Infra-Red thermography and spatially-resolved capillary inlet mass spectrometry (SpaciMS) have been used to characterize propylene oxidation along a Pt/Al2O3 monolith-supported catalyst, before and after heterogeneous deactivation. The combined techniques clearly show reaction location, and therefore catalyst use, and how these change with thermal and sulphur degradation. Following the heterogeneous thermal aging, the reaction zones at steady state were broader and located farther into the catalyst relative to those observed with the fresh catalyst. As well, the time for the temperature and concentration waves to travel through the catalyst during back-to-front ignition increased. These effects were more pronounced with 1500 ppm propylene relative to 4500 ppm propylene. Such trends could not be detected based on standard catalyst-outlet measurements. The light-off behaviour was also impacted by the aging, resulting in complex changes to the temperature front propagation, depending on the propylene concentration. With each sulphur exposure step, light-off temperatures increased and the time for back-to-front ignition during temperature programmed oxidation changed pattern. With 1500 ppm propylene fed, the reaction zones established during steady-state operation shifted farther into the catalyst and increased slightly in width following sulphur treatment; at very high temperature and for 4500 ppm propylene, the reaction zones were very close to the catalyst inlet and virtually indistinguishable between catalyst sulphation states. However, at lower steady-state temperatures for the higher propylene concentration, the catalyst did experience delays in reaction light-off and light-off position moved downstream in the catalyst with sulphur damage.

This thesis presents a framework for a microstructural model of a catalyst layer in a proton exchange membrane (PEM) fuel cell. In this study, a stochastic model that uses individual carbon, platinum and ionomer particles as building blocks to construct a catalyst layer geometry, resulting in optimal porosity and material mass ratios has been employed. The construction rule set in this design is easily variable, enabling a wide range of catalyst layer geometries to be made. The generated catalyst layers were found to exhibit many of the features found in currently poduced catalyst layers. The resulting geometries were subsequently examined on the basis of electronic percolation, mean chord length and effective diffusivity of the pore phase. Catalyst layer percolation was found to be most effected by the number of carbon see particles used and the specified porosity. The mean chord lengths of all of the catalyst layer geometries produced Knudsen numbers ranging in order of magnitude between 0.1 and 10, thus indicating that gas diffusion within the catalyst layers lies in the transition regime between bulk and Knudsen diffusion. Calculated effective diffusivities within the pore space of the model were shown to be relatively insensitive to changes in the catalyst layer composition and construction rule set other then porosity, indicating that the pore size distribution does not significantly vary when the catalyst layer mass ratios vary. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2012-08-31 08:52:55.747

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No description available.

Zinc air batteries are among the most promising energy storage devices due to their high energy density, low cost and environmental friendliness. The low mass and cost of zinc air batteries is a result of traditional active materials replacement with a thin gas diffusion layer which allows the battery to use the oxygen directly from the air. Despite the environmental and electronic advantages offered by this system, challenges related to drying the electrolyte and catalyst, determining a high activity bifictional catalyst, and ensuring durability of the gas diffusion layer need to be optimized during the fabrication of rechargeable zinc-air batteries. To date, platinum on carbon (Pt/C) provides the best electrochemical catalytic activity in acidic and alkaline electrolytes. However, the difficult acquisition and high cost of this catalyst mandates investigation into a new composition or synthesis of a bifunctional catalyst. A number of non-precious metal catalyst have been introduced for zinc-air batteries. Nevertheless, their catalytic activities and durability are still too low for commercial rechargeable zinc-air batteries. Thus, it is very important to synthesize a highly active bifunctional catalyst with good durability for long term charge and discharge use. In this study, it is proposed that a manganese-based perovskite oxide nanoparticle combined with nitrogen doped carbon nanotubes willshow promising electrochemical activity with remarkable cycle stability as a bifunctional catalyst for zinc-air batteries. In the first part of this work, nano-sized LaMnO3 and LaMn0.9Co0.1O3 were prepared to research the effectiveness of Co doping into LaMnO3 and its effect on electrochemical catalytic activities. To prepare LaMnO3 and LaMn0.9Co0.1O3, a hydrothermal reaction method was applied to synthesize nanoparticles which can increase the activity of perovskite type oxides. The result shows that while perovskite oxides replacing 10 wt. % of Mn doped with Co metal did not iv change its crystalline structure, the oxygen evolution reaction (OER) performance was increased by 600%. In the second part, a core-corona structured bifunctional catalyst (CCBC) was synthesized by combining LaMn0.9Co0.1O3 nanoparticles with nitrogen doped carbon nanotubes (NCNT). NCNT was chosen because of its large surface area and high catalytic activity for ORR. SEM and TEM analysis show that metal oxide nanoparticles were surrounded with nanotubes. Based on the electrochemical performances, ORR and OER activity is attributed to NCNT and the metal oxide core, respectively, complementing the activities of each other. Furthermore, its unique morphology introduces synergetic activity especially for OER. Electrochemical test results show that the onset potential was enhanced from -0.2 V (in LaMnO3 and LaMn0.9Co0.1O3) to -0.09 V (in CCBC) and the half wave potential was improved from -0.38 V to -0.19 V. In the third part, a single cell zinc-air battery test was performed using CCBC as the bifunctional catalyst for the air electrode. These results were compared with battery performance against a high-performance and expensive Pt/C based air catalyst. The results show that the battery containing catalytic CCBC consumes less energy during charge/discharge. The single cell long-term durability performance was compared, further proving that CCBC provides a more suitable catalyst for zinc-air battery than Pt/C.

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A series of aluminia and titania promoted, silica- supported chromium (III) acetate catalysts were characterized using X-ray photoelectron spectroscopy (XPS) prior to, and after, activation in oxygen at 780 C. The results indicated that Cr (VI) was formed in each case as a result of the activation process. Increased promoter metal binding energies implied an interaction between the promoter and silica support. It is proposed that there is insertion of aluminium and titanium atoms into the silica network, which leads to formation of surface silicates. A qualitative measure of the metal dispersions has been made using the XPS results. In general, the chromium dispersion fell on activation, but the greatest decline was seen with the lowest chromium loading (0.5% Cr), Promoter metal dispersion was unchanged on activation, except in the case of the highest titanium loading (4.35% Ti), where small titania clusters are formed. Mass spectral analysis of the gases evolved during thermal decomposition in argon led to a mechanism being proposed for the decomposition of the acetate precursor. The first step is dehydration of the silica support, which is followed by decompositon of acetate ligands to form an intermediate, which was thought to be a carbonate, and the final stage is the decomposition of this intermediate to chromium (III) oxide for the unpromoted catalysts. Where a promoter is present a structural and electronic interaction between the chromium complex and the promoter is proposed, which leads to formation of mixed surface oxides of perovskite (M(^II)Ti(^IV)0(_3)) or spinel (M(^II)Al(_2)(^III)0(_4)) structure, where M = Cr. For activation under oxygen the pattern of decomposition was much simpler. Studies of the promoted catalysts showed the oxidation to occur—in two stages. It was not clear which chromium species were present after the first step, but the second step led to the formation of chromium (VI) oxide for all catalysts. Modelling of the adsorption sites on metal surfaces has also been undertaken with a series of triosmium carbonyl complexes containing ligands derived from aniline, phenol, pyrrole, furan, thiophene and benzene. These complexes have been characterized using Fourier Transform Infra Red spectroscopy and their vibrational spectra assigned in full. The usefulness of these complexes as models, and in the assignment of vibrational spectra of adsorbates on metal surfaces, is discussed.

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No description available.

Catalytic supercritical water gasification (SCWG) is a promising technology for hydrogen and methane production from wet organic feedstocks at relatively low temperatures (e.g. <500 oC). However, in order to make this process technically and economically viable, solid catalyst with enhanced activity and improved hydrogen selectivity should be developed. In this study, different aspects of catalytic SCWG have been investigated. The performance of several supported-nickel catalysts were examined to identify catalysts that lead to high carbon conversion and high hydrogen yields under near-critical conditions (i.e. near 374 oC). Moreover, for the first time, the effects of several parameters which dominated the activity of the supported nickel catalysts have been systematically investigated. Among the several different catalyst supports evaluated at 5% nickel loading, α-Al2O3, carbon nanotube (CNT), and MgO supports resulted in highest carbon conversions, while SiO2, Y2O3, hydrotalcite, yttria-stabilized zirconia (YSZ), and TiO2 showed modest activities. Comparing the XRD patterns for the support materials before and after the exposure to supercritical water, α-Al2O3, YSZ, and TiO2 were found to be hydrothermally stable among the metal oxide supports. Using the same amount of nickel on α-Al2O3, the methane yield decreased by increasing the nickel to support ratio whereas the carbon conversion was only slightly affected. At a given nickel to support ratio, a threefold increase in methane yield was observed by increasing the temperature from 350 to 410 oC. The catalytic activity also increased by the addition small quantity of potassium. The activity of Ni/γ-Al2O3 catalyst varied based on the affinity of the catalyst to form nickel aluminate spinel. This is also the first report on the role of oxidative pretreatment of the carbon nanotubes by nitric acid on the performance of these catalysts for the supercritical water gasification process. Using different lignocellulosic feeds, it was found that the gasification of glucose, fructose, cellulose, xylan and pulp resulted in comparable gas yields (± 10%) after 60 min, whereas alkali lignin was substantially harder to gasify. Interestingly, gasification yield of bark, which had a high lignin content, was comparable to those of cellulose. In summary, the Ni/α-Al2O3 catalyst had a higher hydrogen selectivity and comparable catalytic activity to the best commercially available catalysts for SCWG of carbohydrates.