On the oxygen reduction reaction in phosphoric acid electrolyte: Evidence of significantly increased inhibition at steady state conditions

In the presented work, we investigate the oxygen reduction reaction (ORR) in half-cell measurements employing different electrolytes. The aim is to compare the ORR inhibition due to anion adsorption at transient as well as steady state conditions. It is found that the ORR inhibition at the platinum - phosphoric acid electrolyte interface is a relative slow, time dependent process. The major inhibition is not observed in transient polarization curves but only under steady state conditions. This observation is in contrast to the typical ORR inhibition due to anion adsorption as observed for example in sulfuric acid electrolyte. In sulfuric acid the inhibition is fast and then stays more or less constant in time. As a consequence of our findings, common transient measurements of the ORR activity might not be sufficient to investigate suitable mitigation strategies for the ORR inhibition in phosphoric acid electrolyte. Such strategies need to take steady state conditions into account.
In order to explain the slow ORR inhibition in phosphoric acid electrolyte, two possible explanations are discussed. Either the adsorption of phosphate is a slow, complex process, where a fast adsorption step is followed by a consecutive filling of the surface, or a mass transfer barrier develops at the polarized phosphoric acid-electrode interface. The latter might be the viscoelectric effect that is known from colloidal science. (C) 2016 Elsevier Ltd. All rights reserved.