Deconvoluting Kinetics and Transport Effects of Ionic Liquid Layers on FeN4-based Oxygen Reduction Catalysts

Abstract The use of ionic liquid layers has been reported to improve both the activity and durability of several oxygen reduction catalysts. However, the development of this technology has been hindered by the lack of understanding of the mechanism behind this performance enhancement. In this work, we use a library of ionic liquids to modify a model FeN4 catalyst (iron phthalocyanine), to decouple the effects of ionic liquid layers on oxygen reduction kinetics and oxygen transport. Our results show that oxygen reduction activity at low overpotentials it determined by the ionic liquids’ influence on the *OH binding energy on the active sites, while oxygen solubility controls transport at high overpotentials. Finally, using porosimetry, we have demonstrated that the distribution of the ionic liquids on the catalyst is inhomogeneous, and depends on the nature of the ionic liquid used.