Kinetics and Mechanism of Ozone Decomposition and Oxidation of Ethanol on Manganese Oxide Catalysts
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Understanding and establishing reaction mechanisms is an important area in heterogeneous catalysis. This dissertation describes the use of in situ laser Raman spectroscopy combined with kinetic measurements and dynamic experiments to determine the mechanism of catalytic reactions. Two cases involving ozone reactions on manganese oxide catalysts were treated. Manganese oxide was chosen because it is the most active of the transition metal oxides for ozone decomposition and because it is a well-known catalyst for complete oxidation reactions. The first case studied was that of the ozone decomposition reaction on a supported manganese oxide catalyst. An adsorbed species with a Raman signal at 884 cm-1 was observed and assigned to a peroxide species based on results of in situ Raman spectroscopy, 18O isotopic substitution measurements, and ab initio MO calculations. The reaction pathway of ozone decomposition was elucidated with carefully designed isotopic experiments. The reaction sequence was found to involve two irreversible, kinetically significant steps: 1) dissociative adsorption of ozone to form a peroxide species and an atomic oxygen species, and 2) desorption of the peroxide intermediate. The kinetic behavior of the peroxide species and the overall decomposition reaction were investigated to test the validity of the proposed sequence. The transient kinetics were found to be consistent with the steady state kinetics, and both were well represented by the two-step sequence, indicating that the proposed reaction sequence accurately described the mechanism of decomposition. The surface was found to be non-uniform, with activation energies that varied linearly with coverage. At zero surface coverage the activation energy for ozone adsorption was found to be 6.2 kJ mol-1, while that for desorption of the peroxide species was found to be 69.0 kJ mol-1. The second case investigated was that of ethanol oxidation using ozone on alumina and silica supported manganese oxide catalysts. Ethanol was found to react with ozone at lower temperatures than with oxygen, and also with a lower activation energy. The reaction kinetics was found to be well described by a power law equation with the reaction orders on ozone and ethanol being 0.89 and 0.81 respectively. The oxidation reactivity was found to be closely related to that of ozone decomposition, suggesting an important role of ozone decomposition in the reaction mechanism. In situ laser Raman spectroscopic studies showed the existence of adsorbed ethoxide species on the catalyst surface under reaction conditions, however, at a much lower concentration than when oxygen alone was used as the oxidant. Transient experiments provided direct evidence that surface peroxide (an adsorbed species due to ozone) and surface ethoxide (an adsorbed species due to ethanol) reacted with each other on the catalyst surface.
- Doctoral Dissertations