Assembly‐Dissociation‐Reconstruction Synthesis of Covalent Organic Framework Membranes with High Continuity for Efficient CO2 Separation

Abstract Covalent organic frameworks (COFs), at the forefront of porous materials, hold tremendous potential in membrane separation; however, achieving high continuity in COF membranes remains crucial for efficient gas separation. Here, we present a unique approach termed assembly‐dissociation‐reconstruction for fabricating COF membranes tailored for CO 2 /N 2 separation. A parent COF is designed from two‐node aldehyde and three‐node amine monomers and dissociated to high‐aspect‐ratio nanosheets. Subsequently, COF nanosheets are orderly reconstructed into a crack‐free membrane by surface reaction under water evaporation. The membrane exhibits high crystallinity, open pores and a strong affinity for CO 2 adsorption over N 2 , resulting in CO 2 permeance exceeding 1060 GPU and CO 2 /N 2 selectivity surpassing 30.6. The efficacy of this strategy offers valuable guidance for the precise fabrication of gas‐separation membranes.