Is There a Nanosize for the Activity of TiO2 Compounds?

被引：37

作者：

Calatayud, Monica ^{[1
]}

Minot, Christian ^{[1
,2
]}

机构：

[1] UPMC Univ Paris 06, UMR 7616, Chim Theor Lab, CNRS, F-75252 Paris 05, France

[2] City Univ Hong Kong, Dept Phys & Mat Sci, Hong Kong, Hong Kong, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2009年 / 113卷 / 28期

基金：

欧洲研究理事会; 英国科学技术设施理事会;

关键词：

INITIO MOLECULAR-DYNAMICS; DENSITY-FUNCTIONAL THEORY; METAL-OXIDE SURFACES; GAS-PHASE; AB-INITIO; ELECTRONIC-STRUCTURE; TITANIUM-DIOXIDE; OXYGEN SITES; CLUSTERS; REACTIVITY;

D O I：

10.1021/jp901465q

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Reactivity of TiO2 compounds is investigated vs nanosize using atomic hydrogen adsorption as a probe. Small clusters with (TiO2)(n) stoichiometry (n = 1-24) of lowest energy are compared with infinite systems like polymers and Surfaces. The binding energy for the most reactive Clusters reaches similar to 3.5 eV while it is 2.8 eV for the smallest one (the TiO2 molecule) and 2.30 eV for the most reactive surface (rutile-110). No systematic relation with size emerges from this analysis which predicts a large variety of individual structures. High H binding energy is associated with the presence of poorly coordinated 0 atom at the surface and with a favorable reducibility of the substrate. The local topology of the adsorption site and its flexibility play a major role in reactivity, However, the reactivity of nanosized TiO2 clusters is correlated with small electronic gap and low lying LUMOs.

引用

页码：12186 / 12194

页数：9

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