Covalent Organic Frameworks for CO₂ Capture: From Design to Application

The increasing concentration of atmospheric CO₂ has intensified the urgent need for efficient and sustainable carbon capture technologies. Covalent organic frameworks (COFs) have emerged as a highly promising class of porous crystalline materials for CO₂ adsorption and separation owing to their structural tunability, high surface area, and precisely designable pore environments. This review summarizes recent advances in COF-based CO₂ capture systems, covering pristine COFs, functionalized frameworks, composite materials, and membrane-based architectures. In pristine COFs, CO₂ adsorption is mainly governed by micropore confinement and physisorption within well-defined channels, where surface area and pore size distribution play key roles. Functionalized COFs introduce additional active sites, including amine groups, heteroatoms, ionic functionalities, and alkali metal centers, which significantly enhance CO₂ affinity through stronger electrostatic and acid-base interactions, often leading to mixed physisorption-chemisorption behavior. Composite COFs and mixed-matrix membranes further improve performance through synergistic effects, interfacial engineering, and enhanced mass transport. Despite these advantages, challenges remain in achieving an optimal balance between capacity, selectivity, and regenerability under realistic conditions such as humidity, low CO₂ partial pressure, and multicomponent gas streams. Issues related to scalable synthesis, structural stability, and processability also limit practical applications. Overall, this review highlights key structure-property relationships and outlines future directions, including humid-stable COFs, direct air capture, computational design strategies, and advanced membrane technologies, for next-generation CO₂ capture materials.