Interlayer synergistic reaction of radical precursors for ultraefficient 1 O 2 generation via quinone-based covalent organic framework

作者：Yuan Tao, Yu Hou, Huangsheng Yang, Zeyu Gong, Jiaxing Yu, Huajie Zhong, Qi Fu, Junhui Wang, Fang Zhu, Gangfeng Ouyang · 发表于：Proceedings of the National Academy of Sciences · 年份：2024 · DOI：10.1073/pnas.2401175121 · 被引用次数：93 · 研究领域：Covalent Organic Framework Applications、Advanced Photocatalysis Techniques、Metal-Organic Frameworks: Synthesis and Applications

Singlet oxygen ( 1 O 2 ) is important in the environmental remediation field, however, its efficient production has been severely hindered by the ultrafast self-quenching of the as-generated radical precursors in the Fenton-like reactions. Herein, we elaborately designed lamellar anthraquinone-based covalent organic frameworks (DAQ-COF) with sequential localization of the active sites (C═O) at molecular levels for visible-light-assisted peroxymonosulfate (PMS) activation. Theoretical and experimental results revealed that the radical precursors (SO 5 ·− ) were formed in the nearby layers with the migration distance less than 0.34 nm, via PMS donating electrons to the photogenerated holes. This interlayer synergistic effect eventually led to ultraefficient 1 O 2 production (14.8 μM s −1 ), which is 12 times that of the highest reported catalyst. As an outcome, DAQ-COF enabled the complete degradation of bisphenol A in 5 min with PMS under natural sunlight irradiation. This interlayer synergistic concept represents an innovative and effective strategy to increase the utilization efficiency of ultrashort-lived radical precursors, providing inspirations for subtle structural construction of Fenton-like catalysts.