The oxygen reduction reaction (ORR), O2 + 4e– + 4H+ → 2H2O, is a prototypical electrocatalytic proton-coupled electron transfer (PCET) reaction. Systematic studies of the ORR catalyzed by soluble iron porphyrin complexes have explored the kinetics, mechanism(s), and overpotentials. Correlations between the turnover frequencies and effective overpotentials of a soluble electrocatalyst will be developed to demonstrate the presence of multiple scaling relationships. These relationships show that optimization requires consideration of the entire catalytic system, not just the electrocatalyst. A photo-electrocatalytic ORR process will also be described, using porphyrins and other dyes attached to NiO electrodes to produce hydrogen peroxide. The mechanism of this process and the potential difficulties in connecting molecular and semiconductor energetics will be discussed.

Electrocatalysis and photo-electrocatalysis of the oxygen reduction reaction

255th National Meeting (2018)

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