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- Genre: Academic theses
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Description
An urgent need for developing new chemical separations that address the capture of dilute impurities from fluid streams are needed. These separations include the capture of carbon dioxide from the atmosphere, impurities from drinking water, and toxins from blood streams. A challenge is presented when capturing these impurities because the energy cost for processing the bulk fluid stream to capture trace contaminants is too great using traditional thermal separations. The development of sorbents that may capture these contaminants passively has been emphasized in academic research for some time, producing many designer materials including metal-organic frameworks (MOFs) and polymeric resins. Scaffolds must be developed to effectively anchor these materials in a passing fluid stream. In this work, two design techniques are presented for anchoring these sorbents in electrospun fiber scaffolds.
The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.
The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.
The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.
The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.
ContributorsArmstrong, Mitchell (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Seo, Dong (Committee member) / Lackner, Klaus (Committee member) / Holloway, Julianne (Committee member) / Arizona State University (Publisher)
Created2018
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
Among the alternative processes for the traditional distillation, adsorption and membrane separations are the two most promising candidates and metal-organic frameworks (MOFs) are the new material candidate as adsorbent or membrane due to their high surface area, various pore sizes, and highly tunable framework functionality. This dissertation presents an investigation of the formation process of MOF membrane, framework defects, and two-dimensional (2D) MOFs, aiming to explore the answers for three critical questions: (1) how to obtain a continuous MOF membrane, (2) how defects form in MOF framework, and (3) how to obtain isolated 2D MOFs. To solve the first problem, the accumulated protons in the MOF synthesis solution is proposed to be the key factor preventing the continuous growth among Universitetet I Oslo-(UiO)-66 crystals. The hypothesis is verified by the growth reactivation under the addition of deprotonating agent. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium so that an oriented growth of UiO-66 film was achieved in membrane structures. To find the answer for the second problem, the defect formation mechanism in UiO-66 was investigated and the formation of missing-cluster (MC) defects is attributed to the partially-deprotonated ligands. Experimental results show the number of MC defects is sensitive to the addition of deprotonating agent, synthesis temperature, and reactant concentration. Pore size distribution allows an accurate and convenient characterization of the defects. Results show that these defects can cause significant deviations of its pore size distribution from the perfect crystal. The study of the third questions is based on the established bi-phase synthesis method, a facile synthesis method is adopted for the production of high quality 2D MOFs in large scale. Here, pyridine is used as capping reagent to prevent the interplanar hydrogen bond formation. Meanwhile, formic acid and triethylamine as modulator and deprotonating agent to balance the anisotropic growth, crystallinity, and yield in the 2D MOF synthesis. As a result, high quality 2D zinc-terephthalic acid (ZnBDC) and copper-terephthalic acid (CuBDC) with extraordinary aspect ratio samples were successfully synthesized.
ContributorsShan, Bohan (Author) / Mu, Bin (Thesis advisor) / Forzani, Erica (Committee member) / Dai, Lenore (Committee member) / Lin, Jerry (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2019
Description
ABSTRACT
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.
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.
ContributorsKasik, Alexandra Marie (Author) / Lin, Jerry (Thesis advisor) / Tasooji, Amaneh (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2015