Nafion-Induced Reduction of Manganese and its Impact on the Electrocatalytic Properties of a Highly Active MnFeNi Oxide for Bifunctional Oxygen Conversion.

Electrocatalysts for bifunctional oxygen reduction (ORR) and oxygen evolution reactions (OER) are commonly studied under hydrodynamic conditions, rendering the use of binders necessary to ensure the mechanical stability of the electrode films. The presence of a binder, however, may influence the properties of the materials under examination to an unknown extent. Herein, we investigate the impact of Nafion on a highly active ORR/OER catalyst consisting of MnFeNi oxide nanoparticles supported on multi-walled carbon nanotubes. Electrochemical studies revealed that, in addition to enhancing the mechanical stability and particle connectivity, Nafion poses a major impact on the ORR selectivity, which correlates with a decrease in the valence state of Mn according to X-ray absorption spectroscopy. These findings call for awareness regarding the use of electrode additives, since in some cases the extent of their impact on the properties of electrode films cannot be regarded as negligible.