Revealing the Impact of Electrolyte Composition for Co-Based Water Oxidation Catalysts by the Study of Reaction Kinetics Parameters

Recent studies have revealed the critical role played by the electrolyte composition on the oxygen evolution reaction (OER) kinetics on the surface of highly active catalysts. While numerous works were devoted to understand the effect of the electrolyte composition on the physical properties of the catalysts’ surface, very little is known yet about its exact impact on the OER kinetics parameters. In this work, we reveal that the origin for the electrolyte-dependent OER activity for Co-based catalysts originates from two different effects. Increasing the alkaline electrolyte concentration for La1–xSrxCoO3−δ perovskites with x > 0 and for amorphous CoOOH increases the pre-exponential factor, which can be explained either by an increase of the concentration of active sites or by a change in the entropy of activation. However, changing the alkali cation results in a decrease of the apparent activation enthalpy for Fe-containing amorphous films, traducing a change in intermediates’ binding energies.