[Cp*Rh(bpy)H2O]2+自组装CdIn2S4花状微球的高效光催化NADH再生与酶促CO2还原OA

Integrating photocatalytic cofactor regeneration with enzymatic cascades enables sustainable CO2 valorization but faces challenges like limited hydrogen sources and homogeneous mediator and photogenerated holes-induced enzyme deactivation.This study demonstrates that the low oxidation potential of L-ascorbic acid(L-AA)can enhance proton supply and promote the formation of[Cp*Rh(bpy)H]+intermediates.Only 0.26 mg(≈ 0.12 mmol L-1)[Cp*Rh(bpy)Cl]Cl can achieve efficient/selective reduced nicotinamide adenine dinucleotide(NADH)regeneration,which is more than twice as effective as the typical sacrificial agent triethanolamine(TEOA).A novel strategy was developed via electrostatic self-assembly of[Cp*Rh(bpy)H2O]²+onto CdIn2S4 microsphere photocatalysts.This innovative integration physically separated free mediators and photogenerated holes from enzymes,effectively suppressing enzyme deactivation through spatial compartmentalization.The optimal integrated photocatalytic system achieved 90%NADH regeneration efficiency within 40 min of 420 nm light irradiation,outperforming previously reported systems.When coupled with formate dehydrogenase(FDH),the integrated system achieved formic acid generation rates of 443.5 μmol g-1 h-1(one light-dark cycle)and 202.7 μmol g-1 h-1(continuous light),representing 1.2-and 3.2-fold improvements over free mediator systems,respectively.This study provides an efficient and sustainable new strategy for light driven coenzyme regeneration and enzyme catalyzed CO2 synthesis of high value-added chemicals.