Study of Hydrogen Peroxide Reactions on Manganese Oxides as a Tool To Decode the Oxygen Reduction Reaction Mechanism

Hydrogen peroxide has been detected as a reaction intermediate in the electrochemical oxygen reduction reaction (ORR) on transition‐metal oxides and other electrode materials. In this work, we studied the electrocatalytic and catalytic reactions of hydrogen peroxide on a set of Mn oxides, Mn₂O₃, MnOOH, LaMnO₃, MnO₂, and Mn₃O₄, that adopt different crystal structures to shed light on the mechanism of the ORR on these materials. We then combined experiment with kinetic modeling with the objective to correlate the differences in the ORR activity to the kinetics of the elementary reaction steps, and we uncovered the importance of structural and compositional factors in the catalytic activity of the Mn oxides. We concluded that the exceptional activity of Mn₂O₃ in the ORR is due to its high catalytic activity both in the reduction of oxygen to hydrogen peroxide and in the decomposition of the latter, and furthermore, we proposed a tentative link between crystal structure and reactivity.