Chemical and Electrochemical O₂ Reduction on Earth-Abundant M‑N‑C Catalysts and Implications for Mediated Electrolysis

M-N-C catalysts, incorporating non-precious-metal ions (e.g. M = Fe, Co) within a nitrogen-doped carbon support, have been the focus of broad interest for electrochemical O₂ reduction and aerobic oxidation reactions. The present study explores the mechanistic relationship between the O₂ reduction mechanism under electrochemical and chemical conditions. Chemical O₂ reduction is investigated via the aerobic oxidation of a hydroquinone, in which the O–H bonds supply the protons and electrons needed for O₂ reduction to water. Mechanistic studies have been conducted to elucidate whether the M-N-C catalyst couples two independent half-reactions (IHR), similar to electrode-mediated processes, or mediates a direct inner-sphere reaction (ISR) between O₂ and the organic molecule. Kinetic data support the latter ISR pathway. This conclusion is reinforced by rate/potential correlations that reveal significantly different Tafel slopes, implicating different mechanisms for chemical and electrochemical O₂ reduction.