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Pore Engineering in Metal–Organic Frameworks for Sub-Angstrom Molecular Separation

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The continuing increase in atmospheric CO2 to concentrations exceeding 400 ppm has attracted considerable attention from both scientists and policymakers. Industrial fossil fuel consumption generates a significant amount of CO2 emissions, and in particular, energy-intensive molecular separations that require thermal processes, such as distillation, drying, or evaporation, are responsible for a large portion of these emissions and account for 45-55% of the annual US industrial energy use. Molecular separations are vital steps in many indispensable applications ranging from water and air purification to fuel and feedstock chemical production; however, continuing to accept the substantial carbon footprint penalty associated with these processes is unsustainable. The development of effective non-thermal separation methods would not only alleviate the damage to our climate through decarbonization via reduced CO2 emissions, but also reduce monetary costs for these processes.Seven chemical separations, including hydrocarbons, xenon/krypton, and benzene derivatives, have been identified as having the most significant impact on our world. Current methods for these separations are energy-intensive, often involving cryo- or high-temperature distillation or adsorption processes. In this thesis, we focus on the development of novel materials and methods for non-thermal separation processes, specifically using metal–organic frameworks (MOFs). MOFs are a class of porous materials with tunable structures and properties that can be tailored to specific separation applications. We explored the design and synthesis of MOFs for the separation of various target molecules, including xylene and hexane isomers. Through a combination of experimental and computational approaches, we investigated the underlying mechanisms governing the separation performance of these MOFs, identifying key factors that affect their selectivity and efficiency. Our work provides insights into the development of sustainable and cost-effective separation methods, laying the foundation for the rational design of MOFs for a wide range of separation applications. We investigate the structure-function relationship of a sub-class of MOFs that is unique in its choice of linkers.

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