Recent Theoretical Progress on Photochemical Reactions at the Solid/Solution Interface

TiO2 nanoparticles have been widely utilized in photocatalysis, but the atomic level understanding on their working mechanism falls much short of expectations. In this short review, we briefly introduce the recent theoretical progress in photocatalysis carried out in our research group. Extensive density functional theory (DFT) calculations combined with the periodic continuum solvation model have been utilized to compute the electronic structure of extended surfaces, nanoparticles in aqueous solution and provide the reaction energetics for the key elementary reaction. It is demonstrated that the equilibrium shape of nanoparticle is sensitive to its size from 1 to 30 nm, and the sharp crystals possess much higher activity than the flat crystals in oxygen evolution of water splitting, which in combination lead to the morphology dependence of photocatalytic activity.