Tailoring First Coordination Sphere of Dual‐Metal Atom Sites Boosts Oxygen Reduction and Evolution Activities

Abstract It is important to tune the coordination configuration of dual‐atom catalyst (DAC), especially in the first coordination sphere, to render high intrinsic catalytic activities for oxygen reduction/evolution reactions (ORR/OER). Herein, a type of atomically dispersed and boron‐coordinated DAC structure, namely, FeN₄B‐NiN₄B dual sites, is reported. In this structure, the incorporation of boron into the first coordination sphere of FeN₄/NiN₄ atomic sites regulates its geometry and electronic structure by forming “Fe‐B‐N” and “Ni‐B‐N” bridges. The FeN₄B‐NiN₄B DAC exhibits much enhanced ORR and OER property compared to the FeN₄‐NiN₄ counterparts. Density functional theory calculations reveal that the boron‐induced charge transfer and asymmetric charge distributions of the central Fe/Ni atoms optimize the adsorption and desorption behavior of the ORR/OER intermediates and reduce the activation energy for the potential‐determining step. Zinc‐air batteries employing the FeN₄B‐NiN₄B cathode exhibit a high maximum power density (236.9 mW cm⁻²) and stable cyclability up to 1100 h. The result illustrates the pivotal role of the first‐coordination sphere of DACs in tuning the electrochemical energy conversion and storage activities.