Cu-Ag协同表面改性TiO2的第一性原理研究

李宗宝; 王霞; 周瑞雪; 王应; 李勇

doi:10.7498/aps.66.117101

摘要

因在温室气体的降解中扮演重要的角色，通过改性来提高二氧化钛的光催化性能的相关研究备受关注.由于催化反应主要发生在材料表面，因此对材料表面的改性研究尤为重要.本文采用第一性原理方法计算了金属Ag，Cu单掺杂及协同掺杂TiO2（001）和（101）表面不同位置，通过形成能的比较获得了最稳定的晶体结构.通过对能带及态密度的对比得出：离子掺杂（001）表面所形成的活性基团的氧化性较（101）面更强，利于光催化氧化性能的提升；表面协同掺杂较单掺杂具有更强的光响应效率，与前人的实验结果符合较好.

关键词:

Abstract

The photocatalytic properties of TiO2 improved by modifying its surface have attracted more and more attention, because they play an important role in the photocatalytic degradation of greenhouse gases. Based on the fact that the photocatalytic reactions main occur on the catalyst surface, the surface modification becomes an effective method to improve the photocatalyst properties while the reaction mechanism research can give us a clear picture about it. Using the first principle calculations, the formation energies of TiO2 are calculated with doped and codoped by Cu and Ag atoms at different positions of the (001) and (101) surfaces. Comparing the formation energies, the most stable crystal structures are obtained while the electronic structures are calculated. Based on the analysis of the band structures and the density of states of atoms, it is proved that the oxidation activity of the active group formed on the (001) surface is stronger than that on (101) surface, which is more conducive to the improvement of photocatalytic oxidation properties. Meanwhile, the TiO2 compounds codoped by bimetal on the two surfaces have better light response than doped by one species of ions, which is in good agreement with the former experimental results.

Keywords:

作者及机构信息

1.
铜仁学院材料与化学工程学院, 铜仁 554300;

2.
华南师范大学物理与电信工程学院, 广州 510006;

3.
铜仁学院大数据学院, 铜仁 554300

通信作者: 王霞, wxmj1215@126.com

基金项目: 贵州省自然科学基金（批准号：黔科合基础[2016]1150，黔科合LH 字[2015]7232号，黔科合LH 字[2015]7233号）资助的课题.

Authors and contacts

1.
School of Material and Chemical Engineering, Tongren University, Tongren 554300, China;

2.
School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006, China;

3.
School of Big Data, Tongren University, Guizhou 554300, China

Corresponding author: Wang Xia, wxmj1215@126.com

Funds: Project supported by the Natural Science Foundation of Guizhou Province, China (Grant Nos. [2016]1150, LH[2015]7232, LH[2015]7233).

参考文献

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[14]	Li Z B, Wang X, Jia L C, Xing X B 2017 Catal. Commun. 92 23
[15]	Kale M J, Avanesian T, Christopher P 2014 ACS Catal. 4 116
[16]	Park M S, Kang M 2008 Mater. Lett. 62 183
[17]	Park J W, Kang M 2007 Int J. Hydrog. Energy 32 4840
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[19]	Jaafar N F, Jalil A A, Triwahyono S 2017 Appl. Surf. Sci. 392 1068
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[22]	Taner M, Sayar N, Yulug I G, Suzer S 2011 J. Mater. Chem. 21 13150
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[24]	Kumar M K, Bhavani K, Naresh G, Srinivas B, Venugopal A 2016 Appl. Catal. B: Environ. 199 282
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施引文献

[1]	Wang P, Grtze M 2003 Nat. Mater. 21 402
[2]	Li Z B, Wang X, Jia L C, Chi B 2014 J. Mol. Str. 1061 160
[3]	Mills A, Hunte S L 1997 J. Photoch. Photobiol. A 8 1
[4]	Wang X J, Song J K, Huang J Y, Zhang J, Wang X, Ma R R, Wang J Y, Zhao J F 2016 Appl. Surf. Sci. 390 190
[5]	Li L, Zhuang H S, Bu D 2011 Appl. Surf. Sci. 257 9221
[6]	He Z Q, Hong T M, Chen J M, Song S 2012 Sep. Purif. Technol. 96 50
[7]	Wen J, Li X, Liu W, Fang Y, Xie J, Xu Y 2015 Chin. J. Catal. 36 2049
[8]	Larumbe S, Monge M, Gmez-Polo C 2015 Appl. Surf. Sci. 327 490
[9]	Yang G M, Liang Z C, Huang H H 2017 Acta Phys. Sin. 66 057301 (in Chinese) [杨光敏, 梁志聪, 黄海华 2017 66 057301]
[10]	Fang W, Zhou Y, Dong C, Xing M, Zhang J 2016 Catal. Today 266 188
[11]	Singh S A, Madras G 2016 Appl. Catal. A: General 518 102
[12]	Zhang X, Chen Y L, Liu R S, Tsai D P 2013 Rep. Prog. Phys. 76 046401
[13]	Busiakiewicz A, Kisielewska A, Piwoński I, Batory D 2017 Appl. Surf. Sci. 401 378
[14]	Li Z B, Wang X, Jia L C, Xing X B 2017 Catal. Commun. 92 23
[15]	Kale M J, Avanesian T, Christopher P 2014 ACS Catal. 4 116
[16]	Park M S, Kang M 2008 Mater. Lett. 62 183
[17]	Park J W, Kang M 2007 Int J. Hydrog. Energy 32 4840
[18]	Rather R A, Singh S, Pal B 2017 Sol. Energ. Mat. Sol. C 160 463
[19]	Jaafar N F, Jalil A A, Triwahyono S 2017 Appl. Surf. Sci. 392 1068
[20]	Bandara J, Udawatta C P K, Rajapakse C S K 2005 Photochem. Photobiol. Sci. 4 857
[21]	Ghorbani H R, Attar H, Soltani S 2015 Indian J. Appl. Pure Biol. 30 139
[22]	Taner M, Sayar N, Yulug I G, Suzer S 2011 J. Mater. Chem. 21 13150
[23]	Liu J, Chen F 2012 Int. J. Electrochem. Sci. 7 9560
[24]	Kumar M K, Bhavani K, Naresh G, Srinivas B, Venugopal A 2016 Appl. Catal. B: Environ. 199 282
[25]	Li Z B, Wang X, Fan S W 2014 Acta Phys. Sin. 63 157102 (in Chinese) [李宗宝, 王霞, 樊帅伟 2014 63 157102]
[26]	Kresse G, Hafner J 1993 Phys. Rev. B 47 558
[27]	Kresse G, Furthmuller J 1996 Phys. Rev. B 54 11169
[28]	Ernzerhof B K M, Perdew J P 1996 Phys. Rev. Lett. 77 3865
[29]	Jia L C, Wu C C, Han S, Yao N, Li Y Y, Li Z Z, Chi B, Pu J, Li J 2011 J. Alloy. Compd. 509 6067

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