BiV <sub> 1– <i>x</i> </sub> O <sub> <i>y</i> </sub> /Noble Metal Nanoparticle Domains with Reverse Charge Transfer Improves Photoelectrochemical Glycerol to Dihydroxyacetone Conversion
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
Abstract
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.