Storage of Energy in Chemical Bonds Utilizing Earth-Abundant Molecular Electrocatalysts: Improving Catalyst Design Through an Understanding of Mechanism

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.