Direct Imaging of Site-Specific Photocatalytical Reactions of O2 on TiO2(110).

Photostimulated reactions of single O2 molecules on reduced TiO2(110) surfaces were directly observed at an atomic level with high-resolution scanning tunneling microscopy at 50 K. Two distinct reactions of O2 desorption and dissociation occur at different active sites of terminal Ti atoms and bridging O vacancies, respectively. Two reaction channels follow very different kinetics. While hole-mediated O2 desorption is promptly and fully completed, electron-mediated O2 dissociation is much slower and is quenched above some critical O2 coverage. Evidently, the O2 photochemistry on TiO2(110) is quite more complex than thought previously. Density functional theory calculations indicate that both coordination and charge state of an O2 molecule chemisorbed at the specific site largely determine a particular reaction pathway.