Harnessing 4f Electron Itinerancy for Integrated Dual‐Band Redox Systems Boosts Lithium‐Oxygen Batteries Electrocatalysis

In-depth comprehension and manipulation of band occupation at metal centers are crucial for facilitating effective adsorption and electron transfer in lithium-oxygen battery (LOB) reactions. Rare earth elements play a unique role in band hybridization due to their deep orbitals and strong localization of 4 f electrons. Herein, we anchor single Ce atoms onto CoO, constructing a highly active and stable catalyst with d-f a dual-band redox center. It is discovered that the itinerant behavior of 4 f electrons introduces an enhanced spin-orbit coupling effect, which facilitates ideal σ/π bonding and flexible adsorption between the Ce/Co active sites and *O. Simultaneously, the injection of localized Ce 4 f electrons strengthens the orbital bonding capacity of Co-O, effectively inhibits the dissolution of Co sites and improves the structural stability of the cathode material.