Matching Items (4)
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- All Subjects: MOF
- All Subjects: Metals
- Creators: Biyani, Nivedita
- Status: Published
Description
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.
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.
ContributorsMcIntyre, Sean (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2019
Description
Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is the MOF-5 material, specifically its chemical stability in air. The MOF-5 material has a large pore size of 8 Å, and aperture sizes of 15 and 12 Å. The pore size, pore functionality, and physically stable structure makes MOF-5 a desirable material. MOF-5 holds applications in gas/liquid separation, catalysis, and gas storage. The main problem with the MOF-5 material, however, is its instability in atmospheric air. This inherent instability is due to the water in air binding to the zinc-oxide core, effectively changing the material and its structure. Because of this material weakness, the MOF-5 material is difficult to be utilized in industrial applications. Through the research efforts proposed by this study, the stability of the MOF-5 powder and membrane were studied. MOF-5 powder and a MOF-5 membrane were synthesized and characterized using XRD analysis. In an attempt to improve the stability of MOF-5 in air, methyl groups were added to the organic linker in order to hinder the interaction of water with the Zn4O core. This was done by replacing the terepthalic acid organic linker with 2,5-dimethyl terephthalic acid in the powder and membrane synthesis steps. The methyl-modified MOF-5 powder was found to be stable after several days of exposure to air while the MOF-5 powder exhibited significant crystalline change. The methyl-modified membrane was found to be unstable when synthesized using the same procedure as the MOF-5 membrane.
ContributorsAnderson, Anthony David (Author) / Lin, Jerry Y.S. (Thesis director) / Ibrahim, Amr (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
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.
ContributorsClose, Emily Charlotte (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
This thesis examines the composition, flow rate, and recyclability of two abundant materials generated in modern society: municipal sewage sludge (SS) generated during conventional wastewater treatment, and single-use plastic packaging (specifically, plastic bottles) manufactured and dispersed by fast-moving consumer goods companies (FMCG). The study found the presence of 5 precious metals in both American and Chinese sewage sludges. 13 rare elements were found in American sewage sludge while 14 were found in Chinese sewage sludge. Modeling results indicated 251 to 282 million metric tons (MMT) of SS from 2022 to 2050, estimated to contain some 6.8 ± 0.5 MMT of valuable elements in the USA, the reclamation of which is valued at $24B ± $1.6B USD. China is predicted to produce between 819 - 910 MMT of SS between 2022 and 2050 containing an estimated 14.9 ± 1.7 MMT of valuable elements worth a cumulative amount of $94B ± 20B (Chapter 2 and 3). The 4th chapter modeled how much plastic waste Coca-Cola, PespiCo and Nestlé produced and globally dispersed in 21 years: namely an estimated 126 MMT ± 8.7 MMT of plastic. Some 15.6 MMT ± 1.3 MMT (12%) is projected to have become aquatic pollution costing estimated at $286B USD. Some 58 ± 5 MMT or 46% of the total mass were estimated to result in terrestrial plastic pollution, with only minor amounts of 9.9 ± 0.7 MMT, deemed actually recycled. Absent of change, the three companies are predicted to generate an additional 330 ± 15 MMT of plastic by 2050, thereby creating estimated externalities of $8 ± 0.4 trillion USD. The analysis suggests that a small subset of FMCG companies are well positioned to change the current trajectory of global plastic pollution and ocean plastic littering. Chapter 5 examined the barriers to Circular Economy. In an increasingly uncertain post pandemic world, it is becoming progressively important to conserve local resources and extract value from materials that are currently interpreted a “waste” rather than a current or potential future resource.
ContributorsBiyani, Nivedita (Author) / Halden, Rolf U. (Thesis advisor) / Allenby, Braden (Committee member) / Jalbert, Kirk (Committee member) / Arizona State University (Publisher)
Created2022