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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Novel anodes for internal reforming in solid oxide fuel cells

Weston, Michael John January 2001 (has links)
No description available.
2

Investigation of uranium redox chemistry and complexation across the pH range by cyclic voltammetry

Chew, Mei January 2013 (has links)
The current option for the management of Intermediate-Level Waste (ILW) and High-Level Waste (HLW) in the UK is to store it in stainless steel containers and then placed in a deep underground Geological Disposal Facility (GDF). This may subsequently be backfilled with a cementitious material generating very high pH conditions. The eventual corrosion of the stainless steel canisters containing the waste used for disposal will lead to reducing conditions thereby promoting a low Eh environment. Electrochemical experiments are needed to determine which uranium species is/are present at a particular pH and to model the redox behaviour of aqueous uranium in a potential GDF. The main aim of this project is to use cyclic voltammetry to deduce peak potentials for the various uranium redox couples in aqueous solution across the pH range and in particular the hyperalkaline range, as the surroundings of a GDF will be in high pH conditions. Data in the literature have been obtained only under acidic conditions where they were subsequently extrapolated to obtain data for alkaline conditions in some reports. Is this valid however? Experiments are therefore needed to obtain fundamental data under alkaline conditions to fill in gaps in the literature. In addition to radionuclides, complexing organic ligands present in a cementitious repository could have an important effect on the immobilisation of radionuclides in concrete. This is due to the ability of the ligands to form complexes with cations, thereby enhancing their solubility and mobility in the cement pore water. Four different ligands were investigated in this project that are relevant to nuclear waste disposal which comprised of carbonate, ethylenediaminetetraacetic acid (EDTA), gluconic acid and α-isosaccharinic acid (α-ISA). The peak potentials of each uranium redox reaction in aqueous solution were measured and the potentials were compared in ligand and non-ligand systems. The voltammograms were compared to obtain their similarities and differences in terms of the shape of the cyclic voltammograms, peak potentials, reversibility, current responses and etc. Analysis of the similarities and differences was needed to be able to increase the understanding of the complexation effects of these ligands with uranium under different pH conditions in aqueous solution.
3

Heteroaryl carbene complexes : synthesis, reactivity and redox behaviour

Van der Westhuizen, Belinda January 2013 (has links)
A series of Fischer mono- and biscarbene complexes of the type [MLn{C=(XR)R'}] was synthesized and characterized. The redox behavior of the complexes was studied by different techniques, including cyclic voltammetry, spectroelectrochemistry, ESR and computational methods. Different transition metals (M) and carbene substituents (XR, R') were employed to compare both the effect of the central metal atom as well as the carbene substituent. Thienyl, furyl and ferrocenyl chromium(0) mono- and biscarbene complexes with ethoxy and amino substituents were electrochemically studied in CH2Cl2. Results were mutually consistent with computational data showing that the carbene double bond of all complexes is reduced pseudo reversibly to an anion radical, -Cr-C•. The Cr centers are oxidized in two successive one electron transfer steps to Cr(II) via the Cr(I) intermediate. For all ferrocenyl carbene complexes the Fe(II) is oxidized after the first oxidation of Cr. It was found that with respect to the aryl substituents the donating effect decreases from Fc>Fu>Th. Stabilization from the XR substituent, where XR = NHR, also resulted in lower redox potentials compared to their OEt analogues. The inclusion of ferrocene in the carbene substituent was done, as its redox activity and increased donating effect are well known. Mono- and biscarbene complexes with ethoxy and amino substituents of both chromium and tungsten were electrochemically studied. Again experimental data were supported by computational studies. Similar to the ethoxy chromium complexes, reduction of the W=C fragment to -W-C• was observed. However oxidation of the Fc group occurred first before the electrochemically irreversible oxidation process for W(0) involving a three electron-mediated process as seen in chronocoulometric analyses. The tungsten oxidation was restricted to a W0/II, consistent with computational studies, by the use of the electrolyte [NnBu4][B(C6F5)4]. The short-lived W(II) species were calculated to be stabilized by agostic CH···W interactions, similar to the chromium analogues. To extend linkers between the metal-carbene termini and investigate metal-metal interaction, biferrocenyl and 2,5-thienylbiferrocenyl tungsten(0) mono-and biscarbene complexes were synthesized and studied by spectroelectrochemistry. A metal-metal charge transfer transition between the tungsten carbonyl increment and the biferrocenyl / 2,5-thienylbiferrocenyl unit was confirmed by infrared spectroelectrochemical studies. The electronic interaction in the corresponding cationic species can be described as weakly coupled class II systems according to Robin and Day. The cymantrenyl moiety, Mn(η5-C5H4)(CO)3, provides an interesting alternative to ferrocene as an organometallic molecular tag, however the instability of the radical cation impairs its use. Improved stability of the cation, monitored by electrochemical measurements, was accomplished by substituting a carbonyl with a ferrocenyl Fischer carbene ligand resulting in Mn(I) oxidation occuring at lower potentials than ferrocenyl oxidation. These uncommon Fischer carbene complexes is the first organometallic multi-tags reported. The mono cationic species, [CpMn(CO)2{=C(OEt)Fc}][PF6], could be isolated and characterized with ESR analysis. Finally, transmetallation from the tungsten(0) Fischer carbene complexes yielded examples of rare acyclic alkoxy- and aminocarbene complexes of gold(I). Single x-ray structures for all complexes could be obtained including the novel ferrocenophane dinuclear biscarbene Au(I) complex. All structures display unsupported aurophilic interactions, while the bridging biscarbene shows a semi-supported Au-Au interaction. In the case of the furanyl/thienyl methoxy monocarbene complexes, extended Au-Au interactions result in oligomeric structures. Although this study is of a fundamental nature, it is imperative for the understanding and design of gold compounds with specific applications. / Thesis (PhD)--University of Pretoria, 2013. / gm2014 / Chemistry / unrestricted

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