Origin of Selective Production of Hydrogen Peroxide by Electrochemical Oxygen Reduction

Oxygen reduction reaction (ORR) is one of the most important electrochemical reactions. Starting from a common reaction intermediate *-O-OH, the ORR splits into two pathways, either producing hydrogen peroxide (H₂O₂) by breaking the *-O bond or leading to water formation by breaking the O-OH bond. However, it is puzzling why many catalysts, despite the strong thermodynamic preference for the O-OH breaking, exhibit high selectivity for hydrogen peroxide. Moreover, the selectivity is dependent on the potential and pH, which remain not understood. Here we develop an advanced first-principles model for effective calculation of the electrochemical reaction kinetics at the solid-water interface, which were not accessible by conventional models. Using this model to study representative catalysts for H₂O₂ production, we find that breaking the O-OH bond can have a higher energy barrier than breaking *-O, due to the rigidity of the O-OH bond. Importantly, we reveal that the selectivity dependence on potential and pH is rooted into the proton affinity to the former/later O in *-O-OH. For single cobalt atom catalyst, decreasing potential promotes proton adsorption to the former O, thereby increasing the H₂O₂ selectivity. In contrast, for the carbon catalyst, the proton prefers the latter O, resulting in a lower H₂O₂ selectivity in acid condition. These findings explain the experiments and highlight the kinetic origins of the selectivity. Our work improves the understanding of ORR by uncovering the proton affinity as a new factor and provides a new model to effectively simulate the atomic-level kinetics of heterogeneous electrochemistry.