ZnWO ₄ /WO ₃ Heterojunction Photoanodes for Selective Photoelectrochemical Conversion of Glycerol to Glyceraldehyde

ABSTRACT Photoelectrocatalytic (PEC) conversion of glycerol into valuable chemicals represents a promising technology for achieving a green chemical industry. Designing excellent and stable photoelectrode materials with efficient charge separation and interfacial reaction kinetics is crucial for advancing the industrialization of PEC glycerol conversion. Herein, a ZnWO 4 /WO 3 (ZWO/WO) heterojunction photoanode was designed and fabricated via in situ hydrothermal growth of ZnWO 4 nanoparticles on WO 3 nanosheet arrays. Comprehensive structural and spectroscopic analyses revealed the formation of a compact heterostructure with strong electronic coupling between ZnWO 4 and WO 3 . Consequently, the optimized ZWO/WO photoanode exhibits an impressive 1.5‐fold enhancement in the glyceraldehyde (GLD) yield rate (320.1 mmol m −2 h −1 at 1.4 V RHE ) compared to pristine WO 3 . Moreover, the introduction of ZnWO 4 enhances the selectivity of liquid products toward GLD, increasing from 70.8% to 81%. The ZWO/WO photoanode exhibits excellent operational stability over 18 h at 1.0 V RHE . The incident photon‐to‐current efficiency (IPCE) increases from 27.5% to 35% at 400 nm wavelength with glycerol conditions. The synergistic interaction between ZnWO 4 and WO 3 accelerates charge transfer and oxidation kinetics, thereby promoting the selective formation of the C 3 product.