Use in Photoredox Catalysis of Stable Donor–Acceptor Covalent Organic Frameworks and Membrane Strategy

• Published in: Advanced functional materials 2023-11, Vol.33 (48), p.n/a
• Main Authors: Li, Jingjun, Gao, Shui‐Ying, Liu, Jiaying, Ye, Shihua, Feng, Yanan, Si, Duan‐Hui, Cao, Rong
• Format: Article
• Language: English
• Subjects: Bonding strength; Charge transfer; charge transfers; donor–acceptor covalent organic frameworks; H‐bonds; Mass transfer; Materials science; Membranes; membrane‐based mass transfers; Optimization; Optoelectronics; Photocatalysis; Photoredox catalysis; Polyvinylidene fluorides; Stability; Stabilization
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202305735

Optoelectronic attributes notwithstanding donor–acceptor covalent organic frameworks (D–A COFs) are not durable photocatalysts in many cases. Herein, a stabilization strategy of D–A COFs by intramolecular hydrogen (H)‐bonds and a membrane‐based mass transfer strategy for photocatalytic modulation are reported. The crystalline stability design of COF is cored at the strong π–π interactions and the H‐bonds of adjacent tetrakis(4‐formylphenyl)pyrene and naphthalenediimide units and the D–A charge transfer is designed for efficiency optimization. The well‐defined, stable structure and charge dynamics of D–A COF, and the structure‐controlled reactive oxygen species yields are confirmed. In two photoredox models, the COF presents both robust activity and stability and is further integrated with the mass transfer optimization of the COFs/polyvinylidene fluoride membrane. The membrane is recycled at least 15 times, and the turnover frequency value of g‐scale amine coupling is as high as 62.4 h−1. This work offers a facile approach to the stabilization design of D–A COFs and explores a general membrane‐based mass transfer strategy for photocatalysis. Intramolecular hydrogen (H)‐bonds and donor–acceptor (D–A) concepts are integrated into the design of novel covalent organic frameworks (COFs) to fulfill both efficiency and stability targets. Stably ordered skeleton and D–A charge dynamics lead the COF to be efficient for independent photocatalytic coupling and dehalogenation reactions, and the membrane‐based mass transfer strategy selectively boosts the coupling.