Thesis (Ph.D.)--University of Nebraska-Lincoln, 2008. / Title from title screen (site viewed Apr. 9, 2009). PDF text: x, 189 p. : ill. (chiefly col.) ; 1 Mb. UMI publication number: AAT 3338828. Includes bibliographical references. Also available in microfilm and microfiche formats.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1984. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--Pennsylvania State University, 2008. / Thesis (M.S.)--Pennsylvania State University, 2008. Thesis advisor: James S. Shortle.

Direct liquid fuel cells represent an interesting alternative to conventional hydrogen fuel cell technology. A novel analytical method for the monitoring of direct liquid fuel cells is presented. Employing a combination of chronoamperometric, gravimetric and Raman spectroscopic measurements this method allows a straightforward determination of the Faradaic efficiency of a fuel cell. This method was applied in a proof of concept study analysing the operational behaviour of a direct methanol fuel cell. A very low Faradaic efficiency was found for the fuel cell under study. This was attributed to loss of methanol from the fuel mixture due to methanol crossover, stripping of methanol by carbon dioxide as well as evaporation. It is known from the literature that a fuel change from methanol towards higher alcohols and other hydrocarbons can help to mitigate the effects of these loss processes. However, the behaviour of such alternative fuels and their mixtures in an operating fuel cell and hence the performance of the fuel cell depends at least in part on the intermolecular interactions present in those fuel mixtures. Therefore, the intermolecular interactions in binary and ternary mixtures of potential candidates for alternative fuels were investigated in the main part of this thesis. Studies on the intermolecular interactions in binary mixtures of acetone with ethanol and 1-butanol showed a tendency for self association of both compounds albeit in different concentration ranges. It was further found that the alkyl chain length of the alcohols did not have a significant effect on the intermolecular interactions in the binary and ternary mixtures. Further, the behaviour of the ternary mixture was found to closely resemble the effects found in the individual binary mixtures. Finally, binary mixtures of dimethyl sulfoxide (DMSO) and different alcohols did not show self association. It was rather found that alcohol molecules inserted into chains of DMSO molecules eventually leading to the formation of alcohol-DMSO dimers.

Glycerol is a very promising alternative fuel to hydrogen in fuel cells. However, the utilisation of glycerol as a fuel requires a good catalyst, due to the slow kinetics of glycerol electrooxidation. Gold has been identified as a promising catalyst due to its high activity and stability for glycerol electrooxidation – although the overpotentials are higher than on platinum and palladium. Modification of a nano-Au/C catalyst by the addition of MnO2, in an attempt to further improve the activity and lower the overpotential for glycerol oxidation, was therefore first explored. This was followed by investigations into the effects of gold particle size and loading. Finally, the effect of gold particle size on oxidation of gold-catalysed glycerol oxidation intermediates was also briefly explored. Studies into MnO2 addition showed that the pre-deposition of MnO2 yielded catalysts with smaller, more uniform gold particles, and catalysts with MnO2 contents of 5 and 9 wt % had higher mass activities and lower onset- and peak- potentials than Au/C. All the Au/xMnO2/C catalysts were more active than the palladium- and platinum-based catalysts reported in literature, which effectively demonstrated the advantage of using a gold-based catalyst for glycerol oxidation – especially when supported by MnO2 which lowered the overpotential for glycerol oxidation over gold. For the study into gold particle size, small gold particles of average diameter ≤ 4.7 nm had higher gold mass-based activities than medium-sized (14.7 nm) particles and were at least twice as active as catalysts containing large (≥ 43 nm) gold particles. The small gold particles also gave lower glycerol oxidation onset potentials, which was attributed to the predominance of Au(110) planes on those particles. Glycerol oxidation also appeared to proceed further along the oxidation pathway over small gold particles, which was confirmed in preliminary studies into the oxidation of glycerol oxidation intermediates. However, specific activity increased with increasing gold particle size, due mainly to the higher intrinsic activity of the Au(111) plane, which increased relative to Au(110) with increasing gold particle size. The important requirements for fuel cell applications are factors such as high mass activity, low overpotentials and high stability – all of which were met by the catalysts containing small gold particles defined by predominantly Au(110) facets. Investigations into the gold loading effect showed similar mass- and specific- activities for catalysts with 5-20 % gold loading. However, only the catalysts with higher gold loadings (15-20 %) did not deactivate early during CV, indicating that a larger gold surface area is necessary to resist poisoning at high potentials. On the basis of low onset potentials, high mass activity, and stability at low overpotentials, a minimum gold loading of 12.5 % appears to be necessary for a supported gold catalyst with small gold nanoparticles; although even higher loadings may be preferable for a higher power output in a fuel cell. Importantly, the insights gleaned from this study on the fundamental properties required for early activation, activity and stability of the gold catalysts could lead to a more intelligent design of gold-based catalysts in future.

Thesis (M.A.)--Ohio University, June, 2008. / Title from PDF t.p. Includes bibliographical references.

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1990. / Vita. Abstract. Includes bibliographical references (leaves 148-153). Also available via the Internet.

Thesis (M.S.)--University of Tennessee, Knoxville, 2008. / Title from title page screen (viewed on Sept. 30, 2009). Thesis advisor: Dayton M. Lambert. Vita. Includes bibliographical references.

>Magister Scientiae - MSc / Anode catalysts are one of the key components of direct alcohol fuel cells (DAFCs). They play a huge role in the alcohol oxidation reaction (AOR) that occurs on the anode side. Palladium (Pd) supported on carbon material has been reported to have good catalytic activity towards alcohol oxidation reactions. Better stability and activity has been reported for catalysts supported on conductive polymers like polypyrrole (PPy) when compared to traditional carbon support material. This study investigated the effect of support materials on Pd and PdCo electro-catalysts while concurrently determining the support material that can improve the activity and stability of Pd and PdCo electro-catalysts used as direct alcohol fuel cells catalysts. All Pd and PdCo catalysts supported onPPy (prepared using oxidative polymerization method), reduced graphene oxide (rGO) and prepared using modified Hammers method and multi-walled carbon nanotubes and pre-treated by acid. All the catalysts were synthesized using the modified polyol method.

Doctorat en sciences sociales, politiques et économiques / info:eu-repo/semantics/nonPublished