Effects of Fluorination and Molybdenum Codoping on Monoclinic BiVO4 Photocatalyst by HSE Calculations

Abstract

Monoclinic phase bismuth vanadate (BiVO4) is one of the most promising photoelectrochemical materials used in water-splitting photoelectrochemical cells. It could be even better if its band gap and charge transport characteristics were optimized. Although codoping of BiVO4 has proven to be an effective strategy, its effects are remarkably poorly understood. Using the Heyd− Scuseria−Ernzerhof (HSE) hybrid functional, we estimate the formation energy, electronic properties, and photocatalytic activities of F and Mo codoped BiVO4. We find that Mo atoms prefer to replace V atoms, whereas F atoms prefer to replace O atoms (FOMoV-doped BiVO4) under oxygen-poor conditions according to calculated formation energies. BiVO4 doped with FOMoV is found to be shallow-level doped, occurring with some continuum states above the conduction band edge, which is advantageous for photochemical catalysis. Moreover, FOMoV-doped BiVO4 shows absorption stronger than that of pure BiVO4 in the visible spectrum. Based on the band-edge calculation, BiVO4 doped with FOMoV still retains a high oxidizing capacity. It has been shown that FOMoV-doped BiVO4 exhibits a very high photocatalytic activity under visible light.