Neodymium‐Evoked Valence Electronic Modulation to Balance Reversible Oxygen Electrocatalysis

Abstract Suffering from the competition adsorption between oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), the development of high‐efficiency oxygen electrocatalysts with bifunctional properties still remains a challenge. Herein, a novel and effective neodymium‐evoked valence electronic perturbation strategy to improve and balance reversible oxygen electrocatalysis of metallic cobalt sites is proposed. To heighten the coupling between Nd and Co, the metal‐organic‐framework‐induced method is chosen to prepare the target catalyst of atomic Nd‐doped Co on an N‐doped carbon substrate. The as‐prepared catalyst presents excellent bifunctional electrocatalytic properties with a low overpotential of 288 mV at 10 mA cm −2 for the OER and a high half‐wave potential of 0.85 V for the ORR. The robust electrocatalytic stabilities for both the ORR and OER are also proven. The electrochemical in situ Raman spectra confirm the surface dynamic change of the transformation of oxygen intermediates by noting the formation of Co–OOH. Theoretical calculations verify that the adsorption of oxygen intermediates is balanced owing to the strong Co 3d‐Nd 4f orbital electronic coupling effect below the Fermi level. Moreover, the potential practicability of catalyst is further demonstrated in solid‐state rechargeable Zn‐Air batteries, which exhibit large power density and a long cycling life.