物理化学学报2026，Vol.42Issue(3)：63-73,11.DOI:10.1016/j.actphy.2025.100165
[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
Efficient photocatalytic NADH regeneration and enzymatic CO2 reduction over[Cp*Rh(bpy)H2O]2+self-assembled CdIn2S4 flower-like microspheres
摘要
Abstract
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.关键词
光-酶偶联催化/CdIn2S4微球/CO2转化/电子介体集成/NADH再生Key words
Photoenzyme-coupled catalysis/CdIn2S4 microspheres/CO2 conversion/Electronic mediator integration/NADH regeneration分类
化学化工引用本文复制引用
高春慧,李璐嵘,彭官威,沈锦妮,戴文新,张子重..[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[J].物理化学学报,2026,42(3):63-73,11.基金项目
本研究获得国家自然科学基金(项目编号22372041)、福建省科技重大专项(编号2021YZ037005)以及核生化防护化学全国重点实验室(编号SKLNBC2023-07)资助 （项目编号22372041）
