Dynamic Equilibrium of Reversible Reactions and Migration of Hydrogen Atoms Mediated by Diffusive Methanol on Rutile TiO2 (110)-(1 × 1) Surface

Abstract

We report our investigation of the reversible reaction of methanol and the migration of hydrogen adatom (Had) on TiO2(110)-(1 × 1) surface at various temperatures and methanol coverages using scanning tunneling microscopy joint with density functional theory (DFT) calculations. At a relatively low coverage measured at room temperature, the methanol species adsorbed at the oxygen vacancy (OV) sites are immobile and appear only as a dissociative form, and the observed Had migration events are very few. However, when the OV sites are fully filled by methanol in the methanol-overdosed sample, the methanol species at the OV sites keep immobile but frequently switch between molecular and dissociative forms, accompanied by dramatically enhanced Had migration. Meanwhile, an established equilibrium shows a concentration ratio of 1:3 between the molecular and dissociative methanol. At 235 K, we directly visualized and confirmed that the reversible reactions of methanol and the enhanced Had migration are mediated by...