Pt和Au修饰锐钛矿型TiO2(101)面的第一性原理研究

doi:10.15541/jim20150362

无机材料学报 ›› 2016, Vol. 31 ›› Issue (3): 291-297.DOI: 10.15541/jim20150362 CSTR: 32189.14.10.15541/jim20150362

Pt和Au修饰锐钛矿型TiO₂(101)面的第一性原理研究

马新国^1,²(), 严杰¹, 陈紫梦¹, 祝林¹, 徐国旺^1,², 黄楚云^1,²(), 吕辉^1,²

1.湖北工业大学理学院, 武汉 430068
2.湖北工业大学太阳能高效利用湖北省协同创新中心, 武汉 430068

收稿日期:2015-08-10 修回日期:2015-09-16 出版日期:2016-03-20 网络出版日期:2016-02-24
作者简介:
马新国(1978-), 男, 博士, 副教授. E-mail: maxg2013@sohu.com
基金资助:
国家自然科学基金(51472081, 51102150, 61106046);湖北工业大学高层次人才启动基金(GCRC13014);湖北省协同创新中心开放基金(HBSKFMS2014003, HBSKFMS2014011);国家大学生创新创业训练计划(201410500012)

First-principles Calculation on Pt- and Au-modified Anatase TiO₂(101) Surface

MA Xin-Guo^1,²(), YAN Jie¹, CHEN Zi-Meng¹, ZHU Lin¹, XU Guo-Wang^1,², HUANG Chu-Yun^1,²(), LV Hui^1,²

1. School of Science, Hubei University of Technology, Wuhan 430068, China
2. Hubei Collaborative Innovation Center for High-efficiency Utilization of Solar Energy, Hubei University of Technology, Wuhan 430068, China

Received:2015-08-10 Revised:2015-09-16 Published:2016-03-20 Online:2016-02-24
Supported by:
National Natural Science Foundation of China (51472081, 51102150, 61106046);Foundation of Hubei University of Technology for High-Level Talents (GCRC13014);Development Funds of Hubei Collaborative Innovation Center (HBSKFMS2014003, HBSKFMS2014011);National Training Programs of Innovation and Entrepreneurship for Undergraduates (201410500012)

摘要/Abstract

摘要：

采用平面波超软赝势方法研究了Pt和Au修饰锐钛矿型TiO₂(101)面的结构稳定性及电子结构。结果显示贵金属原子在TiO₂(101)符合化学计量比的条件下, 在其表面的吸附作用不强, 对电子结构的影响也较小。但是发现在富O条件下, Pt和Au原子容易吸附在表面Ti空位的位置, 与Au原子不同, Pt原子有从TiO₂表面扩散进入体相晶格中的趋势。而在富Ti条件下, Pt和Au原子容易吸附在O1空位的位置。对可能存在的几种空位缺陷吸附模型进行了电子结构的计算。结果表明: 空位缺陷的产生不仅有利于Pt和Au原子“湿化”TiO₂(101)表面, 也有利于带隙中产生贵金属原子的5d杂质能级。

关键词: 光催化, 二氧化钛, 表面修饰, 电子结构

Abstract:

Structure stability and electronic structures of anatase TiO₂(101) surface modified by noble metal Pt and Au have been investigated using plane-wave ultrasoft pseudopotentials. The results show that the adsorption interaction is weak between noble atoms and anatase TiO₂(101) surface, resulting in a slight effect on its electronic structure. However, under O-rich condition, it is found that Pt and Au atoms are favor of the Ti vacancies. Contrary to Au atom, Pt atom tends to diffuse from surface into bulk. Under Ti-rich condition, Pt and Au atoms are favor of the O vacancies. The calculated electronic structures of possible vacancy defects indicate that the appearance of surface vacancies not only avails to wet anatase TiO₂(101) surfaces, but also enables their atoms to appear 5d impurity energy levels in band gap.

Key words: photocatalysis, titanium dioxide, surface modification, electronic structure

中图分类号:

O485

马新国, 严杰, 陈紫梦, 祝林, 徐国旺, 黄楚云, 吕辉. Pt和Au修饰锐钛矿型TiO₂(101)面的第一性原理研究[J]. 无机材料学报, 2016, 31(3): 291-297.

MA Xin-Guo, YAN Jie, CHEN Zi-Meng, ZHU Lin, XU Guo-Wang, HUANG Chu-Yun, LV Hui. First-principles Calculation on Pt- and Au-modified Anatase TiO₂(101) Surface[J]. Journal of Inorganic Materials, 2016, 31(3): 291-297.

图/表 5

图1 贵金属原子吸附于锐钛矿型TiO2(101)面的侧视(上)和俯视(下)结构图。(a)和(b)是表面上方的吸附, (c)和(d)是表面间隙位置的吸附, (e)和(f)是吸附于表面Ti空位, (g)和(h)吸附于表面O空位。其中小红球和小灰球分别表示O和Ti原子, 大蓝球表示吸附的贵金属原子

Fig. 1 The structure model of anatase TiO2(101) surface modified noble metal from side and top view(a) and (b) indicate the adsorption above surface; (c) and (d) indicate the adsorption between surface atoms; (e) and (f) indicate the adsorption at Ti vacancy; (g) and (h) indicate the adsorption at O vacancy. Small black and gray spheres represent the O and Ti atoms, respectively. Big blue spheres represent the noble metal atoms

表1 贵金属吸附在表面上方和间隙位置的吸附能(eV)

Table 1 Adsorption energies of noble metal adsorbing above surface or adsorbing between surface atoms (eV)

Metal	Type	1×1	1×2
Pt	a1	3.511	1.858
	a2	3.854	―
	i1	―	1.416
	i2	―	2.323
Au	a1	2.423	1.398
	a2	2.405	―
	i1	―	1.455
	i2	―	2.624

表2 贵金属吸附在表面Ti或者O空位的吸附能(eV)

Table 2 The adsorption energies of noble metal adsorbing at Ti or O vacancies in TiO2(101) surface (eV)

Metal	Type	1×1		1×2
Metal	Type	O rich	Ti rich	O rich	Ti rich
Pt	S_Ti1	-0.237	10.064	-0.161	4.990
	S_Ti2	-0.490	9.810	-0.331	4.820
	S_O1	5.548	0.398	2.812	0.237
	S_O2	6.043	0.893	2.950	0.375
Au	S_Ti1	1.248	11.548	0.600	5.751
	S_Ti2	1.956	12.256	0.907	6.057
	S_O1	5.501	0.351	2.793	0.218
	S_O2	6.179	1.029	3.067	0.492

图2 贵金属修饰的TiO2表面结构的吸附能与O化学势之间的关系

Fig. 2 The relation between the adsorption energies of TiO2(101) surface modified noble metal and the relative chemical potential ∆μO

图3 贵金属修饰TiO2表面的能带结构和态密度图(填充部分为贵金属的分态密度)

Fig. 3 The energy band structures and the density of states of TiO2(101) surface modified noble metal, whose shaded parts indicate the density of states of the impurity atoms and the standard dotted lines indicate the Fermi level

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Pt和Au修饰锐钛矿型TiO₂(101)面的第一性原理研究

First-principles Calculation on Pt- and Au-modified Anatase TiO₂(101) Surface

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