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- Creators: Arizona State University
- Creators: Parker, Sara
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.
Wilhelm Pfeffer published his book Osmotische Untersuchungen: Studien Zur Zellmechanik (Osmotic Investigations: Studies on Cell Mechanics) in 1877 during his time as a professor of botany at the University of Basel in Basel, Switzerland. Gordon R. Kepner and Eduard J. Stadelmann translated the book into English in 1985. Verlag von Wilhelm Engelmann in Leipzig, Germany, published the original book in German in 1877 and Van Nostrand Reinhold Company in New York, New York, published the English version in 1985. The book focuses on the cell mechanics of osmotic processes to explain why high pressure exists in plant cells. The book also provides one of the earliest detailed descriptions of the Pfeffer Cell, a devise Pfeffer had created to model and study osmosis in plant cells. The model helped Pfeffer propose theories for how osmosis affected metabolism, growth, and development of plant cells.
The Pfeffer Zelle (Pfeffer Cell Apparatus), invented by Wilhelm Pfeffer in 1877, measured the minimum pressure needed to prevent a pure solvent from passing into a solution across a semi-permeable membrane, called osmotic pressure. The apparatus provided Pfeffer with a way to quantitatively measure osmotic pressure. Pfeffer devised the apparatus in the 1870s at the University of Basel in Basel, Switzerland, and he described the Pfeffer Cell Apparatus in his 1877 book Osmotische Untersuchungen: Studien Zur Zellmechanik (Osmotic Investigations: Studies on Cell Mechanics). Pfeffer relied on nineteenth century experiments of Moritz Traube in Germany, who constructed artificial copper ferrocyanide membranes to study osmosis. The apparatus enabled Pfeffer to study osmosis and osmotic pressure as plants grow, and later researchers used it to explain how plants develop.
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.