Superoxide Decay Pathways in Oxygen Reduction Reaction on Carbon-Based Catalysts Evidenced by Theoretical Calculations.

Superoxide decay behavior is evaluated by contrastive potential energy surface analyses from theoretical calculations. The presence of carbon surfaces enhances the superoxide decay through disproportionation instead of electroreduction, which is a non-electrochemical reaction that impedes the increase in energy efficiency for relevant energy conversion applications. Nitrogen doping of carbon effectively retards the disproportionation by influencing the oxygen stretching vibration and changing the proton-coupled electron transfer trend.