Water-Induced Reversal of the TiO ₂(011)-(2 × 1) Surface Reconstruction: Observed with in Situ Surface X-ray Diffraction

Abstract

The (011) termination of rutile TiO ₂ is reported to be particularly effective for photocatalysis. Here, the structure of the interface formed between this substrate and water is revealed using surface X-ray diffraction. While the TiO ₂(011) surface exhibits a (2 × 1) reconstruction in ultra-high vacuum (UHV), this is lifted in the presence of a multilayer of water at room temperature. This change is driven by the formation of Ti–OH at the interface, which has a bond distance of 1.93 ± 0.02 Å. The experimental solution is in good agreement with density functional theory and first-principles molecular dynamics calculations. These results point to the important differences that can arise between the structure of oxide surfaces in UHV and technical environments and will ultimately lead to an atomistic understanding of the photocatalytic process of water splitting on TiO ₂ surfaces.