| Summary: | Distillation and absorption columns offer significant energy demands for future development in the petrochemical and fine chemical industries. Membranes and adsorbents are attractive alternatives to these classical separation units due to lower operating cost and easy device fabrication; however, membranes possess an upper limit in separation performance that results in a trade-off between selectivity (purity) and permeability (productivity) for the target gas product, and adsorbents require the need to be water-resistant to natural gas streams in order to withstand typical gas compositions. Composite membranes, or mixed-matrix membranes, are an appealing alternative to pure polymeric membrane materials by use of a molecular sieve “filler” phase which has higher separation performance than the pure polymer. In this thesis, the structure-property-processing relationships for a new class of molecular sieves known as zeolitic imidazolate frameworks (ZIFs) are investigated for their use as the filler phase in composite membranes or as adsorbents. These materials show robust chemical and thermal stability and are a promising class of molecular sieves for acid gas (CO₂/CH₄) separations. The synthesis of mixed-linker ZIFs is first investigated. It is shown that the organic linker composition in these materials is controllable without changing the crystal structure or significantly altering the thermal decomposition properties. There are observable changes in the adsorption properties, determined by nitrogen physisorption, that depend on the overall linker composition. The results suggest the proposed synthesis route facilitates a tunable process to control either the adsorption or diffusion properties depending on the linker composition. The structure-property-processing relationship for a specific ZIF, ZIF-8, is then investigated to determine the proper processing conditions necessary for fabricating defect-free composite membranes. The effect of ultrasonication shows an unexpected coarsening of ZIF-8 nanoparticles that grow with increased sonication time, but the structural integrity is shown to be maintained after sonication by using X-ray diffraction, Pair Distribution Function analysis, and nitrogen physisorption. The permeation properties of composite membranes revealed that intense ultrasonication is necessary to fabricate defect-free membranes for CO₂/CH₄ gas separations. Finally, the separation properties of mixed-linker ZIFs is investigated by using adsorption studies of CO₂ and CH₄ and using composite membranes with differing linker compositions. Adsorption properties of mixed-linker ZIFs reveal that these materials possess tunable surface properties, and a selectivity enhancement of six fold over ZIF-8 is observed with mixed-linker ZIFs without changing the crystal structure. Gas permeation studies of composite membranes reveal that the separation properties of mixed-linker ZIFs are different from their parent frameworks. By proper selection of mixed-linker ZIFs, there is an overall improvement of separation properties in the composite membranes when compared to ZIF-8.
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