Rationalizing the Influence of the Mn(IV)/Mn(III) Red-Ox Transition on the Electrocatalytic Activity of Manganese Oxides in the Oxygen Reduction Reaction

• Published in: Electrochimica acta Vol. 187; pp. 161 - 172
• Main Authors: Ryabova, Anna S., Napolskiy, Filipp S., Poux, Tiphaine, Istomin, Sergey Ya, Bonnefont, Antoine, Antipin, Denis M., Baranchikov, Alexander Ye, Levin, Eduard E., Abakumov, Artem M., Kéranguéven, Gwénaëlle, Antipov, Evgeny V., Tsirlina, Galina A., Savinova, Elena R.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01.01.2016; Elsevier
• Subjects: Catalysis; Chemical Sciences; Interfacial Red-ox transition; Manganese oxides; Meanfield kinetic modeling; Other; Oxygen reduction reaction (ORR); Rotating disc electrode (RDE); Meanfield kinetic modeling; Interfacial Red-ox transition; Manganese oxides; Oxygen reduction reaction (ORR); Rotating disc electrode (RDE)
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2015.11.012

Knowledge on the mechanisms of oxygen reduction reaction (ORR) and descriptors linking the catalytic activity to the structural and electronic properties of transition metal oxides enable rational design of more efficient catalysts. In this work ORR electrocatalysis was studied on a set of single and complex Mn(III) oxides with a rotating disc electrode method and cyclic voltammetry. We discovered an exponential increase of the specific electrocatalytic activity with the potential of the surface Mn(IV)/Mn(III) red-ox couple, suggesting the latter as a new descriptor for the ORR electrocatalysis. The observed dependence is rationalized using a simple mean-field kinetic model considering availability of the Mn(III) centers and adsorbate-adsorbate interactions. We demonstrate an unprecedented activity of Mn2O3, ca. 40 times exceeding that of MnOOH and correlate the catalytic activity of Mn oxides to their crystal structure.