南开大学陈瑶团队开发了光酶法还原CO₂的烯烃键合共价有机框架工程。相关研究成果于2022年1月17日发表于国际一流学术期刊《德国应用化学》。

在全球能源和环境危机的背景下，开发新的二氧化碳减排和转化技术具有深远的意义。

为了应对这一挑战，研究人员构建了一种新型的二氧化碳还原人工光酶系统，使用合理设计的介孔烯烃连接共价有机框架（COF）作为多孔固体载体，用于共固定甲酸脱氢酶（FDH）和Rh基电子介体。通过调节Rh电子介体的掺入量，有利于从NAD⁺中再生烟酰胺辅因子（NADH），表观量子产率可高达9.17±0.44%，超过了所有报道的由晶体框架材料构建的NADH再生光催化剂。最后，组装的光触媒-酶耦合系统可以选择性地将CO₂转化为甲酸，效率高，重复使用性好。

该研究展示了第一个使用COFs固定酶的例子，用于利用太阳能生产增值化学品的人工光合作用系统。

附：英文原文

Title: Engineering Olefin-Linked Covalent Organic Frameworks for Photoenzymatic Reduction of CO2

Author: Zhengfeng Zhao, Dong Zheng, Menglei Guo, Jiangyue Yu, Sainan Zhang, Zhenjie Zhang, Yao Chen

Issue&Volume: 2022-01-17

Abstract: It is of profound significance concerning the global energy and environmental crisis to develop new techniques that can reduce and convert CO  2  . To address this challenge, we build a new type of artificial photoenzymatic system for CO  2  reduction, using a rationally designed mesoporous olefin-linked covalent organic framework (COF) as the porous solid carrier for co-immobilizing formate dehydrogenase (FDH) and Rh-based electron mediator. By adjusting the incorporating content of Rh electronic mediator, which facilitates the regeneration of nicotinamide cofactor (NADH) from NAD  +  , the apparent quantum yield can reach as high as 9.17±0.44%, surpassing all reported NADH regenerated photocatalysts constructed by crystalline framework materials. Finally, the assembled photocatalyst-enzyme coupled system can selectively convert CO  2  to formic acid with high efficiency and good reusability. This work demonstrates the first example using COFs to immobilize enzymes for articial photosynthesis systems that utilize solar energy to produce value-added chemicals.

DOI: 10.1002/anie.202200261

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202200261