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

Abstract 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.