Site Sensitivity of Interfacial Charge Transfer and Photocatalytic Efficiency in Photocatalysis: Methanol Oxidation on Anatase TiO2 Nanocrystals.

Photocatalytic oxidation of methanol on various anatase TiO2 nanocrystals was studied by in situ and time-resolved characterizations and DFT calculations. Surface site and resulting surface adsorbates affect the surface band bending/bulk-to-surface charge migration processes and interfacial electronic structure/interfacial charge transfer processes. TiO2 nanocrystals predominantly enclosed by the {001} facets expose a high density of reactive fourfold-coordinated Ti sites (Ti4c ) at which CH3 OH molecules dissociate to form the CH3 O adsorbate (CH3 O(a)Ti4c ). CH3 O(a)Ti4c localized density of states are almost at the valence band maximum of TiO2 surface, facilitating the interfacial hole transfer process; CH3 O(a)Ti4c with a high coverage promotes upward surface band bending, facilitating bulk-to-surface hole migration. CH3 O(a)Ti4c exhibits the highest photocatalytic oxidation rate constant. TiO2 nanocrystals enclosed by the {001} facets are most active in photocatalytic methanol oxidation.