Innovation Program of Institute of Process Engineering Chinese Academy of Sciences (Grant No. COM2015A001).

References

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[21]	Wang Y, Zhang R, Li J, Li L, Lin S 2014 Nanoscale Res. Lett. 9 46
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[25]	Li Z B, Wang X, Fan S W 2014 Acta Sci. Nat. Univ. Sunyatseni 53 114 (in Chinese) [李宗宝, 王霞, 樊帅伟 2014 中山大学学报: 自然科学版 53 114]
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[27]	Ying Y, Feng Q, Wang W, Wang Y 2013 J. Semicond. 34 073004
[28]	Asahi R, Taga Y, Mannstadt W, Freeman A J 2000 Phys. Rev. B 61 7459
[29]	Zhao Z 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]
[30]	Zhao Z, Liu Q 2008 J. Phys. D: Appl. Phys. 41 085417
[31]	He C, Hu Y, Hu X, Larbot A 2002 Appl. Surf. Sci. 200 239
[32]	Yuan Y, Ding J, Xu J, Deng J, Guo J 2010 J. Nanosci. Nanotechnol. 10 4868
[33]	Sharma S D, Singh D, Saini K K, Kant C, Sharma V, Jain S C, Sharma C P 2006 Appl. Catal. A 314 40
[34]	Zhou M, Yu J, Cheng B 2006 J. Hazard. Mater. 137 1838
[35]	Li Z, Shen W, He W, Zu X 2008 J. Hazard. Mater. 155 590
[36]	Lin H J, Yang T S, Hsi C S, Wang M C, Lee K C 2014 Ceram. Int. 40 10633

Cited By

[1]	Fujishima A, Honda K 1972 Nature 238 37
[2]	Hoffmann M R, Martin S T, Choi W, Bahnemann D W 1995 Chem. Rev. 95 69
[3]	Wang R, Hashimoto K, Fujishima A, Chikuni M, Kojima E, Kitamura A, Shimohigoshi M, Watanabe T 1997 Nature 388 431
[4]	Huang X H, Tang Y C 2013 TiO2 Photocatalysis Technology and its Applications in the Field of Environment (Hefei: Hefei University of Technology Press) pp242-252 (in Chinese) [黄显怀, 唐玉朝 2013 TiO2光催化技术及其在环境领域的应用 (合肥: 合肥工业大学出版社) 第242252页]
[5]	Palmisano G, Augugliaro V, Pagliaro M, Palmisano L 2007 Chem. Commun. 33 3425
[6]	Ma H F, Wang X R, Ma F, Ding Y G, Wang Z 2013 Electr. Comp. Mater. 32 1 (in Chinese) [马洪芳, 王小蕊, 马芳, 丁严广, 王振 2013 电子元件与材料 32 1]
[7]	Wang R, Hashimoto K, Fujishima A, Chikuni M, Kojima E, Kitamura A, Shimohigoshi M, Watanabe T 1998 Adv. Mater. 10 135
[8]	Li X Z, Li F B, Yang C L, Ge W K 2001 J. Photochem. Photobiol. A 141 209
[9]	Choi W, Termin A, Hoffmann M R 1994 J. Phys. Chem. 98 13669
[10]	Yu X B, Wang G H, Luo Y Q, Chen X H, Zhu J 2000 J. Shanghai Norm. Univ. Nat. Sci. 29 75 (in Chinese) [余锡宾, 王桂华, 罗衍庆, 陈秀红, 朱建 2000 上海师范大学学报 29 75]
[11]	Wu S X, Ma Z, Qin Y N, Qi X Z, Liang Z C 2004 Acta Phys.-Chim. Sin. 20 138 (in Chinese) [吴树新, 马智, 秦永宁, 齐晓周, 梁珍成 2004 物理化学学报 20 138]
[12]	Wang Y, Hao Y, Cheng H, Ma J, Xu B, Li W, Cai S 1999 J. Mater. Sci. Mater. Electron. 34 2773
[13]	Huang P, Shang B, Li L, Lei J 2015 Chin. J. Chem. Phys. 28 681
[14]	Samat M H, Hussin N H, Taib M F M, Yaakob M K, Samsi N S, Aziz S S S A, Yahya M Z A, Ali A M M 2016 Mater. Sci. Forum. 846 726
[15]	Li C, Zheng Y J, Fu S N, Jiang H W, Wang D 2016 Acta Phys. Sin. 65 037102 (in Chinese) [李聪, 郑友进, 付斯年, 姜宏伟, 王丹 2016 物理学报 65 037102]
[16]	Diebold U 2003 Surf. Sci. Rep. 48 53
[17]	Lazzeri M, Vittadini A, Selloni A 2001 Phys. Rev. B 63 155409
[18]	Lazzeri M, Vittadini A, Selloni A 2002 Phys. Rev. B 65 119901
[19]	Chen Z H, Fang X M, Zhang Z G 2013 Chem. Ind. Eng. Prog. 32 1320 (in Chinese) [陈志鸿, 方晓明, 张正国 2013 化工进展 32 1320]
[20]	Keiji W, Masatoshi S, Hideaki T 1999 J. Electroanal Chem. 473 250
[21]	Wang Y, Zhang R, Li J, Li L, Lin S 2014 Nanoscale Res. Lett. 9 46
[22]	Burdett J K, Hughbanks T, Miller G J, Richardson J W, Smith J V 1987 J. Am. Chem. Soc. 109 3639
[23]	John P P, Mel L 1983 Phys. Rev. Lett. 51 1884
[24]	Ma X G, Tang C Q, Huang J Q, Hu L F, Xue X, Zhou W B 2006 Acta Phys. Sin. 55 4208 (in Chinese) [马新国, 唐超群, 黄金球, 胡连峰, 薛霞, 周文斌 2006 物理学报 55 4208]
[25]	Li Z B, Wang X, Fan S W 2014 Acta Sci. Nat. Univ. Sunyatseni 53 114 (in Chinese) [李宗宝, 王霞, 樊帅伟 2014 中山大学学报: 自然科学版 53 114]
[26]	Boschloo G K, Goossens A, Schoonman J 1997 J. Electrochem. Soc. 144 1311
[27]	Ying Y, Feng Q, Wang W, Wang Y 2013 J. Semicond. 34 073004
[28]	Asahi R, Taga Y, Mannstadt W, Freeman A J 2000 Phys. Rev. B 61 7459
[29]	Zhao Z 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]
[30]	Zhao Z, Liu Q 2008 J. Phys. D: Appl. Phys. 41 085417
[31]	He C, Hu Y, Hu X, Larbot A 2002 Appl. Surf. Sci. 200 239
[32]	Yuan Y, Ding J, Xu J, Deng J, Guo J 2010 J. Nanosci. Nanotechnol. 10 4868
[33]	Sharma S D, Singh D, Saini K K, Kant C, Sharma V, Jain S C, Sharma C P 2006 Appl. Catal. A 314 40
[34]	Zhou M, Yu J, Cheng B 2006 J. Hazard. Mater. 137 1838
[35]	Li Z, Shen W, He W, Zu X 2008 J. Hazard. Mater. 155 590
[36]	Lin H J, Yang T S, Hsi C S, Wang M C, Lee K C 2014 Ceram. Int. 40 10633

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Vol. 66, Issue 6 - 2017-03-20

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