Monomer Symmetry-Regulated Defect Engineering: In Situ Preparation of Functionalized Covalent Organic Frameworks for Highly Efficient Capture and Separation of Carbon Dioxide

Developing crystalline porous materials with highly efficient CO₂ selective adsorption capacity is one of the key challenges to carbon capture and storage (CCS). In current studies, much more attention has been paid to the crystalline and porous properties of crystalline porous materials for CCS, while the defects, which are unavoidable and ubiquitous, are relatively neglected. Herein, for the first time, we propose a monomer-symmetry regulation strategy for directional defect release to achieve in situ functionalization of COFs while exposing uniformly distributed defect-aldehyde groups as functionalization sites for selective CO₂ capture. The regulated defective COFs possess high crystallinity, good structural stability, and a large number of organized and functionalized aldehyde sites, which exhibit one of the highest selective separation values of all COF sorbing materials in CO₂/N₂ selective adsorption (128.9 cm³/g at 273 K and 1 bar, selectivity: 45.8 from IAST). This work not only provides a new strategy for defect regulation and in situ functionalization of COFs but also provides a valuable approach in the design and preparation of new adsorbents for CO₂ adsorption and CO₂/N₂ selective separation.