Developing Oxidation Catalysts, Understanding Mechanisms ofPolyoxometalate-based Oxidations, and Systems for Color-ChangeDetection Technology Público

Abstract

Developing Oxidation Catalysts, Understanding Mechanisms of Polyoxometalate-based Oxidations, and Systems for Color-Change Detection Technology

By Daniel A. Hillesheim

Transition-metal anionic clusters are studied for green oxidation catalysis. Particular attention is paid to understanding the active catalytic species and the mechanism of the reaction. The O2-based oxidation of propane thiol by a gelating nonporous material is presented. The catalytic conversion 2-chloroethyl ethyl sulfide to the corresponding sulfoxide is presented for Ag2[(CH3C(CH2O)3)2V6O13] and a [Fe(H2O)PW11O39]^4- based material. A series of catalytic systems were developed and explored in an attempt to determine the key intermediate in the rapid and selective catalytic aerobic oxidation of sulfides to sulfoxides by nitrogen oxides and bromide Sources of nitrogen oxides and bromide anion were critical to catalysis. The tetra-n-butylammonium salt of [γ-SiW10O32(OH)4]^4- was shown to be the precursor of an active species that catalyzes oxygen transfer from aqueous H2O2 to olefins. An acid dependent H2O2-based reaction generates the active catalyst in solution via decomposition. A catalyst assembled in situ from monomeric components (TBA2WO4, HClO4) exhibits similar properties. The work presented herein continues the pursuit to isolate and characterize palladium and platinum-oxo units stabilized by polyoxometalate ligands. The development, characterization and optimization of a readily deployable color-change detection sensor for the chemical warfare agent mustard is also described.

Table of Contents

Table of Contents Abstract Acknowledgements List of Figures List of Tables List of Schemes Chapter One: Polyoxometalates, Organic-Inorganic Hybrid Materials, and Color-Change Agents for the Oxidative Decontamination and Detection of Sulfur-Containing Chemical Warfare Agents and Other Toxic Chemicals...1 Chapter Two: Understanding the Role of Nitrogen Oxides and Halide in the Aerobic Catalytic Oxidation of Sulfides: The NOx/Br System...58 Chapter Three: Decomposition of γ-[(SiO4)W10O28(OH)4]^4- as a Pathway to an Active Catalyst in Hydrogen Peroxide-based Homogeneous Epoxidations...98 Chapter Four: Disorder Free Palladium and Platinum Oxo Complexes...128

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School	Laney Graduate School
Department	Chemistry
Degree	PhD
Submission	Dissertation
Language	English
Research Field	Chemistry, Inorganic Chemistry, General
Palabra Clave	Polyoxometalate Oxidation Catalysis
Committee Chair / Thesis Advisor	Hill, Craig L, Emory University
Committee Members	Conticello, Vincent, Emory University Hagen, Karl S, Emory University

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