A Universal Room‐Temperature Approach to Large‐Area Continuous COFs Film for Photocatalytic Coupling of Amines

Abstract Large‐area continuous covalent organic frameworks (COFs) film is highly desirable for the large‐scale continuous selective photocatalytic coupling of benzylamine (BA); however, traditional synthetic methods for preparing COFs films still suffer from the issues of harsh reaction condition, film breakage, and high energy‐consumption. Herein, a room‐temperature strategy is reported for making large‐area continuous imine‐based COFs film through the “infiltration‐reaction‐assembly” mechanism, demonstrating that such strategy is quite universal for making four types of large‐area COFs films. The as‐made PyTTA‐TPA (PyTTA: 1，3，6，8‐tetrakis(4‐aminophenyl)pyrene, TPA: p‐benzaldehyde) COFs film exhibits excellent catalytic performance for selective photocatalytic coupling of benzylamine (BA) with a high conversion rate of 98.2% and high selectivity of 97% in 3 h, which is the best photocatalytic performance in all reported photocatalysts. In addition, the as‐made COFs film is quite general for achieving photocatalytic coupling of other amine derivatives with outstanding photocatalytic performance of ≈100% conversion rate. Overall, this work brings a significant development for the room‐temperature synthesis of large‐area continuous COFs film to photocatalytic reaction.