Recently, Fe porphyrins featuring carboxyphenyl were synthesized and found to be selective for O2 reduction to water. It was suggested that the carboxylic acid groups behave as proton relays to O2. In this presentation, DFT calculations are performed to test this hypothesis by comparing the ortho-substituted isomer, in which the COOH ligands are close to the bound O2, with the para-substituted isomer, where the ligands are distant. Two protonation pathways are considered for each O2 reduction intermediate in each isomer: indirect protonation via COOH relays and direct protonation from the acid.

Proton relay vs. non-relay behavior on the O<sub>2</sub> electrocatalytic reduction of O<sub>2</sub> to water

248th National Meeting (2014)

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Proton relay vs. non-relay behavior on the O2 electrocatalytic reduction of O2 to water

Proton relay vs. non-relay behavior on the O₂ electrocatalytic reduction of O₂ to water