  The interaction of water with TiO2 is crucial to many of its practical
applications, including photocatalytic water splitting. Following the first
demonstration of this phenomenon 40 years ago there have been numerous studies
of the rutile single-crystal TiO2(110) interface with water. This has provided
an atomic-level understanding of the water-TiO2 interaction. However, nearly
all of the previous studies of water/TiO2 interfaces involve water in the
vapour phase. Here, we explore the interfacial structure between liquid water
and a rutile TiO2(110) surface pre-characterized at the atomic level. Scanning
tunnelling microscopy and surface X-ray diffraction are used to determine the
structure, which is comprised of an ordered array of hydroxyl molecules with
molecular water in the second layer. Static and dynamic density functional
theory calculations suggest that a possible mechanism for formation of the
hydroxyl overlayer involves the mixed adsorption of O2 and H2O on a partially
defected surface. The quantitative structural properties derived here provide a
basis with which to explore the atomistic properties and hence mechanisms
involved in TiO2 photocatalysis.
