Customizing Axially‐Oriented Dual‐Atomic Synergy for Orchestrating Cascade Alkaline Hydrogen Evolution

ABSTRACT The full orchestration of synergistic geometric and electronic interaction at atomic scale is fundamental to surmounting cascade kinetic bottlenecks inherent in multistep electrochemical processes. Here, an axially‐oriented, sulfur‐bridged hetero‐atomic motif (Ru─S─Co) is customized to achieve synergistic regulation throughout alkaline hydrogen evolution reaction (HER). The top‐positioned Ru atoms are tailored for enhanced water capture, and the bottom‐inserted Co atoms in lattice activate middle S atoms for balanced hydrogen adsorption–desorption. This customized multi‐site synergy conspicuously lowers the energy barrier for rate‐determining water scission step. The proportion of reactive free water is elevated on this modified interface to prompt alkaline HER initiation. Furthermore, the intrinsically asymmetric charge distribution along the dual‐atom bridge enhances charge transfer during HER, and the prominent orbital coupling induces an upshift in the Ru d ‐band center together with increased density of states in S p‐orbitals around the Fermi level, further augmenting Ru‐S dual‐site activity. With this catalyst adopted as cathode, the anion‐exchange‐membrane electrolysis cell maintains an industrial current density of 1000 mA cm −2 at a small voltage of 1.79 V with negligible performance decay after long‐term stability test. This work provides insights into precise customization of atomic‐scale synergy toward effective management of kinetically mismatched multisteps in HER‐related energy conversion.