Well-Defined Co₂ Dual-Atom Catalyst Breaks Scaling Relations of Oxygen Reduction Reaction

The 4-electron oxygen reduction reaction (ORR) under alkaline conditions is central to the development of non-noble metal-based hydrogen fuel cell technologies. However, the kinetics of ORR are constrained by scaling relations, where the adsorption free energy of *OOH is intrinsically linked to that of *OH with a nearly constant difference larger than the optimal value. In this study, a well-defined binuclear Co₂ complex was synthesized and adsorbed onto carbon black, serving as a model dual-atom catalyst. This catalyst achieved a record half-wave potential of 0.972 V versus the reversible hydrogen electrode in an alkaline electrolyte. Density functional theory simulations and in situ infrared spectroscopy revealed that the dual-atom site stabilizes the *OOH intermediate through bidentate coordination, thereby reducing the free energy gap between *OOH and *OH. By altering the adsorption configuration of *OOH on the dual-atom site, the scaling relations are effectively disrupted, leading to a significant enhancement in ORR activity. © 2024 American Chemical Society.