A Versatile Method for Preparation of BrCOFs Aerogels and Efficient Functionalization via Suzuki–Miyaura Reaction

Abstract Covalent organic frameworks (COFs) aerogels solve the restrictions on processability and application caused by the insolubility and non‐fusibility of powders while avoiding the inaccessibility of pore structures by dense stacking. At the current start‐up stage where COFs aerogels are scarce and difficult to synthesize, design of generalized synthetic methods play an indispensable role in guiding and developing COFs aerogels. Moreover, evolving the functionality of COF aerogels is equal vital, which achieves higher performance and broader practical applications. In this work, for the first time, processable BrCOFs aerogels have been synthesized without vacuum by seven kind polar solvents, which realizes general preparation of BrCOFs aerogels. It is extremely friendly to the inapplicability for some scenarios. Furthermore, by Suzuki‐Miyaura cross‐coupling reaction, BrCOFs aerogels are endows with cyano groups (‐CN), trifluoromethyl (‐CF 3 ) and methyl sulfonyl (‐SO 2 ‐CH 3 ) efficiently. As a proof‐of‐concept, BrCOFs‐SO 2 ‐CH 3 aerogels served as a quasi‐solid electrolyte for lithium‐metal batteries (LMBs), which effectively enhance the performance of batteries.