Photocatalytic hydrogen evolution on P-type tetragonal zircon BiVO4

Tetragonal zircon BiVO4 (P-BiVO4) were grown on fluorine-doped tin oxide (PTO) glass via hydrothermal method. The cathodic photocurrent and Mott-Schottky analysis indicate that the tetragonal zircon BiVO4 is a p-type semiconductor. Inductively coupled plasma (ICP) analysis and X-ray photoelectron spectrum showed that there are Bi vacancies and interstitial oxygen exist in the crystal, which are the origin of the p-type conductivity. The flat band potential of the P-BiVO4 is about 1.33 V (vs Ag/AgCl) inferred from Mott-Schottky plots. Combining with diffuse reflection spectrum and valence band X-ray photoelectron spectrum, the calculated conduction band value of the P-BiVO4 is about 0.06 V vs RHE, slightly higher than the reduction potential of hydrogen. However, the P-BiVO4 exhibit hydrogen production activity under Xe light irradiation even though its conduction band level is not negative enough. This can be attributed to the hot carrier processes in p-type semiconductors.