BiV 1– x O y /Noble Metal Nanoparticle Domains with Reverse Charge Transfer Improves Photoelectrochemical Glycerol to Dihydroxyacetone Conversion

Photoelectrochemical glycerol oxidation (PecGO) using a BiVO4 photoanode is a promising strategy for producing high-value-added dihydroxyacetone (DHA), but the selectivity and efficiency are limited to inferior adsorption and activation ability of secondary hydroxyl groups via surface-exposed Bi atoms. Herein, we report a strong metal–support interaction (SMSI) strategy to enrich the surface Bi atom exposure ratio in a BiVO4 photoanode, while modulating the Bi p-band center through a reverse charge transfer from core/shell like BiV1–xOy/Au nanoparticle (NP) domains. These BiV1–xOy/Au NP domains not only increase the adsorption sites of glycerol secondary hydroxyl groups but also reduce the energy barrier for activating secondary hydroxyl groups. As a result, the photoanode with BiV1–xOy/Au NP domains achieves a photocurrent density of 5.5 mA cm–2 at 1.23 V vs reversible hydrogen electrode, along with a record DHA production rate of 470.5 mmol m–2 h–1 for PecGO that far surpasses other reported values, accompanied by a high selectivity of 75.2%. Furthermore, this SMSI-driven p-band modulation via reverse charge transfer is also applicable with other noble metals such as Pt, Pd, and Ir, offering a universal method to tune the electronic structure of supports beyond the metal NPs themselves and broadening the SMSI applicability across diverse reaction systems.