Storage of Energy in Chemical Bonds Utilizing Earth-Abundant Molecular Electrocatalysts: Improving Catalyst Design Through an Understanding of Mechanism
Nichols, Asa, Chemistry - Graduate School of Arts and Sciences, University of Virginia
Machan, Charles, AS-Chemistry, University of Virginia
The studies described in this dissertation focus on the use of N2O2 ligands in the CO2 reduction reaction and the oxygen reduction reaction. The use of Fe and Co metal centers in these ligand frameworks leads to different reactivity profiles. Chapter 2 of this dissertation focuses on the synthesis, characterization, and reactivity of an Fe(N2O2) compound towards CO2 under electrochemically reducing conditions in the presence of phenol for the production of formate. These studies are continued in Chapter 3 with a focus on studying how secondary-sphere moieties oriented towards the protonation-sensitive Fe-bound phenolate ligands affect catalytic reactivity towards CO2. Chapter 4 focuses on synthesis, characterization, and reactivity of a Co(N2O2) compound towards the oxygen reduction reaction. These oxygen reduction studies are continued in Chapter 5 with a focus on studying how secondary-sphere moieties oriented towards the catalytically active Co metal center affect catalytic reactivity towards O2. Finally, Chapter 6 summarizes the previous chapters and outlines preliminary results and future directions for new projects.
PHD (Doctor of Philosophy)
electrocatalysis, carbon dioxide reduction, oxygen reduction, secondary-sphere effects
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