化学
共价有机骨架
共价键
催化作用
光化学
光催化
电子供体
亚胺
电子受体
分子内力
接受者
电子转移
烟酰胺腺嘌呤二核苷酸磷酸
电子传输链
组合化学
有机化学
酶
物理
凝聚态物理
生物化学
氧化酶试验
作者
Hao Zhao,Fei Huang,Guanhua Liu,Yunting Liu,Yujie Wang,Xinlong Liu,Chengfen Xing,Jing Wang,Xiaoyang Yue,Yanjun Jiang
出处
期刊:ACS Sustainable Chemistry & Engineering
[American Chemical Society]
日期:2024-08-12
标识
DOI:10.1021/acssuschemeng.4c02542
摘要
A nicotinamide adenine dinucleotide phosphate (NADPH)-mediated photoenzyme-coupled catalytic system is an attractive and green strategy for chemical conversion. However, artificial photocatalytic NADPH regeneration with low activity and selectivity has posed a challenge when it is coupled with enzyme catalysis. Therefore, we developed a strategy to prepare an "all-in-one" photocatalyst (Rh-sp2c-COF) by immobilizing an electron mediator ([Cp*Rh(bpy)(H2O)]2+) in a covalent organic framework (COF) with a donor−π–acceptor structure for efficient photocatalytic NADPH regeneration. The immobilized [Cp*Rh(bpy)(H2O)]2+ not only achieves specific regeneration of 1,4-NADPH but also improves the efficiency of electron transfer and utilization by constructing intramolecular electron transfer channels and electron buffer tanks. In addition, the donor−π–acceptor structure expands the range of light absorption and promotes effective carrier separation and directional transfer. The turnover frequency of NADPH regeneration by Rh-sp2c-COF reaches 2.17 mmol·gCOF–1·h–1, which is 3.28, 1.99, and 4.5 times higher than those of sp2c-COF, sp2c-COF + free [Cp*Rh(bpy)(H2O)]2+, and imine-COF, respectively. Finally, Rh-sp2c-COF coupled with ene reductase achieves efficient asymmetric hydrogenation of C═C. This work provides an approach for accurate predesign of photocatalysts to achieve efficient conversion and utilization of solar energy.
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