Thiophene-Conjugated Porous C₃N₄ Nanosheets for Boosted Photocatalytic Nicotinamide Cofactor Regeneration to Facilitate Solar-to-Chemical Enzymatic Reactions

Abstract

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 diffusion 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 non-incorporated 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.

Keywords

Photobiocatalytic hybrid system / Photocatalytic NAD(P)H regeneration / Graphitic carbon nitride / Solar-to-chemical conversion

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