Thiophene-Conjugated Porous C_(3)N_(4) Nanosheets for Boosted Photocatalytic Nicotinamide Cofactor Regeneration to Facilitate Solar-to-Chemical Enzymatic Reactions

摘要

The low catalytic efficiency of redox-active cofactor photoregeneration severely limits the performance of photoenzymatic hybrid systems. Herein, we synthesized thiophene-conjugated porous C3N4 nanosheets(CN-ATCN) exhibiting boosted photoregeneration activity of nicotinamide cofactors(NADH and NADPH), which are the most common redox cofactors of oxidoreductases, with regeneration rates of 59.00 μM/min for NADH and 40.99 μM/min for NADPH, ~ 84.3 and 24.7 times higher than those of bulk g-C3N4, respectively. The thin nanosheet structure of CN-ATCN facilitates the exposure of active sites to reactants and favors the diff usion of reactants and products. Upon conjugation of a thiophene moiety into the carbon nitride framework, the optical and photoelectric properties of CN-ATCN were considerably enhanced by an extended π-conjugation system in the frameworks and molecular type II heterojunctions formed between the incorporated and nonincorporated portions of CN-ATCN. Upon coupling NAD(P)H photoregeneration reaction by CN-ATCN with NAD(P)H-dependent enzymatic systems, sustainable synthesis of L-tert-leucine and styrene oxide was achieved with rates of 964 and 14.9 μM/h, respectively.