Single‐Atomic‐Site Platinum Steers Middle Hydroxyl Selective Oxidation on Amorphous/Crystalline Homojunction for Photoelectrochemical Glycerol Oxidation Coupled with Hydrogen Generation

Abstract Photoelectrochemical (PEC) organic conversion is a promising approach to convert low‐cost organics to value‐added chemicals, which urgently needs the development of efficient and highly selective photoanodes. Here, a Pt single‐atom dispersed WO 3 amorphous/crystalline homojunction for anodic glycerol oxidation reaction (GOR) coupled with cathodic hydrogen generation is reported. In the coupled photoelectrocatalytic system, the novel Pt‐SA/WO x photoanode reaches a photocurrent density of 2.85 mA cm −2 at 1.2 V versus RHE, with up to 297.3 mmol m −2 h −1 of glycerol conversion rate and 60.2% of dihydroxyacetone (DHA) selectivity, realizing green synthesis of high‐value chemicals. The experimental data and theoretical calculations reveal the regulated band structure, build‐in electric field, and surface charge density of Pt‐SA/WO x , which can improve the carrier lifetime, accelerate charge transfer, and reduce the energy barrier for the GOR process, thus boosting PEC activity and DHA selectivity. This work provides a feasible plan for designing atomic‐level engineering and constructing amorphous/crystalline homojunction on photoanodes for efficient PEC high‐value products from biomass.