Facile manufacture of COF-based mixed matrix membranes for efficient CO2 separation

Mixed-matrix membranes containing covalent-organic frameworks (COFs) and polymer phase hold great promise for effective and economical CO2 separation due to the robust and tunable porous framework structures of COFs. However, the pore sizes of most reported COFs are larger than gas molecules. Meanwhile, the undesired COF aggregation impedes the preparation of continuous and defect-free membranes. Herein, we describe a new strategy for the facile manufacture of 2D-COF based mixed-matrix membranes via in situ "bottom-up" growth approach which involved the admixing of COF precursors with PEO monomers at the molecular level in a solvent-free system. Free radical polymerization allowed the formation of polymer membranes containing welldispersed COF precursors. The 2D-COFs with uniform distributions were further generated via the covalent linkages of precursors within the cross-linked polymer network under microwave assisted Zincke reaction. The resulting mixed-matrix membrane exhibited a remarkable permeability of 803.9 barrer for CO2 and selectivities of 61.4, 19.8, 15.0 for CO2/N2, CO2/CH4, CO2/H2, respectively, exceeding the known upper-bound limits reported for polymer membranes. Meanwhile, the membranes displayed a one-month stability confirming its exceptional long-term operational stability and great potential for industrial gas separations.