Altering Oxygen Binding by Redox‐Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System. Issue 8 (12th January 2023)

• Record Type: Journal Article
• Authors: Wu, Yi‐Hsuan; Mehta, Harshit; Willinger, Elena; Yuwono, Jodie A.; Kumar, Priyank V.; Abdala, Paula M.; Wach, Anna; Kierzkowska, Agnieszka; Donat, Felix; Kuznetsov, Denis A.; Müller, Christoph R.
• Is Part Of: Angewandte Chemie international edition. Volume 62:Issue 8(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-01-12
• Subjects: Electrocatalysis -- Manganese -- Oxygen Binding Energy -- Oxygen Reduction Reaction -- X-Ray Absorption Spectroscopy; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202217186
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 M 2+ 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. Abstract : Substituted manganese oxide nanoparticles, Mn3 O4 :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 Mn3 O4 :M correlates with the enthalpy of formation of the binary MO oxide and the Lewis acidity of the M 2+ site. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis.