Effect of Rh Doping on Optical Absorption and Oxygen Evolution Reaction Activity on BaTiO3 (001) Surfaces

In the present work, we investigate the potential of modified barium titanate (BaTiO₃), an inexpensive perovskite oxide derived from earth-abundant precursors, for developing efficient water oxidation electrocatalysts using first-principles calculations. Based on our calculations, Rh doping is a way of making BaTiO₃ absorb more light and have less overpotential needed for water to oxidize. It has been shown that a TiO₂-terminated BaTiO₃ (001) surface is more promising from the point of view of its use as a catalyst. Rh doping expands the spectrum of absorbed light to the entire visible range. The aqueous environment significantly affects the ability of Rh-doped BaTiO₃ to absorb solar radiation. After Ti→Rh replacement, the doping ion can take over part of the electron density from neighboring oxygen ions. As a result, during the water oxidation reaction, rhodium ions can be in an intermediate oxidation state between 3+ and 4+. This affects the adsorption energy of reaction intermediates on the catalyst’s surface, reducing the overpotential value.