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, Mn(3)O(4):M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn(3)O(4):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 M(2+) substituent. Incorporation of elements M with low Δ( f )H°(MO) enhances the oxygen binding strength in Mn(3)O(4):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.