The structure of water on rutile TiO2(110) for applications in solar hydrogen production: towards a predictive model using hybrid-exchange density functional theory

Abstract

ABSTRACTPeriodic hybrid-exchange density functional theory (DFT) simulations are used to develop a predictive model of the structure of water on the rutile TiO2(110) surface (Θ ≤ 1 ML). A description of the adsorbed species is given: dissociated water molecules and either mixed or dissociative dimers. The behaviour of the adsorbates is rationalised by considering both direct intermolecular and surface-mediated interactions. Some of these results are then compared with those from water adsorption on the rutile SnO2(110) sur- face, isostructural to TiO2(110). Lastly, the electronic structure of the surface in contact with monolayer water (Θ = 1 ML) reveals the contributions of adsorbate states involved in the photocatalytic reaction that controls the water oxidation process.