近日，南方科技大学徐强团队实现了光催化生产H₂O₂的共价有机框架的酶-点击合成修饰。该项研究成果发表在2025年9月11日出版的《美国化学会志》上。

合成后修饰（PSM）是调整共价有机框架（COFs）结构和功能的一种强有力的策略。

研究组提出了一种新的酶促PSM策略，用于COFs内的官能团工程。利用酶催化，2-羟乙基硫（-S-EtOH）和乙基硫（-S-Et）基团在环境水条件下以高接枝效率共价植入COF孔通道，突出了该方法温和、高效和生态友好的性质。理论计算和原位实验表明，-S-EtOH的加入不仅促进了激子解离，具有较高的电荷分离效率，而且增加了氢化中间体形成的质子供应，降低了吉布斯自由能差（ΔG），从而促进了光催化生成H₂O₂。该工作弥合了酶催化和网状材料工程之间的差距，为COF合成后改性和功能化提供了概念上的突破。

附：英文原文

Title: Enzyme-Click Postsynthetic Modification of Covalent Organic Frameworks for Photocatalytic H2O2 Production

Author: Quan Zuo, Bingxian Chu, Xinhe Ye, Fayan Li, Lei Li, Qiang Xu

Issue&Volume: September 11, 2025

Abstract: Postsynthetic modification (PSM) is a powerful strategy for tailoring the structure and functionality of covalent organic frameworks (COFs). In this work, we present a novel enzymatic PSM strategy for functional group engineering within COFs. By taking advantage of enzymatic catalysis, 2-hydroxyethylthio (-S-EtOH) and ethylthio (-S-Et) groups were covalently implanted within the COF pore channels with high grafting efficiency under ambient aqueous conditions, highlighting the mild, efficient, and ecofriendly nature of this approach. Theoretical calculations and in situ experiments revealed that the incorporation of -S-EtOH not only promotes exciton dissociation with a superior charge separation efficiency but also strengthens the proton supply for the formation of hydrogenation intermediates and lowers the Gibbs free energy difference (ΔG), thereby facilitating the photocatalytic H2O2 production. Our work bridges the gap between enzymatic catalysis and reticular materials engineering, offering a conceptual breakthrough in COF postsynthetic modification and functionalization.

DOI: 10.1021/jacs.5c09922

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c09922