Zhonghao Wang, Yuan Gao, Yuan Lu, Jun Bum Park, Jun Bum Park, Jeong-Hyun Hwang, Tae‐Kyung Liu, Zongkun Bian, Yong Xia, Botao Qiao, Kan Zhang, Jong Hyeok Park, Jong Hyeok Park
High Resolution Image Download MS PowerPoint Slide Photoelectrochemical glycerol oxidation (PecGO) using a BiVO 4 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 BiVO 4 photoanode, while modulating the Bi p -band center through a reverse charge transfer from core/shell like BiV 1– x O y /Au nanoparticle (NP) domains. These BiV 1– x O y /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– x O y /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.