TiO2 /ferroelectric heterostructures as dynamic polarization-promoted catalysts for photochemical and electrochemical oxidation of water

Using first-principles density functional theory calculations, we explore the chemical activity of epitaxial heterostructures of TiO2 anatase on strained polar SrTiO3 films focusing on the oxygen evolution reaction (OER), the bottleneck of water splitting. Our results show that the reactivity of the TiO2 surface is tuned by electric dipoles dynamically induced by the adsorbed species during the intermediate steps of the reaction while the initial and final steps remain unaffected. Compared to the OER on unsupported TiO2, the combined effects of the dynamically induced dipoles and epitaxial strain strongly reduce rate-limiting thermodynamic barriers and significantly improve the efficiency of the reaction.