High-Performance Mixed-Matrix Membranes Using a Zeolite@MOF Core-Shell Structure Synthesized via Ion-Exchange-Induced Crystallization and Post-Synthetic Conversion.

ABSTRACT

Strategic design of nanostructures, such as the core-shell configuration, offers a promising avenue to harness the desired properties while mitigating the inherent limitations of individual materials. In our pursuit of synergizing the advantages of two distinct porous materials, namely, zeolites and metal-organic frameworks (MOFs), we aimed to develop the zeolite@MOF core-shell structures. To synthesize this targeted material while minimizing undesirable side reactions, we devised an innovative approach involving ion-exchange-induced crystallization and post-synthetic conversion. This method enabled the exclusive growth of a MOF on the zeolite surface. Specifically, we successfully crafted a CaA@ZIF-8 core-shell structure, employing it in the fabrication of mixed-matrix membranes for CO2 separation. Within this core-shell configuration, the ZIF-8 in the shell played a crucial role in enhancing the filler-polymer interfaces, leading to the development of defect-free membranes. Simultaneously, the CaA zeolite core exhibited a highly selective transport of CO2. The synergistic effects resulted in a membrane incorporating a CaA@ZIF-8 core-shell filler, which demonstrated a high CO2 permeability of 1142 Barrer and a CO2/CH4 selectivity of 43.3, significantly surpassing the established upper limits for polymeric membranes. Our findings underscore the potential of core-shell structures composed of microporous materials for achieving the coveted properties necessary for high-performance gas separation membranes.