Methanol adsorption and reactivity on clean and hydroxylated anatase(101) surfaces

被引:103
作者
Tilocca, A [1 ]
Selloni, A [1 ]
机构
[1] Princeton Univ, Dept Chem, Princeton, NJ 08540 USA
关键词
D O I
10.1021/jp046440k
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
The adsorption and reactivity of methanol on TiO2 anatase(101) surfaces are studied through first-principles total energy calculations and Car-Parrinello molecular dynamics simulations. The effects of different methanol coverages up to one monolayer and different surface oxidation states are investigated. The most stable monolayer state involves two different molecular adsorption states, with specific vibrational and electronic properties. Molecular adsorption is always favored on the stoichiometric surface, even though dissociation becomes increasingly more favorable with increasing coverage. Oxygen vacancies shift the energy balance in favor of the dissociated state, whereas dissociative and molecular adsorption appear competitive on the hydroxylated surface. On the latter, a specific molecular adsorption mode, not available on the clean surface, turns out to be stable. The vibrational and electronic properties of adsorbed methanol and methoxy are determined and compared to available experimental data.
引用
收藏
页码:19314 / 19319
页数:6
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