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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

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
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Description
The goals of the styrene oxide adsorption experiments were to develop reliable isotherms of styrene oxide onto Dowex Optipore L-493 resin and onto mesoporous carbon adsorbents, in addition to determining the ideal conditions for styrene oxide production from E. coli. Adsorption is an effective means of separation used in industry

The goals of the styrene oxide adsorption experiments were to develop reliable isotherms of styrene oxide onto Dowex Optipore L-493 resin and onto mesoporous carbon adsorbents, in addition to determining the ideal conditions for styrene oxide production from E. coli. Adsorption is an effective means of separation used in industry to separate compounds, often organics from air and water. Styrene oxide adsorption runs without E. coli were conducted at concentrations ranging from 0.15 to 3.00 g/L with resin masses ranging from 0.1 to 0.5 g of Dowex Optipore L-493 and 0.5 to 0.75 g of mesoporous carbon adsorbent. Runs were conducted on a shake plate operating at 80 rpm for 24 hours at ambient temperature. Isotherms were developed from the results and then adsorption experiments with E. coli and L-493 were performed. Runs were conducted at glucose concentrations ranging from 20-40 g/L and resin masses of 0.100 g to 0.800 g. Samples were incubated for 72 hours and styrene oxide production was measured using an HPLC device. Specific loading values reached up to 0.356 g/g for runs without E. coli and nearly 0.003 g of styrene oxide was adsorbed by L-493 during runs with E. coli. Styrene oxide production was most effective at low resin masses and medium glucose concentrations when produced by E. coli.
ContributorsHsu, Joshua (Co-author) / Oremland, Zachary (Co-author) / Nielsen, David (Thesis director) / Staggs, Kyle (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / School of Sustainability (Contributor)
Created2014-05
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Description
This study details the construction and operation of a dry-jet wet spinning apparatus for extruding hollow fiber membranes (HFMs). The main components of the apparatus are a spinneret, a coagulation bath, and an automatic collection reel. Continuous fiber formation was achieved using two syringe pumps simultaneously delivering polymer dope and

This study details the construction and operation of a dry-jet wet spinning apparatus for extruding hollow fiber membranes (HFMs). The main components of the apparatus are a spinneret, a coagulation bath, and an automatic collection reel. Continuous fiber formation was achieved using two syringe pumps simultaneously delivering polymer dope and bore fluid to the spinneret. Based on apparatus runs performed with Polysulfone (PSF) dopes dissolved in N,N-Dimethylacetamide and supporting rheological analysis, the entanglement concentration, ce, was identified as a minimum processing threshold for creating HFMs. Similarly, significant increases in the ultimate tensile strength, fracture strain, and Young's modulus for extruded HFMs were observed as polymer dope concentration was increased at levels near ce. Beyond this initial increase, subsequent tests at higher PSF concentrations yielded diminishing changes in mechanical properties, suggesting an asymptotic approach to a point where the trend would cease. Without further research, it is theorized that this point falls on a transition from the semidiute entangled to concentrated concentration regimes. SEM imaging of samples revealed the formation of grooved structures on the inner surface of samples, which was determined to be a result of the low flowrate and polymer dope concentrations used in processing the HFMs during apparatus runs. Based on continued operation of the preliminary apparatus design, many areas of improvement were noted. Namely, these consisted of controlling the collector speed, eliminating rubbing of nascent fibers against the edge of the coagulation bath by installing an elevated roller, and replacing tygon tubing for the polymer line with a luer lock adapter for direct syringe attachment to the spinneret.
ContributorsBridge, Alexander Thomas (Author) / Green, Matthew D. (Thesis director) / Lin, Jerry Y. S. (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
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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

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
Styrene, a component of many rubber products, is currently synthesized from petroleum in a highly energy-intensive process. The Nielsen Laboratory at Arizona State has demonstrated a biochemical pathway by which E. coli can be engineered to produce styrene from the amino acid phenylalanine, which E. coli naturally synthesizes from glucose.

Styrene, a component of many rubber products, is currently synthesized from petroleum in a highly energy-intensive process. The Nielsen Laboratory at Arizona State has demonstrated a biochemical pathway by which E. coli can be engineered to produce styrene from the amino acid phenylalanine, which E. coli naturally synthesizes from glucose. However, styrene becomes toxic to E. coli above concentrations of 300 mg/L, severely limiting the large-scale applicability of the pathway. Thus, styrene must somehow be continuously removed from the system to facilitate higher yields and for the purposes of scale-up. The separation methods of pervaporation and solvent extraction were investigated to this end. Furthermore, the styrene pathway was extended by one step to produce styrene oxide, which is less volatile than styrene and theoretically simpler to recover. Adsorption of styrene oxide using the hydrophobic resin L-493 was attempted in order to improve the yield of styrene oxide and to provide additional proof of concept that the flux through the styrene pathway can be increased. The maximum styrene titer achieved was 1.2 g/L using the method of solvent extraction, but this yield was only possible when additional phenylalanine was supplemented to the system.
ContributorsMcDaniel, Matthew Cary (Author) / Nielsen, David (Thesis director) / Lind, Mary Laura (Committee member) / McKenna, Rebekah (Committee member) / Barrett, The Honors College (Contributor) / Department of Chemistry and Biochemistry (Contributor) / Chemical Engineering Program (Contributor)
Created2013-05