Chemical and electrochemical studies to improve homogeneous electrocatalysts
- Elizabeth A. McLoughlin.
- [Stanford, California] : [Stanford University], 2019.
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- The electricity derived from renewable energy sources (e.g. solar, wind) is intermittent and not perfectly matched with consumer demand. The widespread adoption of these renewable energy sources as a replacement for fossil fuels subsequently depends upon the development of energy storage systems. Homogeneous electrocatalysts are promising energy storage systems as they can mediate the efficient interconversion of electrical and chemical energy in a highly tuneable fashion. In this thesis, various electrochemical and spectroscopic studies have been conducted in order to improve homogeneous electrocatalysts along various metrics of activity (i.e. turnover frequency, overpotential), selectivity (i.e. Faradaic efficiency), and stability. Chapter 1 reviews the electrochemical and spectroscopic techniques used to assess homogeneous electrocatalysts; highlights the key metrics by which electrocatalysts are evaluated; and provides selected examples of homogeneous electroreduction and electrooxidation catalysts relevant to the work presented in this thesis. Chapter 2 examines the reactivity of a cyclopentadienyl Co complex bearing a protonated phenylazopyridine ligand towards proton, hydride, and hydrogen atom transfer. Chapter 3 uses Co K-edge X-ray absorption spectroscopy (XAS), extended X-ray absorption fine structure (EXAFS), density functional theory (DFT), and time-dependent DFT methods to investigate the effect that various bidentate ligands have on the electrochemical and protonation properties of cyclopentadienyl Co complexes. Chapter 4 uses Mn K-edge XAS, Mn-Kβ X-ray emission spectroscopy (XES), and DFT to understand the impact that redox active ligands have on the electrochemical properties and speciation of Mn tricarbonyl complexes. Chapter 5 examines the ability of an electrochemically regenerable hydrogen atom transfer reagent to lower the overpotential of electrocatalytic alcohol oxidation. Chapter 6 investigates the use of an Fe-based acceptorless alcohol dehydrogenation catalyst for the electrooxidation of alcohols. Chapter 7 examines the factors that mediate demographic performance gaps and the impact that various pedagogical changes have had on student performance in the introductory chemistry sequence.
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- Submitted to the Department of Chemistry.
- Thesis Ph.D. Stanford University 2019.