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- All Subjects: chemical engineering
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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
This study aims to provide a foundation for future work on photo-responsive polymer composite materials to be utilized in additive manufacturing processes. The curing rate of 2,2-dimethoxy-2-phenyl-acetophenone (DMPA) in thin (<20 µm) and thick (>2 mm) layers of DMPA and poly(ethylene glycol) diacrylate (PEG-DA) mixtures was assessed for 5.0 w/v% (grams per 100 mL) concentrations of DMPA dissolved in PEG-DA. The polymerization rate and quality of curing was found to decrease as the concentration of DMPA increased beyond 1.0 w/v%; thus, confirming the existence of an optimum photo-initiator concentration for a specific sheet thickness. The optimum photo-initiator concentration for a 3-3.1 mm thick sheet of PEG-DA microstructure was determined to be between 0.3 and 0.38 w/v% DMPA. The addition of 1,6-hexanediol or 1,3-butanediol to the optimum photo-initiator concentrated solution of DMPA and PEG-DA was found to increase the Tg of the samples; however, the samples could not fully cure within 40-50 s, which suggested a decrease in polymerization rate. Lastly, the DMPA photo-initiator does not produce gaseous byproducts and is translucent when fully cured, which makes it attractive for infusion with strengthening materials because quality light penetration is paramount to quick polymerization rates. It is recommended that more trials be conducted to evaluate the mechanical properties of the optimum curing rate for DMPA and PEG-DA microstructures as well as a mechanical property comparison following the addition of either of the two alcohols.
ContributorsPiper, Tyler Irvin (Author) / Green, Green (Thesis director) / Lind, Mary Laura (Committee member) / School of Sustainability (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
This report investigates the effects of autolyzing, fermentation medium, fermentation temperature, and proofing medium on the growth and porosity of 50% whole wheat sourdough bread. A model was designed using a 24 statistical design of experiment with replicates to screen and quantify the individual and combined effects of the aforementioned factors on the area of a 1 cm cross-sectional cut from each loaf. Fermentation temperature had the single largest effect, with colder fermented loaves being on average 10 cm2 larger than their warmer fermented counter parts. Autolyzing had little individual effect, but the strengthened gluten network abated some of the degassing and overproofing that is a consequent handling the dough or letting it ferment too much. This investigation quantifies how to maximize gluten development and yeast growth to create the airiest whole wheat sourdough, a healthier and easier to digest bread than many commercially available.
ContributorsLay, Michael Loren (Author) / Emady, Heather (Thesis director) / Adepu, Manogna (Committee member) / School of Sustainability (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
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
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.
ContributorsNkuutu, John (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
Improvement in carbon capture percentage was calculated as most effective in 10 mg/L-MEA BG-11 media, with improvement in carbon capture of 1.012% over the control. In studying the effect of agitation at 150 revolutions-per-minute (RPM) with a magnetic stir bar, it was found that mass transfer actually decreased. Future investigations are warranted to fully characterize the effect of different alkanolamine types, concentrations, and mixing regimens on mass transfer of CO2. In this thesis, emphasis was placed on experimental setup to allow for a discussion of the unexpected characteristics of the findings of the mass transfer experiments. Understanding the effect of experimental setup on mass transfer will be important in designing more effective methods of CO2 absorption for improving growth of cyanobacteria.
ContributorsMcallister, Cameron William (Author) / Nielsen, David (Thesis director) / Nannenga, Brent (Committee member) / School of Sustainability (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
Optimizing cathodes for microbial fuel cells is important to maximize energy harvested from wastewater. Cathodes were made by modifying a recipe from previous literature and testing the current of the cathode using linear sweep voltammetry. The cathodes contained an Fe-N-C catalyst combined with a Polytetrafluoroethylene binder. Optimizing the power resulting from the microbial fuel cells will help MFCs be an alternative energy source to fossil fuels. The new cathodes did improve in current production from −16 𝐴/𝑚 to −37 𝐴/𝑚 at -0.4 V. When fitted using a Butler-Volmer model, the cathode linear-sweep voltammograms did not follow the expected exponential trend. These results show a need for more research on the cathodes and the Butler-Volmer model, and they also show that the cathode is ready for further and longer application in a microbial fuel cell.
ContributorsRussell, Andrea Christine (Author) / Torres, Cesar (Thesis director) / Young, Michelle (Committee member) / School of Sustainable Engineering & Built Envirnmt (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05