Surface Reconstruction-Induced Site-Specific Charge Separation and Photocatalytic Reaction on Anatase TiO2(001) Surface

Photocatalytic reaction of methanol on an anataseTiO(2)(001)-(1 x 4) reconstructed' surface, a prototype reaction for photocatalysis, was studied by means of X-ray photoelectron spectroscopy, thermal desorption spectrum, and densityfunctional theory calculations, Photocatalytic oxidation reaction, was observed toexclusively occur at the Ti-4C sites of the (1 x 4) added row but not at the Ti-5C sites-of the (1 x 1) basal surface, The accompanying density functional theory calculation results demonstrate that the valence band maximum is localized at the-oxygen atoms of the (1 x 4) added row and the methoxy species bonded to the Ti-4C sites, respectively, for the clean and methanol-covered, anatase TiO2(001)-(1 x 4) surfaces. This leads to-a Ti-4C site-specific oxidation of the methoxy species by photogenerated holes. These results reveal a concept of surface reconstruction-induced site-specific charge separation and photocatalytic reaction on oxide ph-otocatalysts that will greatly deepen the understanding of the vital role of oxide surface structure in photocatalytic reactions.