Adsorption and dissociation of COCl2 on the rutile TiO2(110) surfaces: a systematic first-principles study

Abstract

The adsorption and dissociation of phosgene (COCl₂) molecules on three kinds of rutile TiO₂(110) surfaces (stoichiometric: TiO₂-Sto; oxygen defective: TiO₂-Ov; and substoichiometric: TiO_1.875) were investigated based on density functional theory calculations. The nature of interactions between the COCl₂ molecule and rutile TiO₂(110) surfaces with different degrees of reduction was researched by the analysis of geometries, electron density difference, adsorption energies and density of states (DOS). Computational results show that COCl₂ indicates instability and will dissociate directly without the presence of transition states on a substoichiometric TiO_1.875(110) surface. The adsorption and dissociation behavior of COCl₂ on the rutile surface is not only helpful in providing theoretical support for the clean and efficient degradation of COCl₂, but also helpful in elucidating the role of COCl₂ as an intermediate product in the carbochlorination of titanium ore.