Metal–organic framework (MOF) glasses are promising candidates for membrane fabrication due to their significant porosity, the ease of processing, and most notably, the potential to eliminate the grain boundary that is unavoidable for polycrystalline MOF membranes. Herein, we developed a ZIF‐62 MOF glass membrane and exploited its intrinsic gas‐separation properties. The MOF glass membrane was fabricated by melt‐quenching treatment of an in situ solvothermally synthesized polycrystalline ZIF‐62 MOF membrane on a porous ceramic alumina support. The molten ZIF‐62 phase penetrated into the nanopores of the support and eliminated the formation of intercrystalline defects in the resultant glass membrane. The molecular sieving ability of the MOF membrane is remarkably enhanced via vitrification. The separation factors of the MOF glass membrane for H2/CH4, CO2/N2 and CO2/CH4 mixtures are 50.7, 34.5, and 36.6, respectively, far exceeding the Robeson upper bounds.

Metal–organic framework (MOF) glasses are promising candidates for membrane fabrication due to their significant porosity, the ease of processing, and most notably, the potential to eliminate the grain boundary that is unavoidable for polycrystalline MOF membranes. Herein, we developed a ZIF‐62 MOF glass membrane and exploited its intrinsic gas‐separation properties. The MOF glass membrane was fabricated by melt‐quenching treatment of an in situ solvothermally synthesized polycrystalline ZIF‐62 MOF membrane on a porous ceramic alumina support. The molten ZIF‐62 phase penetrated into the nanopores of the support and eliminated the formation of intercrystalline defects in the resultant glass membrane. The molecular sieving ability of the MOF membrane is remarkably enhanced via vitrification. The separation factors of the MOF glass membrane for H2/CH4, CO2/N2 and CO2/CH4 mixtures are 50.7, 34.5, and 36.6, respectively, far exceeding the Robeson upper bounds.

ZIF-8 membranes have emerged as the most promising candidate for propylene/propane (C 3 H 6 /C 3 H 8) separation through its precise molecular sieving characteristics. The poor reproducibility and durability, and high cost, thus far hinder the scalable synthesis and industrial application of ZIF-8 membranes. Herein, we report a semi-solid process featuring ultrafast and high-yield synthesis, and outstanding scalability for reproducible fabrication of ZIF-8 membranes. The membranes show excellent C 3 H 6 /C 3 H 8 separation performance in a wide temperature and pressure range, and remarkable stability over 6 months. The ZIF-8 membrane features dimethylacetamide entrapped ZIF-8 crystals retaining the same diffusion characteristics but offering enhanced adsorptive selectivity for C 3 H 6 /C 3 H 8. The ZIF-8 membrane was prepared on a commercial flat-sheet ceramic substrate. A prototypical plate-and-frame membrane module with an effective membrane area of about 300 cm 2 was used for efficient C 3 H 6 /C 3 H 8 separation.

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ZIF-8 membranes have emerged as the most promising candidate for propylene/propane (C 3 H 6 /C 3 H 8) separation through its precise molecular sieving characteristics. The poor reproducibility and durability, and high cost, thus far hinder the scalable synthesis and industrial application of ZIF-8 membranes. Herein, we report a semi-solid process featuring ultrafast and high-yield synthesis, and outstanding scalability for reproducible fabrication of ZIF-8 membranes. The membranes show excellent C 3 H 6 /C 3 H 8 separation performance in a wide temperature and pressure range, and remarkable stability over 6 months. The ZIF-8 membrane features dimethylacetamide entrapped ZIF-8 crystals retaining the same diffusion characteristics but offering enhanced adsorptive selectivity for C 3 H 6 /C 3 H 8. The ZIF-8 membrane was prepared on a commercial flat-sheet ceramic substrate. A prototypical plate-and-frame membrane module with an effective membrane area of about 300 cm 2 was used for efficient C 3 H 6 /C 3 H 8 separation.