Dual‐Atom Catalysts for Bifunctional Oxygen Electrocatalysis: Controllable Construction and Synergistic Mechanisms

ABSTRACT Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the core reactions that determine the energy conversion efficiencies of rechargeable metal–air batteries and regenerative fuel cells. Dual atom catalysts (DACs) overcome the scaling‐relationship constraints inherent in single‐atom catalysts (SACs) through hetero/homonuclear active sites that facilitate bridge‐site adsorption and synergistic electronic coupling. These characteristics permit independent modulation of the binding energies of *O, *OH, and *OOH, thereby reducing the overpotentials for both the ORR and OER and enabling efficient bifunctional oxygen electrocatalysis that is difficult to achieve with isolated single‐atom sites. This review systematically summarizes the rational design and controllable construction strategies for the DACs, and comprehensively discusses characterization methods for dual‐atom sites based on synchrotron X‐ray absorption spectroscopy and aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy. It further elaborates on the synergistic modulation mechanisms of the dual‐metal centers on the ORR/OER pathways, and reveals their intrinsic superiority in breaking the linear scaling relationship of oxygen‐containing intermediates. Finally, the current bottlenecks in controllable synthesis, precise characterization, and mechanistic exploration are analyzed, and future optimization directions are outlined. This review is expected to provide theoretical guidance and experimental foundations for the rational design, fabrication, and application of efficient bifunctional DACs for oxygen electrocatalysis.