| The work presented herein is a summary of the experimental and computational studies that I have designed and conducted as a PhD student in the department of Chemical and Biological Engineering at the University of Wisconsin, Madison. At the heart of this work is a strong motivation to extend the applicability of environmentally benign technologies to the bulk of the chemical industry. Heterogeneous catalysts have played and will continue to play a major role in providing commercially viable means of conducting clean chemistry. As such, I have done my part to contribute to the total understanding of their nature in chemical transformations. The chapters herein contain extensive discussion of the synthesis of tin containing, Lewis acidic MCM-41 materials and their application in the Baeyer-Villiger oxidation using the environmentally benign hydrogen peroxide as oxidant in lieu of classical peroxy-carboxylic acid reagents. We have established synthetic capabilities of high quality materials and characterized them using standard techniques such as X-Ray Diffraction, Nitrogen Adsorption, Solid State NMR, Elemental Analysis, and catalytic activity in selected probe reactions.;Having established the synthesis of high quality tin containing mesoporous materials, we investigated the Baeyer-Villiger oxidation further using initial rate studies to highlight mechanistic dependencies on a model ketone, hydrogen peroxide, and water. We have documented a very strong inhibitive effect of water present in the reaction media and subsequently carried out both experimental and computational studies to probe the nature of its inhibition. These studies ultimately yielded a theoretically sound mechanistic model and plausible rate law that we have shown to effectively model kinetic data with a plausible parameter set.;This thesis presents a summary of the insights gained from this work as well as some interesting potential future directions that will no doubt have an impact on the collective understanding of tin-containing silicates and their application green, selective oxidations. |
