Altering oxygen binding by redox-inactive metal substitution to control catalytic activity: oxygen reduction on manganese oxide nanoparticles as a model system

01 June 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Electrocatalytic transformations of oxygen, i.e., the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), are key processes in renewable energy conversion, defining to a large extent, the efficiency of numerous energy conversion technologies, such as fuel cells, metal-air batteries or water electrolyzers. However, the development of highly effective, stable and inexpensive materials for such conversion processes is a bottleneck. Hence, establishing generic catalyst design principles by identifying structural features of catalysts that influence their performance would constitute a major step towards the rational engineering of advanced electrocatalysts. In this study, by investigating a series of metal-substituted manganese oxide (spinel), Mn3O4:M (M = Sr, Ca, Mg, Zn, Cu), nanoparticles as a model system, we demonstrate experimentally and rationalized the dependence of the activity of Mn3O4:M for ORR and the oxygen binding strength in Mn3O4:M oxides on the properties of the M substituent, viz. the enthalpy of formation of the binary MO oxide and the Lewis acidity of the M2+ substituent. Incorporation of elements M that have a low enthalpy of formation of MO (i.e., highly exothermic oxides featuring relatively strong M‒O bonding) enhances the oxygen binding strength in Mn3O4:M, which increases its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species on the catalyst surface. Our work provides a new perspective on the design of new compositions for oxygen electrocatalysis relying on the substitution by redox-inactive elements affecting the binding energy of oxygen to the surface of the complex metal oxide catalysts (ORR/OER activity descriptor). We speculate that this concept is general and transferrable to a broad selection of materials and processes involving oxygen adsorption and redox, beyond electrocatalysis.

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