Surface chemistry and interfacial charge-transfer mechanisms in photoinduced oxygen exchange at O2-TiO2 interfaces

Experimental results obtained over the last three decades on photoinduced oxygen isotopic exchange (POIE) of TiO₂ oxygen atoms with those of adsorbed water molecules and gaseous O₂ are analyzed in the light of recent information from the literature on the interaction of water and O₂ species with the TiO₂ surface (obtained by application of surface spectroscopy techniques in combination with high-resolution scanning tunnelling microscopy). The analysis emphasizes the singular role that bridging oxygen ions and bridging oxygen vacancies play in TiO₂ surface chemistry and interfacial electron transfer at the gas phase-TiO₂ interface in the absence and presence of water. The observed competition between POIE and the photo-oxidation (PO) of organic compounds is analyzed in terms of the recently developed direct-indirect (D-I) kinetic model for heterogeneous photocatalysis (D. Monllor-Satoca et al., Catal. Today, 2007, 129, 247, and references therein).