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Bi-phase Synthesis of the Zirconium Metal-Organic Framework, UiO-66

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Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward

Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their high stability under standard temperature and pressure due to the strength of the Zirconium-Oxygen coordination bond. However, the acid modulator needed to ensure long range order of the product also prevents complete linker deprotonation. This leads to a powder product that cannot easily be incorporated into continuous MOF membranes. This study therefore implemented a new bi-phase synthesis technique with a deprotonating agent to achieve intergrowth in UiO-66 membranes. Crystal intergrowth will allow for effective gas separations and future permeation testing. During experimentation, successful intergrown UiO-66 membranes were synthesized and characterized. The degree of intergrowth and crystal orientations varied with changing deprotonating agent concentration, modulator concentration, and ligand:modulator ratios. Further studies will focus on achieving the same results on porous substrates.

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2016-12

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Synthesis and Characterization of 2D Metal-organic Frameworks for Mixed-matrix Membrane Gas Separations

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Membrane-based technology for gas separations is currently at an emerging stage of advancement and adoption for environmental and industrial applications due to its substantial advantages like lower energy and operating costs over the conventional gas separation technologies. Unfortunately, the available

Membrane-based technology for gas separations is currently at an emerging stage of advancement and adoption for environmental and industrial applications due to its substantial advantages like lower energy and operating costs over the conventional gas separation technologies. Unfortunately, the available polymeric (or organic) membranes suffer a trade-off between permeance and selectivity. Mixed matrix membranes (MMMs) containing two-dimensional (2D) metal-organic frameworks (MOFs) as fillers are a highly sought approach to redress this trade-off given their enhanced gas permeabilities and selectivities compared to the pure polymeric membrane. These MMMs are increasingly gaining attention by researchers due to their unique properties and wide small- and large-scale gas separation applications. However, straightforward and scalable methods for the synthesis of MOFs nanosheets have thus far been persistently elusive. This study reports the single-phase preparation, and characterization of MMMs with 2D MOFs nanosheets as fillers. The prepared MOF and the polymer matrix form the ‘dense’ MMMs which exhibit increased gas diffusion resistance, and thus improved separation abilities. The single-phase approach was more successful than the bi-phase at synthesizing the MOFs. The influence of sonication power and time on the characteristics and performance of the membranes are examined and discussed. Increasing the sonication power from 50% to 100% reduces the pore size. Additionally, the ultimate effect on the selectivity and permeance of the MMMs with different single gases is reported. Analysis of results with various gas mixers indicates further performance improvements in these MMMs could be achieved by increasing sonication time and tuning suitable membrane thicknesses. Reported results reveal that MMMs are excellent candidates for next-generation gas mixture separations, with potential applications in CO2 capture and storage, hydrogen recovery, alkene recovery from alkanes, and natural gas purification.

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2019-05

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Stability, Transport and Modification of Zeolitic Imidazolate Framework-8 Membranes for Light Hydrocarbon Separations

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Membrane technology is a viable option to debottleneck distillation processes and minimize the energy burden associated with light hydrocarbon mixture separations. Zeolitic imidazolate frameworks (ZIFs) are a new class of microporous metal-organic frameworks with highly tailorable zeolitic pores and unprecedented

Membrane technology is a viable option to debottleneck distillation processes and minimize the energy burden associated with light hydrocarbon mixture separations. Zeolitic imidazolate frameworks (ZIFs) are a new class of microporous metal-organic frameworks with highly tailorable zeolitic pores and unprecedented separation characteristics. ZIF-8 membranes demonstrate superior separation performance for propylene/propane (C3) and hydrogen/hydrocarbon mixtures at room temperature. However, to date, little is known about the static thermal stability and ethylene/ethane (C2) separation characteristics of ZIF-8. This dissertation presents a set of fundamental studies to investigate the thermal stability, transport and modification of ZIF-8 membranes for light hydrocarbon separations.

Static TGA decomposition kinetics studies show that ZIF-8 nanocrystals maintain their crystallinity up to 200○C in inert, oxidizing and reducing atmospheres. At temperatures of 250○C and higher, the findings herein support the postulation that ZIF-8 nanocrystals undergo temperature induced decomposition via thermolytic bond cleaving reactions to form an imidazole-Zn-azirine structure. The crystallinity/bond integrity of ZIF-8 membrane thin films is maintained at temperatures below 150○C.

Ethane and ethylene transport was studied in single and binary gas mixtures. Thermodynamic parameters derived from membrane permeation and crystal adsorption experiments show that the C2 transport mechanism is controlled by adsorption rather than diffusion. Low activation energy of diffusion values for both C2 molecules and limited energetic/entropic diffusive selectivity are observed for C2 molecules despite being larger than the nominal ZIF-8 pore aperture and is due to pore flexibility.

Finally, ZIF-8 membranes were modified with 5,6 dimethylbenzimidazole through solvent assisted membrane surface ligand exchange to narrow the pore aperture for enhanced molecular sieving. Results show that relatively fast exchange kinetics occur at the mainly at the outer ZIF-8 membrane surface between 0-30 minutes of exchange. Short-time exchange enables C3 selectivity increases with minimal olefin permeance losses. As the reaction proceeds, the ligand exchange rate slows as the 5,6 DMBIm linker proceeds into the ZIF-8 inner surface, exchanges with the original linker and first disrupts the original framework’s crystallinity, then increases order as the reaction proceeds. The ligand exchange rate increases with temperature and the H2/C2 separation factor increases with increases in ligand exchange time and temperature.

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2017

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Design of Metal-Organic Frameworks for Carbon Capture Applications: Approaches for Adsorptive Separation of CO2/N2 and O2/N2 Mixtures

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The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be

The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.

First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.

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2019