BiV _{1– <i>x</i>} O _<i>y</i> /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 <i>p</i>-band center through a reverse charge transfer from core/shell like BiV_1-<i>x</i>O_<i>y</i>/Au nanoparticle (NP) domains. These BiV_1-<i>x</i>O_<i>y</i>/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 BiV_1-<i>x</i>O_<i>y</i>/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 <i>p</i>-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.