Sustainable Photocatalytic Biological Cofactor Regeneration Fueled by Selective Alcohol Oxidation over Polarized ZnIn2S4

Photocatalytic conversion of cofactor NAD+ to NADH could inspire versatile and valuable biosynthesis using renewable solar energy. However, most previous photocatalytic systems necessitate leveraging sacrificial electron donors due to the complexity of kinetics coupling, resulting in a real “sacrifice”. Herein, we report an integrated path for photocatalytic NADH regeneration fueled by selective alcohol oxidation over polarized ZnIn2S4 (ZIS). Notably, the conventional electron mediator Rh complex was found to be facilely coordinated onto the ZIS surface, rendering the modulation of the internal and interfacial dipole field. The pronounced charge redistribution establishes favorable kinetics for seamlessly integrating photocatalysis and enzymatic catalysis. The maximum cofactor regeneration efficiency could reach 13.5 mmol g–1 h–1 with AQY up to 26.8% under 420 nm. Concurrently, the induced interfacial polarization promotes benzyl alcohol adsorption and subsequent C–H and O–H bond cleavage, thereby boosting the oxidation half-reaction rate and selectivity. This study bridges the gap in photoenzymatic CO2 conversion by combining selective oxidative upgrading with efficient cofactor recycling.