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Description
We report the synthesis of novel boronic acid-containing metal-organic frameworks (MOFs), which was synthesized via solvothermal synthesis of cobalt nitride with 3,5-Dicarboxyphenylboronic acid (3,5-DCPBC). Powder X-ray diffraction and BET surface area analysis have been used to verify the successful synthesis of this microporous material.
We have also made the attempts of using zinc nitride and copper nitride as metal sources to synthesize the boronic acid-containing MOFs. However, the attempts were not successful. The possible reason is the existence of copper and zinc ions catalyzed the decomposition of 3,5-Dicarboxyphenylboronic acid, forming isophthalic acid. The ended product has been proved to be isophthalic acid crystals by the single crystal X-ray diffraction. The effects of solvents, reaction temperature, and added bases were investigated. The addition of triethylamine has been shown to tremendously improve the sample crystallinity by facilitating ligand deprotonation
We have also made the attempts of using zinc nitride and copper nitride as metal sources to synthesize the boronic acid-containing MOFs. However, the attempts were not successful. The possible reason is the existence of copper and zinc ions catalyzed the decomposition of 3,5-Dicarboxyphenylboronic acid, forming isophthalic acid. The ended product has been proved to be isophthalic acid crystals by the single crystal X-ray diffraction. The effects of solvents, reaction temperature, and added bases were investigated. The addition of triethylamine has been shown to tremendously improve the sample crystallinity by facilitating ligand deprotonation
ContributorsYu, Jiuhao (Author) / Mu, Bin (Thesis advisor) / Forzani, Erica (Committee member) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2014
Description
Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications.
In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.
An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.
An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
ContributorsIbrahim, Amr Fatehy Muhammad (Author) / Lin, Jerry Y.S. (Thesis advisor) / Mu, Bin (Committee member) / Lind, Mary (Committee member) / Green, Matthew (Committee member) / Wang, Qing (Committee member) / Arizona State University (Publisher)
Created2018
Description
Ethylene vinyl acetate (EVA) is the most commonly used encapsulant in photovoltaic modules. However, EVA degrades over time and causes performance losses in PV system. Therefore, EVA degradation is a matter of concern from a durability point of view.
This work compares EVA encapsulant degradation in glass/backsheet and glass/glass field-aged PV modules. EVA was extracted from three field-aged modules (two glass/backsheet and one glass/glass modules) from three different manufacturers from various regions (cell edges, cell centers, and non-cell region) from each module based on their visual and UV Fluorescence images. Characterization techniques such as I-V measurements, Colorimetry, Different Scanning Calorimetry, Thermogravimetric Analysis, Raman spectroscopy, and Fourier Transform Infrared Spectroscopy were performed on EVA samples.
The intensity of EVA discoloration was quantified using colorimetric measurements. Module performance parameters like Isc and Pmax degradation rates were calculated from I-V measurements. Properties such as degree of crystallinity, vinyl acetate content and degree of crosslinking were calculated from DSC, TGA, and Raman measurements, respectively. Polyenes responsible for EVA browning were identified in FTIR spectra.
The results from the characterization techniques confirmed that when EVA undergoes degradation, crosslinking in EVA increases beyond 90% causing a decrease in the degree of crystallinity and an increase in vinyl acetate content of EVA. Presence of polyenes in FTIR spectra of degraded EVA confirmed the occurrence of Norrish II reaction. However, photobleaching occurred in glass/backsheet modules due to the breathable backsheet whereas no photobleaching occurred in glass/glass modules because they were hermetically sealed. Hence, the yellowness index along with the Isc and Pmax degradation rates of EVA in glass/glass module is higher than that in glass/backsheet modules.
The results implied that more acetic acid was produced in the non-cell region due to its double layer of EVA compared to the front EVA from cell region. But, since glass/glass module is hermetically sealed, acetic acid gets entrapped inside the module further accelerating EVA degradation whereas it diffuses out through backsheet in glass/backsheet modules. Hence, it can be said that EVA might be a good encapsulant for glass/backsheet modules, but the same cannot be said for glass/glass modules.
This work compares EVA encapsulant degradation in glass/backsheet and glass/glass field-aged PV modules. EVA was extracted from three field-aged modules (two glass/backsheet and one glass/glass modules) from three different manufacturers from various regions (cell edges, cell centers, and non-cell region) from each module based on their visual and UV Fluorescence images. Characterization techniques such as I-V measurements, Colorimetry, Different Scanning Calorimetry, Thermogravimetric Analysis, Raman spectroscopy, and Fourier Transform Infrared Spectroscopy were performed on EVA samples.
The intensity of EVA discoloration was quantified using colorimetric measurements. Module performance parameters like Isc and Pmax degradation rates were calculated from I-V measurements. Properties such as degree of crystallinity, vinyl acetate content and degree of crosslinking were calculated from DSC, TGA, and Raman measurements, respectively. Polyenes responsible for EVA browning were identified in FTIR spectra.
The results from the characterization techniques confirmed that when EVA undergoes degradation, crosslinking in EVA increases beyond 90% causing a decrease in the degree of crystallinity and an increase in vinyl acetate content of EVA. Presence of polyenes in FTIR spectra of degraded EVA confirmed the occurrence of Norrish II reaction. However, photobleaching occurred in glass/backsheet modules due to the breathable backsheet whereas no photobleaching occurred in glass/glass modules because they were hermetically sealed. Hence, the yellowness index along with the Isc and Pmax degradation rates of EVA in glass/glass module is higher than that in glass/backsheet modules.
The results implied that more acetic acid was produced in the non-cell region due to its double layer of EVA compared to the front EVA from cell region. But, since glass/glass module is hermetically sealed, acetic acid gets entrapped inside the module further accelerating EVA degradation whereas it diffuses out through backsheet in glass/backsheet modules. Hence, it can be said that EVA might be a good encapsulant for glass/backsheet modules, but the same cannot be said for glass/glass modules.
ContributorsPatel, Aesha Parimalbhai (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Green, Matthew (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2018
Description
The search for highly active, inexpensive, and earth abundant replacements for existing transition metal catalysts is ongoing. Our group has utilized several redox non-innocent ligands that feature flexible arms with donor substituents. These ligands allow for coordinative flexibility about the metal centre, while the redox non-innocent core helps to overcome the one electron chemistry that is prevalent in first row transition metals. This dissertation focuses on the use of Ph2PPrDI, which can adopt a κ4-configuration when bound to a metal. One reaction that is industrially useful is hydrosilylation, which allows for the preparation of silicones that are useful in the lubrication, adhesive, and cosmetics industries. Typically, this reaction relies on highly active, platinum-based catalysts. However, the high cost of this metal has inspired the search for base metal replacements. In Chapter One, an overview of existing alkene and carbonyl hydrosilylation catalysts is presented. Chapter Two focuses on exploring the reactivity of (Ph2PPrDI)Ni towards carbonyl hydrosilylation, as well as the development of the 2nd generation catalysts, (iPr2PPrDI)Ni and (tBu2PPrDI)Ni. Chapter Three presents a new C-O bond hydrosilylation reaction for the formation of silyl esters. It was found the (Ph2PPrDI)Ni is the most active catalyst in the literature for this transformation, with turnover frequencies of up to 900 h-1. Chapter Four explores the activity and selectivity of (Ph2PPrDI)Ni for alkene hydrosilylation, including the first large scope of gem-olefins for a nickel-based catalyst. Chapter Five explores the chemistry of (Ph2PPrDI)CoH, first through electronic structure determinations and crystallography, followed by an investigation of its reactivity towards alkyne hydroboration and nitrile dihydroboration. (Ph2PPrDI)CoH is the first reported cobalt nitrile dihydroboration catalyst.
ContributorsRock, Christopher L (Author) / Trovitch, Ryan J (Thesis advisor) / Kouvetakis, John (Committee member) / Pettit, George R. (Committee member) / Arizona State University (Publisher)
Created2018
Description
Chemical modification of (semi)conducting surfaces with soft-material coatings containing electrocatalysts provides a strategy for developing integrated constructs that capture, convert, and store solar energy as fuels. However, a lack of effective strategies for interfacing electrocatalysts with solid-state materials, and an incomplete understanding of performance limiting factors, inhibit further development. In this work, chemical modification of a nanostructured transparent conductive oxide, and the III-V semiconductor, gallium phosphide, is achieved by applying a thin-film polymer coating containing appropriate functional groups to direct, template, and assemble molecular cobalt catalysts for activating fuel-forming reactions. The heterogeneous-homogeneous conducting assemblies enable comparisons of the structural and electrochemical properties of these materials with their homogeneous electrocatalytic counterparts. For these hybrid constructs, rational design of the local soft-material environment yields a nearly one-volt span in the redox chemistry of the cobalt metal centers. Further, assessment of the interplay between light absorption, charge transfer, and catalytic activity in studies involving molecular-catalyst-modified semiconductors affords models to describe the rates of photoelectrosynthetic fuel production as a function of the steady-state concentration of catalysts present in their activated form. These models provide a conceptual framework for extracting kinetic and thermodynamic benchmarking parameters. Finally, investigation of molecular ‘proton wires’ inspired by the Tyrosine Z-Histidine 190 redox pair in Photosystem II, provides insight into fundamental principles governing proton-coupled electron transfer, a process essential to all fuel-forming reactions relevant to solar fuel generation.
ContributorsWadsworth, Brian Lawrence (Author) / Moore, Gary F (Thesis advisor) / Moore, Thomas A. (Committee member) / Trovitch, Ryan J (Committee member) / Arizona State University (Publisher)
Created2020
Description
Thermal Energy Storage (TES) is of great significance for many engineering applications as it allows surplus thermal energy to be stored and reused later, bridging the gap between requirement and energy use. Phase change materials (PCMs) are latent heat-based TES which have the ability to store and release heat through phase transition processes over a relatively narrow temperature range. PCMs have a wide range of operating temperatures and therefore can be used in various applications such as stand-alone heat storage in a renewable energy system, thermal storage in buildings, water heating systems, etc. In this dissertation, various PCMs are incorporated and investigated numerically and experimentally with different applications namely a thermochemical metal hydride (MH) storage system and thermal storage in buildings. In the second chapter, a new design consisting of an MH reactor encircled by a cylindrical sandwich bed packed with PCM is proposed. The role of the PCM is to store the heat released by the MH reactor during the hydrogenation process and reuse it later in the subsequent dehydrogenation process. In such a system, the exothermic and endothermic processes of the MH reactor can be utilized effectively by enhancing the thermal exchange between the MH reactor and the PCM bed. Similarly, in the third chapter, a novel design that integrates the MH reactor with cascaded PCM beds is proposed. In this design, two different types of PCMs with different melting temperatures and enthalpies are arranged in series to improve the heat transfer rate and consequently shorten the time duration of the hydrogenation and dehydrogenation processes. The performance of the new designs (in chapters 2 and 3) is investigated numerically and compared with the conventional designs in the literature. The results indicate that the new designs can significantly enhance the time duration of MH reaction (up to 87%). In the fourth chapter, organic coconut oil PCM (co-oil PCM) is explored experimentally and numerically for the first time as a thermal management tool in building applications. The results show that co-oil PCM can be a promising solution to improve the indoor thermal environment in semi-arid regions.
ContributorsAlqahtani, Talal (Author) / Phelan, Patrick E (Thesis advisor) / Shuaib, Abdelrahman (Committee member) / Mellouli, Sofiene (Committee member) / Wang, Robert (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2020
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