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

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 CO2/N2 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 CO2 adsorption over N2, resulting in CO2 permeance exceeding 1060 GPU and CO2/N2 selectivity surpassing 30.6. The efficacy of this strategy offers valuable guidance for the precise fabrication of gas‐separation membranes.