Orbital Hybridization at Au─O─Zr Interface Promotes Synergistic Single‐Atom/Cluster Catalysis for Durable Zinc–Air Batteries

Single‐atom catalysts (SACs) are fundamentally limited by the activity–stability trade‐off in oxygen electrocatalysis, primarily due to the high surface energy and aggregation tendency of isolated metal atoms. Herein, we develop a low‐temperature (200 °C) in situ thermal anchoring strategy to construct a hybrid Au catalyst (Au ACSA–ZrO 2 ) comprising atomically dispersed Au single atoms and clusters stabilized on ZrO 2 nanoparticles. This mild yet effective process induces strong metal‐support interactions (SMSI), leading to the formation of covalent Au‐O‐Zr interfacial bonds. These bonds effectively inhibit atomic migration and coalescence while simultaneously promoting interfacial charge transfer. Electronic coupling between Au single atoms and adjacent clusters induces significant hybridization between O 2 p and Zr 4 d orbitals, which modulates the local coordination environment and optimizes the adsorption energetics of oxygenated intermediates, thereby accelerating both oxygen reduction and evolution reaction kinetics. When applied in a Zn–air battery, this dual‐site catalyst exhibits exceptional durability with 71.07% round‐trip efficiency and negligible decay over 260 h of continuous cycling, demonstrating that precise orbital interaction, achievable even at low synthesis temperatures, is crucial for high‐performance bifunctional electrocatalysis.