Electron Itinerancy Mediated by Oxygen Vacancies Breaks the Inert Electron Chain to Boosts Lithium‐Oxygen Batteries Electrocatalysis

The complex interaction between dopants and oxygen vacancies (Vo) in metal oxides is crucial for enhancing the adsorption and electron transfer processes of Li‐O2 batteries. However, the synergetic mechanism among Vo, dopants, and the host matrix remains unclear. Herein, Ru single‐atom‐modified TiO2 nanorod (Ru1‐TiO2‐x) with abundant Vo were fabricated, serving as an efficient catalyst for Li‐O2 batteries. Experimental and theoretical investigations have demonstrated that Vo as an "electron pump", facilitating electron itinerant behavior, while Ru1 serves as an "electron buffer" to further activate the [Ru‐O‐Ti] electronic chain, implements the Li‐O2 batteries highly active and stable in the process of circulation two‐way self‐adjusting characteristics. Consequently, the Ru1‐TiO2‐x‐based Li‐O2 batteries exhibit an ultra‐low charge polarization and stable performance. Vo and Ru1 synergistically coordinate their control over the d‐band center at the Ti site to establish a flexible and tunable Ru‐Ti dual active site. This adjustment effectively balances the binding strength with the interface oxygen intermediate (*O), thereby significantly reducing the activation barrier. The Hamiltonian layout further revealed the crucial role of remote orbital coupling in maintaining the structural stability. This study provides insights into Vo‐dependent electron transfer kinetics and introduces new strategies for activating catalytically inert materials.