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Thesis (Ph. D.) -- California Institute of Technology, 2010. / Title from home page (viewed 02/25/2010). Advisor and committee chair names found in the thesis' metadata record in the digital repository. Includes bibliographical references.

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The rising environmental and financial consequences of using fossil fuels as an energy source and energy carrier are a global concern. Described herein are two hydrogen-storing technologies, each of which was envisioned as a potential solution to said consequences: hydrogen-storing polymethylpyridylsiloxanes for use as an alternative energy carrier to fossil fuels; and thermally regenerative fuel cell systems to supplement or supplant vehicular alternators. A thermally regenerative fuel cell (TRFC) system is being developed to convert waste heat from an internal combustion engine (ICE) system into electricity that can be used to power auxiliary vehicular components. The TRFC system will comprise a dehydrogenation reactor and a fuel cell positioned relative to the ICE system such that the two components are held at 200 °C and 100 °C, respectively. 1-Phenyl-1-propanol has been identified as an optimal hydrogen storing liquid (XH2) that will selectively dehydrogenate over a heterogeneous catalyst to give a dehydrogenated liquid (propiophenone, X) and H2. The heterogeneous catalyst that currently provides the best selectivity (99.65%) for X at 200 °C is Pd/SiO2. A selectivity of ≥ 99.9% was desired to obtain the longest possible operational lifetime for the working fluids XH2/X. To increase the selectivity for X from 99.65% to ≥ 99.9%, size and shape specific Pd nanoparticles were synthesized. Pd nanocubes (20 nm) provided the best selectivity for X at 99.26%. It was concluded that a reproducible selectivity for X of ≥ 99.9% was not currently obtainable, and that a selectivity for X no greater than 99 % should be assumed when calculating the working fluids’ operational lifetime. Hydrogen-storing polymethylpyridylsiloxanes were proposed as energy carrier alternatives to fossil fuels. Polymethylpyridylsiloxanes were considered, in part, due to the expansive liquid ranges of siloxane polymers [-40 ˚C to 250 ˚C]; this would allow the polymethylpyridylsiloxanes to be stored and pumped into vehicles using existing refueling infrastructure. Polymethylpyridylsiloxanes, and analogs thereof, however, were not successfully synthesized and reversibly hydrogenated: either the desired product(s) could not be synthesized, isolated, and/or purified; or, hydrogenation resulted in product decomposition. It was concluded, therefore, that implementing polymethylpyridylsiloxanes as hydrogen-storing liquids is not viable. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-12-24 01:01:16.857

TiO2 supported MoO3 catalysts were prepared by aqueous impregnation of low area anatase (10 m2g-1) with solutions of (NH4)6Mo7024,4H20 (MT/C series), and H2[Mo03(C204)].H20 (MOT /C series), Three series of CoOx/Ti02 catalysts were fabricated by aqueous impregnation of the same support with solutions of Co(N03)2,6H20 (CT/C series), and Co(CH3COO)2.4H20 (CAT/C series), and by homogeneous precipitation using Co(N03)2,6H20 (CT/HP series), CoO and Mo03 were deposited on Degussa P-25 (55 m2g-1) by aqueous impregnation using (NH4)6Mo7024,4H20 and Co(N03)2,6H20 in three ways: ( i) CoO impregnated first, Mo03 second (CMT series); (ii) Mo03 impregnated first, CoO second (MCT series); and (iii) CoO and Mo03 together (CMTg series). The catalysts were characterized by laser Raman spectroscopy (LRS) , temperature-programmed reduction (TPR) , X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), Monolayer coverage by XPS was independent of the precursor for the MoOx/Ti02 catalysts, but a function of the method of preparat ion and the precursor for the CoOx /Ti02 catalysts. XPS results for the CMTg series differed from those for the CMT and MCT series, suggesting different surface species had been formed by varying the mode of impregnation, Phase diagrams relating semiquantitatively to the oxide contents are presented. 2-propanol decomposition was studied to probe the acid-base properties of the catalysts, Ti02 and Mo03 exhibi ted dehydration activity, whereas CoO showed dehydrogenation activity, All the supported catalysts gave activation energies for dehydration higher than dehydrogenation. In the sub-monolayer region, the catalytic activity for dehydration was in the order: MCT > CMTg > CMT > MT/C > CT/C, while the selectivity remained almost unchanged, In the monolayer region, the activity was: MT/C > CMT > CMTg > MCT > CT/C and the selectivity increased compared with the sub-monolayer region. In the four-monolayer reg ion, the activity decreased compared with the sub-monolayer and monolayer regions, but the selectivity increased relative to the previous two regimes. "Compensation effect 0, plots revealed different types of active centres responsible for dehydration and dehydrogenation processes in the MoOx /Ti02 and CoO-Mo03/Ti02 catalysts, while active centres were almost identical with the CoOx /Ti02 system.