Same FeN4 Active Site, Different Activity: How Redox Peaks Control Oxygen Reduction on Fe Macrocycles

Macrocycles show high activity for the electrochemical reduction of oxygen in alkaline media. However, even macrocycles with the same metal centers and MN4 active site can vary significantly in activity and selectivity, and to this date, a quantitative insight into the cause of these staggering differences has not been unambiguously reached. These macrocycles form a fundamental platform, similarly to platinum alloys for metal ORR catalyst, to unravel fundamental properties of FeNx catalysts. In this manuscript, we present a systematic study of several macrocycles, with varying active site motif and ligands, using electrochemical techniques, operando spectroscopy, and density functional theory (DFT) simulations. Our study demonstrates the existence of two families of Fe macrocycles for oxygen reduction in alkaline electrolytes: (i) weak *OH binding macrocycles with one peak in the voltammogram and high peroxide selectivity and (ii) macrocycles with close to optimal *OH binding, which exhibit two voltametric peaks and almost no peroxide production. Here, we also propose three mechanisms that would explain our experimental findings. Understanding what differentiates these two families could shed light on how to optimize the activity of pyrolyzed FeNx catalysts.