Facet engineered Ag3PO4 for efficient water photooxidation

The photooxidation of water using faceted Ag3PO4 was investigated, guided by theoretical modelling. Firstly, theoretical calculations were performed to predict the optimum morphology for solar energy conversion by probing the surface energies of three primary low index facets of Ag3PO4: {100}, {110} and {111}. It was elucidated that the {111} facet possessed considerably higher surface energy (1.65 J m−2) than either {110} or {100} (0.78 and 0.67 J m−2 respectively). We therefore attempted to fabricate Ag3PO4 crystals with {111} facets. Tetrahedral Ag3PO4 crystals, composed of {111} facets, were then successfully synthesised using a novel kinetic control method in the absence of surfactants. In comparison to rhombic dodecahedron {110} and cubic {100} structures, tetrahedral crystals show an extremely high activity for water photooxidation, with an initial oxygen evolution rate exceeding 6 mmol h−1 g−1, 10 times higher than either {110} or {100} facets. Furthermore, to the best of our knowledge it is the first time that the internal quantum yield for water photooxidation is almost unity at 400 nm, and greater than 80% from 365 to 500 nm, achieved by {111} terminated tetrahedrons. The excellent and reproducible performance is attributed to a synergistic effect between high surface energy and a small hole mass, leading to high charge carrier mobility and active surface reaction sites.