Multiple selectivity-determining mechanisms of H2O2 formation in iron porphyrin-catalysed oxygen reduction.

Multiple H2O2-forming mechanisms are accessible in Fe(porphyrin)-catalysed oxygen reduction, a key reaction in both fuel cell technologies and oxygen-utilizing enzymes. Our kinetic analysis reveals that the porphyrin secondary structure dictates the pathway for H2O2 formation. This approach is generalizable to other electrocatalytic processes and provides insight into the selectivity-determining steps.