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, Mn3O4:M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn3O4:M for the electrocatalytic oxygen reduction reaction (ORR) on the enthalpy of formation of the binary MO oxide, ΔfH°(MO), and the Lewis acidity of the M2+ substituent. Incorporation of elements M with low ΔfH°(MO) enhances the oxygen binding strength in Mn3O4: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. Substituted manganese oxide nanoparticles, Mn3O4:M, were studied as a model system to generalize the electronic effect of redox‐inactive substituents on the electrocatalytic activity of the oxides. The oxygen reduction activity of Mn3O4:M correlates with the enthalpy of formation of the binary MO oxide and the Lewis acidity of the M2+ site. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis.