Spatially Decoupled S‐Scheme and Schottky Heterojunction in CeO 2 /ZnIn 2 S 4 /WC for Synergistic Photocatalytic H 2 Evolution and Benzyl Alcohol Oxidation

The dual‐utilization of photogenerated electrons and holes for concurrent energy production and biomass valorization represents a sustainable pathway for solar‐to‐chemical conversion, yet it remains challenging due to rapid charge recombination and the lack of spatially defined redox sites. Herein, we report a spatially decoupled ternary heterojunction, denoted as CeO 2 /ZnIn 2 S 4 /WC (CZW), which integrates CeO 2 nanoparticles and WC nanoparticles onto ZnIn 2 S 4 nanosheets for photocatalytic H 2 evolution coupled with selective benzyl alcohol oxidation. This unique architecture integrates two distinct charge‐transfer pathways: an S‐scheme heterojunction between CeO 2 and ZnIn 2 S 4 , and a Schottky junction between ZnIn 2 S 4 and WC. The S‐scheme configuration preserves highly reductive electrons in ZnIn 2 S 4 and highly oxidative holes in CeO 2 , whereas the Schottky junction directionally extracts electrons to WC with Pt‐like properties. This dual‐path design not only achieves efficient spatial charge separation but also enables precise reaction site functionalization. Consequently, H 2 evolution selectively occurs on WC surfaces, whereas benzyl alcohol oxidation proceeds exclusively on CeO 2 valence bands, completely eliminating active site competition and suppressing reverse reactions. The optimized CZW heterojunction exhibits remarkable photocatalytic performance without any noble metal or sacrificial agent, achieving an H 2 evolution rate of 28.4 mmol g −1 h −1 and a benzyl alcohol conversion rate of 99.9%. This work provides a blueprint for designing advanced photocatalytic systems through the synergistic integration of junction engineering and site‐specific functionalization for sustainable energy and chemical synthesis.