Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System

Establishing generic catalyst design principles by identifying structural features of materials that influence their performance will advance the rational engineering of new catalytic materials. In this study, by investigating metal-substituted manganese oxide (spinel) nanoparticles, Mn₃ O₄ :M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn₃ O₄ :M for the electrocatalytic oxygen reduction reaction (ORR) on the enthalpy of formation of the binary MO oxide, Δ_f H°(MO), and the Lewis acidity of the M²⁺ substituent. Incorporation of elements M with low Δ_f H°(MO) enhances the oxygen binding strength in Mn₃ O₄ :M, which affects its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis relying on the rational substitution/doping by redox-inactive elements.