Chemisorbed and Physisorbed Water at the TiO/Water Interface.

The interfacial structure of water in contact with TiO is the key to understand the mechanism of photocatalytic water dissociation as well as photoinduced superhydrophilicity. We investigate the interfacial molecular structure of water at the surface of anatase TiO, using phase-sensitive sum frequency generation spectroscopy together with spectra simulation using ab initio molecular dynamic trajectories. We identify two oppositely oriented, weakly and strongly hydrogen-bonded subensembles of O-H groups at the superhydrophilic UV irradiated TiO surface. The water molecules with weakly hydrogen-bonded O-H groups are chemisorbed, i.e. form hydroxyl groups, at the TiO surface with their hydrogen atoms pointing toward bulk water. The strongly hydrogen-bonded O-H groups interact with the oxygen atom of the chemisorbed water. Their hydrogen atoms point toward the TiO. This strong interaction between physisorbed and chemisorbed water molecules causes superhydrophilicity.