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 4f 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 4f 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 4f 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. Bracingly, the Ce1/CoO‐based LOB exhibits an ultra‐low charge‐discharge polarization (0.46 V) and stable cyclic performance (1088 hours). This work breaks through the traditional limitations in catalyst activity and stability, providing new strategies and theoretical insights for developing high‐performance LOBs powered by rare‐earth elements.

中文翻译：

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利用 4f 电子循环进行集成双波段氧化还原系统可增强锂氧电池的电催化作用


深入理解和操纵金属中心的能带占据对于促进锂氧电池（LOB）反应中的有效吸附和电子转移至关重要。稀土元素由于其深轨道和4f电子的强局域化而在能带杂化中发挥着独特的作用。在此，我们将单个Ce原子锚定在CoO上，构建了具有d-fa双带氧化还原中心的高活性和稳定的催化剂。研究发现，4f电子的巡回行为引入了增强的自旋轨道耦合效应，有利于Ce/Co活性位点和*O之间理想的σ/π键合和灵活吸附。同时，局域Ce 4f电子的注入增强了Co-O的轨道键合能力，有效抑制了Co位点的溶解，提高了正极材料的结构稳定性。令人振奋的是，基于 Ce1/CoO 的 LOB 表现出超低的充放电极化（0.46 V）和稳定的循环性能（1088 小时）。这项工作突破了催化剂活性和稳定性的传统限制，为开发稀土元素驱动的高性能LOB提供了新的策略和理论见解。