Mixed matrix membranes, with well-designed pore structure inside the polymeric matrix via the incorporation of inorganic components, offer a promising solution for addressing CO emissions. Here, we synthesized a series of novel metal organic cages (MOCs) with aperture pore size precisely positioned between CO and N or CH. 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 CO permeability of 8803.4 barrer and CO/N selectivity of 59.9, far exceeding the 2019 upper bound. This approach opens opportunities for improving the porous structure of polymeric membranes for CO capture and other separation applications.
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