Coupling Benzylamine Oxidation with CO2 Photoconversion to Ethanol over a Black Phosphorus and Bismuth Tungstate S‐Scheme Heterojunction

Photoconversion of CO2 and H2O into ethanol is an ideal strategy to achieve carbon neutrality. However, the production of ethanol with high activity and selectivity is challenging owing to the less efficient reduction half‐reaction involving multi‐step proton‐coupled electron transfer (PCET), a slow C−C coupling process, and sluggish water oxidation half‐reaction. Herein, a two‐dimensional/two‐dimensional (2D/2D) S‐scheme heterojunction consisting of black phosphorus and Bi2WO6 (BP/BWO) was constructed for photocatalytic CO2 reduction coupling with benzylamine (BA) oxidation. The as‐prepared BP/BWO catalyst exhibits a superior photocatalytic performance toward CO2 reduction, with a yield of 61.3 μmol g−1 h−1 for ethanol (selectivity of 91 %).In situ spectroscopic studies and theoretical calculations reveal that S‐scheme heterojunction can effectively promote photogenerated carrier separation via the Bi−O−P bridge to accelerate the PCET process. Meanwhile, electron‐rich BP acts as the active site and plays a vital role in the process of C−C coupling. In addition, the substitution of BA oxidation for H2O oxidation can further enhance the photocatalytic performance of CO2 reduction to C2H5OH. This work opens a new horizon for exploring novel heterogeneous photocatalysts in CO2 photoconversion to C2H5OH based on cooperative photoredox systems. Photocatalytic CO2 reduction for efficient ethanol production is challenging. A 2D/2D S‐Scheme heterojunction comprised of black phosphorus and bismuth tungstate (BP/BWO) was constructed for CO2 reduction, coupled with benzylamine (BA) oxidation to N‐benzylidenebenzylamine (BDA). The catalyst generates ethanol with high yield and selectivity. This work provides insight into heterogeneous photocatalysts based on cooperative photoredox systems.