Integrating P‐Doped Carbon Nitride Dots as Active Sites on P/Mo Co‐Doped BiVO₄ Photoanodes Promotes H₂O₂ Production

Abstract The indirect anthraquinone method is currently used to produce H₂O₂, but it leads to high energy consumption and a large amount of chemical waste. Alternatively, water oxidation reactions offer a potential green approach for H₂O₂ production, although it is constrained by low selectivity. Herein, the functional photoanodes are rationally designed for H₂O₂ production via photocatalytic water oxidation. Specifically, P/Mo co‐doped BiVO₄ films are achieved on a conductive glass to serve as the photocatalytic layer, which is coated with an ultrathin amorphous TiO₂ film to achieve good stability. Importantly, metal‐free P‐doped polymeric carbon nitride dots are deposited on the photoanode, acting as the reaction centres. This innovative approach moves away from the traditional reliance on inorganic materials as co‐catalysts in order to suppress the thermodynamically favoured O₂ evolution, which, in turn, significantly enhances the selectivity, efficiency and stability of H₂O₂ production. Consequently, an optimal selectivity of ≈64% for H₂O₂ production is achieved at an applied voltage bias of 1.7 V versus RHE in a 1.0 m KHCO₃ solution, achieving a yield of ≈34.2 µmol hr⁻¹ cm⁻². This research offers a novel strategy for developing photocatalytic films with optimised co‐catalysts for a photoanode in photocatalytic H₂O₂ synthesis.