Metal–organic frameworks (MOFs) are hybrid organic–inorganic nanoporous materials that exhibit regular crystalline lattices with relatively well-defined pore structures. Chemical functionalization of the organic linkers in the structures of MOFs affords facile control over pore size and chemical/physical properties, making MOFs attractive for a variety of industrial applications including membrane-based gas separations. A wealth of reports exists discussing the synthesis and applications of MOFs; however, relatively few reports exist discussing MOF membranes. This disparity owes to challenges associated with fabricating films of MOF materials, including poor substrate–film interactions, moisture sensitivity, and thermal/mechanical instability. Since even nanometer-scale cracks and defects can affect the performance of a membrane for gas separation, these challenges are particularly acute for the fabrication of MOF membranes. Here, we review recent progress on MOF membranes with an emphasis on their fabrication techniques, challenges involved in membrane synthesis, reported strategies to address these challenges (issues), and gas separation performance. Finally, we conclude with our perspectives on future research directions in this area.

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Metal-organic frameworks (MOFs) are attractive for gas separation membrane applications due to their microporous channels with tunable pore shape, size, and functionality. Conventional MOF membrane fabrication techniques, namely in situ and secondary growth, pose challenges for their wider commercial applications. These challenges include reproducility, scalability, and high manufacturing cost. Recognizing that the coordination chemistry of MOFs is fundamentally different from the covalent chemistry of zeolites, we developed a radically different strategy for MOF membrane synthesis. Using this new technique, we were able to produce continuous well-intergrown membranes of prototypical MOFs, HKUST-1 and ZIF-8, in a relatively short period of time (tens of min). With a minimal consumption of precursors and a greatly simplified synthesis protocol, our new technique provides potential for a continuous, scalable, reproducible, and easily commercializable route for the rapid synthesis of MOF membranes. RTD-prepared MOF membranes show greatly improved gas separation performances as compared to those prepared by conventional solvothermal methods, indicating improved membrane microstructure.