Site Sensitivity of Interfacial Charge Transfer and Photocatalytic Efficiency in Photocatalysis: Methanol Oxidation on Anatase TiO ₂ Nanocrystals

Photocatalytic oxidation of methanol on various anatase TiO2 nanocrystals was studied by in situ and time-resolved characterizations DFT calculations. Surface site resulting surface adsorbates affect the band bending/bulk-to-surface charge migration processes interfacial electronic structure/interfacial transfer processes. predominantly enclosed {001} facets expose a high density reactive fourfold-coordinated Ti sites (Ti4c) at which CH3OH molecules dissociate to form CH3O adsorbate (CH3O(a)Ti4c). CH3O(a)Ti4c localized states are almost valence maximum surface, facilitating hole process; with coverage promotes upward bending, bulk-to-surface migration. exhibits highest photocatalytic rate constant. most active oxidation.