Revealing the Orbital Interactions between Dissimilar Metal Sites during Oxygen Reduction Process

Abstract A FeCo/DA@NC catalyst with the well‐defined FeCoN 6 moiety is customized through a novel and ultrafast Joule heating technique. This catalyst demonstrates superior oxygen reduction reaction activity and stability in an alkaline environment. The power density and charge–discharge cycling of znic–air batteries driven by FeCo/DA@NC also surpass those of Pt/C catalyst. The source of the excellent oxygen reduction reaction activity of FeCo/DA@NC originates from the significantly changed charge environment and 3d orbital spin state. These not only improve the bonding strength between active sites and oxygen‐containing intermediates, but also provide spare reaction sites for oxygen‐containing intermediates. Moreover, various in situ detection techniques reveal that the rate‐determining step in the four‐electron oxygen reduction reaction is *O 2 protonation. This work provides strong support for the precise design and rapid preparation of bimetallic catalysts and opens up new ideas for understanding orbital interactions during oxygen reduction reactions.