Metal-organic cages improving microporosity in polymeric membrane for superior CO₂ capture

Mixed matrix membranes, with well-designed pore structure inside the polymeric matrix via the incorporation of inorganic components, offer a promising solution for addressing CO₂ emissions. Here, we synthesized a series of novel metal organic cages (MOCs) with aperture pore size precisely positioned between CO₂ and N₂ or CH₄. These MOCs were uniformly dispersed in the polymers of intrinsic microporosity (PIM-1). Among them, the MOC-Ph cage effectively modulated chain packing and optimized the microporous structure of the membrane. Remarkably, the PIM-Ph-5% membrane shows superior performance, achieving an excellent CO₂ permeability of 8803.4 barrer and CO₂/N₂ selectivity of 59.9, far exceeding the 2019 upper bound. This approach opens opportunities for improving the porous structure of polymeric membranes for CO₂ capture and other separation applications.