Merging Polymers of Intrinsic Microporosity and Porous Carbon-Based Zinc Oxide Composites in Novel Mixed Matrix Membranes for Efficient Gas Separation

Mixed matrix membranes (MMMs) have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers. However, achieving a simultaneous enhancement of permeability and selectivity remains a formidable challenge, due to the difficulty of achieving an optimal match between polymers and fillers. In this study, we incorporate a porous carbon- based zinc oxide composite (C@ZnO) into high-permeability polymers of intrinsic microporosity (PIMs) to fabricate MMMs. The dipole-dipole interaction between C@ZnO and PIMs ensures their exceptional compatibility, mitigating the formation of non-selective voids in the resulting MMMs. Concurrently, C@ZnO with abundant interconnected pores can provide additional low- resistance pathways for gas transport in MMMs. As a result, the CO₂ permeability of the optimized C@ZnO/PIM-1 MMMs is elevated to 13215 barrer, while the CO₂/N₂ and CO₂/CH₄ selectivity reached 21.5 and 14.4, respectively, substantially surpassing the 2008 Robeson upper bound. Additionally, molecular simulation results further corroborate that the augmented membrane gas selectivity is attributed to the superior CO₂ affinity of C@ZnO. In summary, we believe that this work not only expands the application of MMMs for gas separation but also heralds a paradigm shift in the application of porous carbon materials.