The interconversion of O2/H2O is an important half reaction for biological processes and next-generation energy technologies. Metalloporphyrins are known to catalyze the reduction of O2 both chemically and electrochemically. Quite often, electrocatalytic O2 reduction activity is evaluated by adsorbing the catalyst to the electrode surface. While this approach is useful, electrocatalytic activity can be highly dependent on the preparation method for surface confinement and complicates mechanistic understanding. In this work, a series of iron porphyrin complexes were prepared and evaluated homogenously using DMF as a solvent and [H-DMF]OTf as a proton source. A mechanism has been proposed involving O2 binding and subsequent protonation as the rate-determing step. The rate-law for O2 reduction will be discussed in the context of catalyst structure.

Investigating the mechanism of O2 reduction with iron porphyrin electrocatalysts in the context of structure: Activity relationships

251st National Meeting (2016)

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