Chemical Ordering Command Dynamic Reconstruction for Enhanced Water Oxidation

ABSTRACT Dynamic surface reconstruction fundamentally dictates the active state of electrocatalysts. However, the lack of mastery over reconstruction kinetics typically imposes a trade‐off between high activity and long‐term stability. Here, we demonstrate that the degree of chemical ordering (long‐range atomic site occupancy) deterministically governs the evolution of alloy surfaces under operating conditions. In this design, the chemical ordering acts as a structural template that commands the reconstruction trajectory. During anodic dealloying, the ordered lattice facilitates a controlled, mild pre‐oxidation. This process generates high‐valence Fe/Co/Ni sites that trigger a well‐balanced, synergistic adsorbate evolution mechanism (AEM)/lattice oxygen mechanism (LOM) dual pathway. Unlike disordered counterparts that suffer from severe deterioration, the thermodynamically stable intermetallic core prevents excessive metal dissolution, reducing elemental leaching by 97.2%, guiding the formation of a homogeneous active reconstruction layer. As a result, the catalyst achieves an overpotential of only 335 mV at 1 A cm −2 and maintains exceptional stability for over 1000 h. Even under industrial conditions (6 M KOH, 353 K), it reaches 3 A cm −2 at only 1.50 V. This work establishes chemical ordering as a predictive parameter to govern dynamic reconstruction, offering a robust framework for designing self‐adaptive catalysts that harmonize extreme activity with industrial‐grade durability.