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Despite their potential for the scalable production of mixed-matrix membranes (MMMs), the MMMs prepared by the polymer-modification-enabled in situ metal–organic framework formation (PMMOF) process showed a considerable reduction in gas permeability as the filler loading increased. It was hypothesized that a correlation existed between the decrease in permeability and the change in the properties of the polymer, such as free volume and chain flexibility, upon in situ MOF formation. Herein, we aim to address the permeability reduction by using a cross-linked polyimide (6FDA-DAM:DABA (3:2)). It was found the degree of cross-linking affected not only the properties of the polymer, but also the in situ formation of the ZIF-8 filler particles in the cross-linked polymer. The proper degree of cross-linking resulted in suppressing C3H6 permeability reduction, suggesting a possible strategy to overcome the issue of PMMOF. The swelling of the polymer followed by chain rearrangement during the PMMOF, as well as the structural rigidity of the polymer, were found to be critical in mitigating permeability reduction. 

In the last decade, zeolitic imidazolate frameworks (ZIFs) have been studied extensively for their potential as selective separation membranes. In this review, we highlight unique structural properties of ZIFs that allow them to achieve certain important separations, like that of propylene from propane, and summarize the state of the art in ZIF thin-film deposition on porous substrates and their modification by postsynthesis treatments. We also review the reported membrane performance for representative membrane synthesis approaches and attempt to rank the synthesis methods with respect to potential for scalability. To compare the dependence of membrane performance on membrane synthesis methods and operating conditions, we map out fluxes and separation factors of selected ZIF-8 membranes for propylene/propane separation. Finally, we provide future directions considering the importance of further improvements in scalability, cost effectiveness, and stable performance under industrially relevant conditions. 

Sodalite zeolitic-imidazole frameworks (ZIFs) show great potential due to their effective aperture sizes suitable for small gas separations. Numerous efforts have, therefore, been made in tuning their effective aperture sizes to control and enhance their molecular sieving properties. Herein, we present a new strategy to finely tune the effective aperture size of CdIF-1, a cadmium-substituted ZIF-8 analogue, based on thermal amorphization. Among several ZIF-8 analogues screened, CdIF-1 was found to be the only one that could be thermally amorphized. The controlled amorphization reduced the long-range structural order while preserving the short-range order, thereby systematically densifying the ZIF structure and consequently affecting its effective aperture. Meanwhile, it was found that amorphization enhanced the flexibility of the framework, resulting in accessible pores at temperatures above 273 K. As compared to its crystalline counterpart, partially amorphized CdIF-1 showed significantly improved diffusion and adsorption selectivities of n -C 4 H 10 /i-C 4 H 10 ( i.e. , 1.5 → 40.7 and 1.1 → 4.9, respectively), likely due to the amorphization-induced tuning of its effective aperture size. 

Zeolitic-imidazole framework-8 (ZIF-8) membranes have shown exceptional propylene/propane separation performances. Their commercial applications have, however, been impeded by several challenges. One such challenge is the difficulty of managing microstructural defects ( i.e. , grain boundary defects) in a consistent manner, leading to poor membrane performances and ultimately to a reproducibility issue. Herein, we introduce a new effective strategy to seal the microstructural defects of polycrystalline ZIF-8 membranes using post-synthetic surface polymerization which consists of two steps: (1) introduction of initiator ligands on the membrane surface by post-synthetic ligand exchange and (2) in situ polymerization of poly(methyl methacrylate) (PMMA) via atom transfer radical polymerization. The ZIF-8 membranes were fully covered with ultra-thin PMMA layers of sub-10 nm thickness, increasing the propylene/propane separation factor from ∼60 to ∼106 with unexpectedly increased propylene permeance, effectively improving the membrane reproducibility. The enhanced separation properties of the PMMA-coated ZIF-8 membranes were attributed to the ultra-thin PMMA layers as well as to the possible facilitated propylene transport by Cu ions in the PMMA layers.