High‐Valence Metal‐Photoelectrocatalytic Biomass Conversion to Aldehyde on Integrated Photoelectrodes

Abstract Photoelectrochemical (PEC) biomass conversion represents an attractive strategy for the sustainable conversion of low‐value biomass into value‐added chemicals. Nonetheless, sluggish charge transfer kinetics and insufficient density of catalytic active sites critically impede PEC performance, constraining conversion efficiency and product selectivity. Herein, photoelectrocatalytic biomass oxidation of glycerol to C3 products on the integrated Au‐Ni 2 P/ZnO/WO 3 photoanode, achieving 82.9% Faraday efficiency, is reported. From the analysis of bandgap structure and time‐resolved photoluminescence spectroscopy, ZnO/WO 3 heterostructure significantly accelerates charge transfer and separation owing to the formation of a built‐in electric field. Especially, surface reconstruction induces the generation of high‐valence nickel species as active centers, facilitating proton‐coupled electron transfer (PCET) process and expediting surface reaction kinetics. Mechanism investigations combining in situ infrared spectroscopy and electron paramagnetic resonance spectroscopy elucidate the reaction pathway and intermediate evolution. This work presents a rational design paradigm for integrated photoanodes and provides a promising high‐valence metal‐photoelectrocatalytic strategy advancing high‐efficiency biomass‐to‐chemical conversion.