广东工业大学韩彬团队实现了全共轭Sp²碳链共价有机框架加速激子过程用于水修复的单线态氧光合作用。相关论文于2025年5月26日发表在《德国应用化学》杂志上。

通过能量转移的光催化氧气（O₂）活化为单线态氧气（¹O₂）合成提供了一种可持续的方法，但其性能受到超快激子解离和缓慢的系统间交叉（ISC）过程的影响。迄今为止，激子调控仍处于起步阶段。

通过共价有机框架（COF）的连接工程，研究组提出了一种具有强激子相互作用和快速ISC的全共轭sp²碳连接COF（sp²c-Py-Bpy-COFs），用于增强¹O₂光合作用。 sp²c-Py-Bpy-COF以100%的选择性提供了创纪录的高¹O₂收率（624 μM min^-1），约为传统亚胺桥联COF（Im-Py-Bpy-COF，约95.8%的选择性）的8倍，优于有记录的系统。

瞬态吸收光谱和理论研究表明，sp²c-Py-Bpy-COFs的全共轭sp²碳键可以增强库仑相互作用，促进ISC，并推动三重态激子转移到整个COFs基质中的O₂吸附位点，共同促进能量转移过程，实现高效的¹O₂光合作用，绕过传统的电子转移过程。因此，sp²c-Py-Bpy-COFs可以在可见光照射下在几分钟内选择性降解对乙酰氨基酚，并能够在利用自然阳光和溶解氧气的连续流膜反应器（20×30×2 cm）中稳定降解新出现的污染物。

附：英文原文

Title: Fully Conjugated Sp2 Carbon-Linked Covalent Organic Frameworks Enables Accelerated Exciton Process for Superior Singlet Oxygen Photosynthesis for Water Remediation

Author: Siyuan Guo, Kun Zhao, Luwen Liang, Zifan Li, Bin Han, Xinwen Ou, Shan Yao, Zhiqing Lin, Zhimin Dong, Yunhai Liu, Liqun Ye, Bo Weng, Yanpeng Cai, Zhifeng Yang

Issue&Volume: 2025-05-26

Abstract: Photocatalytic oxygen (O2) activation via energy transfer offers a sustainable approach for singlet oxygen (1O2) synthesis, while its performance suffers from the ultrafast exciton dissociation and sluggish intersystem crossing (ISC) process. Up to date, exciton regulation is still in its infancy. Here, via linkage engineering of covalent organic frameworks (COFs), we propose a fully conjugated sp2 carbon-linked COFs (sp2c-Py-Bpy COFs) with strong exciton interaction and fast ISC for boosted 1O2 photosynthesis. The sp2c-Py-Bpy COFs delivers a record-high 1O2 yield (624 μM min–1) with 100% selectivity, which is ca. 8 times that of the traditional imine-bridged COFs (Im-Py-Bpy COFs, ca. 95.8% selectivity), outperforming documented systems. Transient absorption spectroscopy and theoretical investigations demonstrate that the fully conjugated sp2 carbon linkage of sp2c-Py-Bpy COFs can enhance Coulomb interaction, promote ISC and push forward the transfer of triplet exciton to the O2 adsorption sites throughout the COFs matrix, jointly facilitating the energy transfer process for efficient 1O2 photosynthesis and bypassing the traditional electron transfer process. Hence, sp2c-Py-Bpy COFs can selectively degrade acetaminophen within minutes under visible light irradiation and enables stable degradation of emerging pollutants in a continuous flow membrane reactor (20 × 30 × 2 cm) utilizing natural sunlight and dissolved O2.

DOI: 10.1002/anie.202509141

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202509141