College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P. R. China) E-mail: l.qust.edu.cn.
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Shandong Energy Institute, Qingdao, 266101, P. R. China.
Chemistry. 2022 Oct 4;28(55):e202201430. doi: 10.1002/chem.202201430. Epub 2022 Aug 8.
Natural photosynthesis is a highly unified biocatalytic system, which coupled cofactor (NAD(P)H) regeneration and enzymatic CO reduction efficiently for solar energy conversion. Mimicking nature, a novel system with Rh complex covalently grafted onto NH -functionalized polymeric carbon nitride (NH -PCN) was constructed. The integrated connection of the light-harvesting and electron mediation modules as Rh -N-PCN could promote the efficient NAD reduction to NADH. As a result, the integrated system exhibited a conversion of ∼66 % within 20 minutes. By further coupling in situ generated NADH with formate dehydrogenase (FDH), a photoenzymatic production of formic acid (HCOOH) from CO was accomplished. Moreover, by immobilizing FDH onto a hydrophobic membrane, an enhanced HCOOH production of ∼5.0 mM can be obtained due to the concentrated CO on the gas-liquid-solid three-phase interface. Our work herein provides an integrated strategy for coupling the anchored electron mediator with immobilized enzyme for enhanced artificial photosynthesis.
自然光合作用是一个高度统一的生物催化体系，它有效地将辅助因子（NAD(P)H）再生和酶促 CO 还原偶联起来，用于太阳能转换。受自然启发，构建了一种将 Rh 配合物共价接枝到 NH-功能化聚合物氮化碳（NH-PCN）上的新型体系。光收集和电子传递模块的集成连接作为 Rh-N-PCN 可以促进 NAD 的有效还原为 NADH。因此，该集成系统在 20 分钟内实现了约 66%的转化。通过进一步将原位生成的 NADH与甲酸脱氢酶（FDH）偶联，可以从 CO 完成光酶法生产甲酸（HCOOH）。此外，通过将 FDH 固定在疏水性膜上，由于在气-液-固三相界面上浓缩的 CO，可以获得约 5.0 mM 的增强 HCOOH 产量。本工作为通过固定化酶与锚定电子介体偶联来增强人工光合作用提供了一种综合策略。
