Electron self exchange reactions of electroactive ionic liquid and nanoparticle materials Public Deposited

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  • March 20, 2019
Creator
  • Weaver, Joshua E.F.
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • Chapter One is a basic introduction to the background and basic chemistry of both ionic liquid and gold nanoparticle materials. This chapter sets in place many concepts that are expanded upon in greater detail in later chapters. Chapter Two contains the synthesis and electrochemical analysis of a series of redox functionalized phosphonium ionic liquid materials. These materials were synthesized and characterized using NMR (1H, 13C, and 31P) and mass spectroscopy by Paul Ragogna's laboratory at the University of Western Ontario. Solution and neat melt electrochemistry (including cyclic voltammetry, chronoamperometry, and AC Impedance) was carried out to characterize the electrochemical behavior of these compounds and compare them to previous studies of other similar molecules. Chapter Three contains the successful synthesis of redox functionalized dendritic ionic liquids base on tris(2-aminoethyl)amine, poly(propylene imine) (PPI), and polyamidoamine (PAMAM) dendrimers. These redox functionalized dendritic ionic liquid materials were analyzed using NMR, mass spectroscopy, and solution and solid state electrochemistry. Despite the high melting points of these materials, electrochemical data was obtained for some neat materials at elevated temperatures and some were obtained using a special CO2 plasticization method. Chapter Four contains the use of the updated Au25(SCH2CH2Ph)18 synthesis, ligand exchange of Au25(L)18 nanoparticles, and the ligand effects on electron self exchange kinetics in solid state mixed valency films. The updated synthetic method has proven to be of great consequence by significantly increasing nanoparticle yield, purity, and ease of synthesis. MALDI data is presented to show purity of the materials and also to accurately show the extent of ligand exchange achieved. Linear sweep voltammetry was used to measure conductivity in solid state films of nanoparticles over the temperature range -10 degrees C to 30 degrees C with various para-substituted (electron withdrawing, donating, or neutral) mercaptobenzene ligands. The results of the solid state linear sweep measurements are also compared to a short study of the same ligand effect measured using AC impedance data. The results of this study indicate that nanoparticle film conductivity may be tuned by careful ligand selection.
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  • "... in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry."
Advisor
  • Murray, Royce W.
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  • Chapel Hill, NC
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  • Open access
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