Intensifying Electron Utilization by Surface-Anchored Rh Complex for Enhanced Nicotinamide Cofactor Regeneration and Photoenzymatic CO_(2)Reduction  

作　　者：Yuqing Cheng Jiafu Shi Yizhou Wu Xueying Wang Yiying Sun Ziyi Cai Yu Chen Zhongyi Jiang 

机构地区：[1]Key Laboratory for Green Chemical Technology of Ministry of Education,School of Chemical Engineering and Technology,Tianjin University,92 Weijin Road,Nankai District,Tianjin 300072,China [2]Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),92 Weijin Road,Nankai District,Tianjin 300072,China [3]School of Environmental Science&Engineering,Tianjin University,92 Weijin Road,Nankai District,Tianjin 300072,China [4]State Key Laboratory of Biochemical Engineering,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 10090,China

出　　处：《Research》2021年第1期507-517,共11页研究（英文）

基　　金：supported by the National Natural Science Funds of China(21776213 and 21621004);the Natural Science Fund of Tianjin(19JCYBJC19700);the Open Funding Project of the State Key Laboratory of Biochemical Engineering(2020KF-06);the Open Funding Project of the State Key Laboratory of Chemical Engineering(SKL-ChE19B01);the Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project(TSBICIP-KJGG-003);the Royal Society International Collaboration Award(ICA\R1\180317)for the financial support.

摘　　要：Solar-driven photocatalytic regeneration of cofactors,including reduced nicotinamide adenine dinucleotide(NADH),reduced nicotinamide adenine dinucleotide phosphate(NADPH),and reduced flavin adenine dinucleotide(FADH_(2)),could ensure the sustainable energy supply of enzymatic reactions catalyzed by oxidoreductases for the efficient synthesis of chemicals.However,the elevation of cofactor regeneration efficiency is severely hindered by the inefficient utilization of electrons transferred on the surface of photocatalysts.Inspired by the phenomenon of ferredoxin-NADP+reductase(FNR)anchoring on thylakoid membrane,herein,a homogeneous catalyst of rhodium(Rh)complex,[Cp_(∗)Rh(bpy)H_(2)O]^(2+),was anchored on polymeric carbon nitride(PCN)mediated by a tannic acid/polyethyleneimine(TA/PEI)adhesive layer,acquiring PCN@TA/PEI-Rh core@shell photocatalyst.Illuminated by visible light,electrons were excited from the PCN core,then transferred through the TA/PEI shell,and finally captured by the surface-anchored Rh for instant utilization during the regeneration of NADH.The TA/PEI-Rh shell could facilitate the electron transfer from the PCN core and,more importantly,achieved~1.3-fold elevation of electron utilization efficiency compared with PCN.Accordingly,the PCN@TA/PEI-Rh afforded the NADH regeneration efficiency of 37.8%after 20 min reaction under LED light(405 nm)illumination,over 1.5 times higher than PCN with free Rh.Coupling of the NADH regeneration system with formate dehydrogenase achieved continuous production of formate from carbon dioxide(CO_(2)).Our study may provide a generic and effective strategy to elevate the catalytic efficiency of a photocatalyst through intensifying the electron utilization.

关 键 词：ENZYMATIC DINUCLEOTIDE CATALYST 

分 类 号：O64[理学—物理化学]