Two‐in‐One Strategy for Photoinduced Atom Transfer Radical Polymerization Using Cu(I)‐Phenothiazine Integrated Covalent Organic Frameworks
Abstract
Abstract The concurrent development of innovative photocatalysts (PCs) that achieve fast reaction rates while ensuring efficient catalyst recycling remains a significant challenge for large‐scale polymer production. Herein, we present a “two‐in‐one” strategy that combines a photoactive component with a cyclic trinuclear Cu(I)‐incorporated triangular complex as the intrinsic copper source within three imine‐linked covalent organic frameworks (COFs). As‐synthesized photoactive Cu(I)‐containing COFs demonstrated exceptional performance in aqueous photoinduced atom transfer radical polymerization (photo‐ATRP), achieving a record‐breaking turnover number (TON) of 1640 and turnover frequency (TOF) of 82 min −1 , while maintaining narrow polymer dispersity of 1.20. Such performance surpasses previously reported heterogeneous PCs designed for photo‐ATRP. Notably, the COF‐encapsulated “two‐in‐one” catalytic design endows the system with remarkable operational stability and near‐quantitative catalyst recovery. More importantly, such new COFs demonstrate outstanding process compatibility, enabling scalable production of well‐defined block copolymers in a single microreactor, without intermediate purification.
Article Details
Authors (9)
Qiongshan Zhang
College of Chemistry and Molecular Sciences, State Key Laboratory of Power Grid Environmental Protection Wuhan University Wuhan Hubei 430072 China
Congying Song
Shandong Provincial Key Laboratory for Science of Material Creation and Energy Conversion Science Center for Material Creation and Energy Conversion Institute of Frontier Chemistry School of Chemistry and Chemical Engineering Shandong University Qingdao P.R. China
Xue Li
Xuanzi Ye
State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Synergistic Chem‐Bio Synthesis, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University Dongchuan Road 800 Shanghai 200240 China
Kaiyue Jiang
The Soft2D Lab, State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 130 Dongchuan Road, Shanghai 200240, China
Bin Zhang
Tao Cai
Academy for Advanced Interdisciplinary Studies, Frontiers Science Center of New Organic Matters, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, College of Outstanding Engineers
Xiaodong Zhuang
The Soft2D Lab, State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 130 Dongchuan Road, Shanghai 200240, China
Fuzhen Xuan
School of Mechanical and Power Engineering East China University of Science and Technology–Utrecht University Joint Research Center for Sustainable and Circular Chemistry and Chemical Engineering East China University of Science and Technology Shanghai 200237 China