Origin of hydroxyl pair formation on reduced anatase TiO2(101)

Abstract

The interaction of water with metal oxide surfaces is of key importance to several research fields and applications. Because of its ability to photo-catalyze water splitting, reducible anatase TiO₂ (a-TiO₂) is of particular interest. Here, we combine experiments and theory to study the dissociation of water on bulk-reduced a-TiO₂(101). Following large water exposures at room temperature, point-like protrusions appear on the a-TiO₂(101) surface, as shown by scanning tunneling microscopy (STM). These protrusions originate from hydroxyl pairs, consisting of terminal and bridging OH groups, OH_t/OH_b, as revealed by infrared reflection absorption spectroscopy (IRRAS) and valence band experiments. Utilizing density functional theory (DFT) calculations, we offer a comprehensive model of the water/a-TiO₂(101) interaction. This model also explains why the hydroxyl pairs are thermally stable up to ∼480 K.