Manipulation of Charge Transport by Metallic V13O16 Decorated on Bismuth Vanadate Photoelectrochemical Catalyst

Conductive metal oxides represent a new category of functional material with vital importance for many modern applications. The present work introduces a new conductive metal oxide V13O16, which is synthesized via a simplified photoelectrochemical procedure and decorated onto the semiconducting photocatalyst BiVO4 in controlled mass percentages ranging from 25% to 37%. Owing to its excellent conductivity and good compatibility with oxide materials, the metallic V13O16‐decorated BiVO4 hybrid catalyst shows a high photocurrent density of 2.2 ± 0.2 mA cm−2 at 1.23 V versus reversible hydrogen electrode (RHE). Both experimental characterization and density functional theory calculations indicate that the superior photocurrent derives from enhanced charge separation and transfer, resulting from ohmic contact at the interface of mixed phases and superior electrical conductivity from V13O16. A Co–Pi coating on BiVO4–V13O16 further increases the photocurrent to 5.0 ± 0.5 mA cm−2 at 1.23 V versus RHE, which is among the highest reported for BiVO4‐based photoelectrodes. Surface photovoltage and transient photocurrent measurements suggest a charge‐transfer model in which photocurrents are enhanced by improved surface passivation, although the barrier at the Co–Pi/electrolyte interface limits the charge transfer. BiVO4 is a promising photocatalyst for water oxidation but its high recombination rate limits performance. This shortcoming is addressed by decorating BiVO4 with metallic V13O16. Both experimental characterization and modeling results indicate that the superior photocurrent derives from enhanced charge separation and transfer, resulting from ohmic contact at the interface of mixed phases and superior electrical conductivity from V13O16.