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Description
Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2*-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O}). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm+ cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.
ContributorsZeller, Robert August (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
Description
The nucleon resonance spectrum consists of many overlapping excitations. Polarization observables are an important tool for understanding and clarifying these spectra. While there is a large data base of differential cross sections for the process, very few data exist for polarization observables. A program of double polarization experiments has been conducted at Jefferson Lab using a tagged polarized photon beam and a frozen spin polarized target (FROST). The results presented here were taken during the first running period of FROST using the CLAS detector at Jefferson Lab with photon energies ranging from 329 MeV to 2.35 GeV. Data are presented for the E polarization observable for eta meson photoproduction on the proton from threshold (W=1500 MeV) to W=1900 MeV. Comparisons to the partial wave analyses of SAID and Bonn-Gatchina along with the isobar analysis of eta-MAID are made. These results will help distinguish between current theoretical predictions and refine future theories.
ContributorsMorrison, Brian (Author) / Ritchie, Barry (Thesis advisor) / Dugger, Michael (Committee member) / Shovkovy, Igor (Committee member) / Davies, Paul (Committee member) / Alarcon, Ricardo (Committee member) / Arizona State University (Publisher)
Created2011
Description
Proton beam therapy (PBT) is a state-of-the-art radiotherapy treatment approach that uses focused proton beams for tumor ablation. A key advantage of this approach over conventional photon radiotherapy (XRT) is the unique dose deposition characteristics of protons, resulting in superior healthy tissue sparing. This results in fewer unwanted side effects and improved outcomes for patients. Current available dosimeters are intrinsic, complex and expensive; hence cannot be used to determine the dose delivered to the tumor routinely. Here, we report a hydrogel based plasmonic nanosensor for measurements of clinical doses in ranges between 2-4 GyRBE. In this nanosensor, gold ions, encapsulated in a hydrogel, are reduced to gold nanoparticles following irradiation with proton beams. Formation of gold nanoparticles renders a color change to the originally colorless hydrogel. The intensity of the color can be used to calibrate the hydrogel nanosensor in order to quantify different radiation doses employed during treatment. The potential of this nanosensor for clinical translation was demonstrated using an anthropomorphic phantom mimicking a clinical radiotherapy session. The simplicity of fabrication, detection range in the fractionated radiotherapy regime and ease of detection with translational potential makes this a first-in-kind plasmonic colorimetric nanosensor for applications in clinical proton beam therapy.
ContributorsInamdar, Sahil (Author) / Rege, Kaushal (Thesis advisor) / Anand, Aman (Committee member) / Nannenga, Brent (Committee member) / Arizona State University (Publisher)
Created2017
Description
A series of experiments using a polarized beam incident on a polarized frozen spin target
(FROST) was conducted at Jefferson Lab in 2010. Results presented here were taken
during the second running period with the FROST target using the CEBAF Large Acceptance
Spectrometer (CLAS) detector at Jefferson Lab, which used transversely-polarized
protons in a butanol target and a circularly-polarized incident tagged photon beam with
energies between 0.62 and 2.93 GeV. Data are presented for the F and T polarization observables
for h meson photoproduction on the proton from W = 1.55 GeV to 1.80 GeV.
The data presented here will improve the world database and refine theoretical approaches
of nucleon structure.
(FROST) was conducted at Jefferson Lab in 2010. Results presented here were taken
during the second running period with the FROST target using the CEBAF Large Acceptance
Spectrometer (CLAS) detector at Jefferson Lab, which used transversely-polarized
protons in a butanol target and a circularly-polarized incident tagged photon beam with
energies between 0.62 and 2.93 GeV. Data are presented for the F and T polarization observables
for h meson photoproduction on the proton from W = 1.55 GeV to 1.80 GeV.
The data presented here will improve the world database and refine theoretical approaches
of nucleon structure.
ContributorsTucker, Ross (Author) / Ritchie, Barry (Thesis advisor) / Dugger, Michael (Committee member) / Alarcon, Ricardo (Committee member) / Lebed, Richard (Committee member) / Arizona State University (Publisher)
Created2016
Description
The field of Ionic Liquid (IL) research has received considerable attention during the past decade. Unique physicochemical properties of these low melting salts have made them very promising for applications in a many areas of science and technology such as electrolyte research, green chemistry and electrodeposition. One of the most important parameters dictating their physicochemical behavior is the basicity of their anion. Using four sets of Protic Ionic Liquids (PILs) and spectroscopic characterization of them, a qualitative order for anion basicity of ILs is obtained.
Protic Ionic Liquids are made by proton transfer form a Brønsted acid to a base. The extent of this transfer is determined by the free energy change of the proton transfer process. For the cases with large enough free energy change during the process, the result is a fully ionic material whereas if the proton transfer is not complete, a mixture of ions, neutral molecules and aggregates is resulted. NMR and IR spectroscopies along with electrochemical and mechanical characterization of four sets of PILs are used to study the degree of ionicity.
Protic Ionic Liquids are made by proton transfer form a Brønsted acid to a base. The extent of this transfer is determined by the free energy change of the proton transfer process. For the cases with large enough free energy change during the process, the result is a fully ionic material whereas if the proton transfer is not complete, a mixture of ions, neutral molecules and aggregates is resulted. NMR and IR spectroscopies along with electrochemical and mechanical characterization of four sets of PILs are used to study the degree of ionicity.
ContributorsHasani, Mohammad (Author) / Angell, C. Austen (Thesis advisor) / Yarger, Jeffrey L (Committee member) / Gould, Ian R (Committee member) / Arizona State University (Publisher)
Created2016