Chemical and electrochemical studies to improve homogeneous electrocatalysts

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Abstract/Contents

Abstract
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.

Description

Type of resource text
Form electronic resource; remote; computer; online resource
Extent 1 online resource.
Place California
Place [Stanford, California]
Publisher [Stanford University]
Copyright date 2019; ©2019
Publication date 2019; 2019
Issuance monographic
Language English

Creators/Contributors

Author McLoughlin, Elizabeth Ann
Degree supervisor Waymouth, Robert M
Thesis advisor Waymouth, Robert M
Thesis advisor Xia, Yan, 1980-
Thesis advisor Zare, Richard N
Degree committee member Xia, Yan, 1980-
Degree committee member Zare, Richard N
Associated with Stanford University, Department of Chemistry.

Subjects

Genre Theses
Genre Text

Bibliographic information

Statement of responsibility Elizabeth A. McLoughlin.
Note Submitted to the Department of Chemistry.
Thesis Thesis Ph.D. Stanford University 2019.
Location electronic resource

Access conditions

Copyright
© 2019 by Elizabeth Ann McLoughlin
License
This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).

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