Oxygen vacancies as active sites for water dissociation on rutile TiO(2)(110)

Phys Rev Lett. 2001 Dec 24;87(26):266104. doi: 10.1103/PhysRevLett.87.266104. Epub 2001 Dec 6.


Through an interplay between scanning tunneling microscopy experiments and density functional theory calculations, we determine unambiguously the active surface site responsible for the dissociation of water molecules adsorbed on rutile TiO(2)(110). Oxygen vacancies in the surface layer are shown to dissociate H(2)O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water is able to diffuse to the active site.