Membrane-based gas separations are energy efficient processes; however, major challenges remain to develop high-performance membranes enabling the replacement of conventional separation processes. Herein, a new fluorinated MOF-based mixed-matrix membrane is reported, which is formed by incorporating the MOF crystals into selected polymers via a facile mixed-matrix approach. By finely controlling the molecular transport in the channels through the MOF apertures tuned by metal pillars and at the MOF-polymer interfaces, the resulting fluorinated MOF-based membranes exhibit excellent molecular sieving properties. These materials significantly outperform state-of-the-art membranes for simultaneous removal of H S and CO from natural gas-a challenging and economically important application. The robust fluorinated MOFs (NbOFFIVE-1-Ni, AlFFIVE-1-Ni), pave a way to efficient membrane separation processes that require precise discrimination of closely sized molecules.

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Membrane-based gas separations are energy efficient processes; however, major challenges remain to develop highperformance membranes enabling replacement of conventional separation processes. Here, a new fluorinated MOF-based mixedmatrix membrane is reported, which is formed by incorporating the MOF crystals into selected polymers via a facile mixed-matrix approach. By finely controlling the molecular transport in the channels through MOF apertures tuned by metal pillars and at the MOFpolymer interfaces, the resulting fluorinated MOF-based membranes exhibit excellent molecular sieving properties. We show that these materials significantly outperform state-of-the-art membranes for simultaneous removal of H 2 S and CO 2 from natural gas-a challenging and economically-important application. The robust fluorinated MOFs (NbOFFIVE-1-Ni, AlFFIVE-1-Ni), with tunable channel apertures provided by tuning the metal pillars and/or organic linker, pave a new avenue to efficient membrane separation processes that require precise discrimination of closely sized molecules.

Demand for energy-efficient gas separations exists across many industrial processes, and membranes can aid in meeting this demand. Carbon molecular sieve (CMS) membranes show exceptional separation performance and scalable processing attributes attractive for important, similar-sized gas pairs. Herein, we outline a mathematical and physical framework to understand these attributes. This framework shares features with dual-mode transport theory for glassy polymers; however, physical connections to CMS model parameters differ from glassy polymer cases. We present evidence in CMS membranes for a large volume fraction of microporous domains characterized by Langmuir sorption in local equilibrium with a minority continuous phase described by Henrys law sorption. Using this framework, expressions are provided to relate measurable parameters for sorption and transport in CMS materials. We also outline a mechanism for formation of these environments and suggest future model refinements.

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