Synergistic Integration of Porous Sponge Architecture and Alloy Catalysis Unlocks the Green Code for Industrial‐Scale Alkaline Water Splitting

Green hydrogen production via water electrolysis is the critical pathway to sustainable energy, yet conventional alkaline electrolysis relies on scarce noble metal catalysts, limiting large-scale application. In this study, a self-supporting CoZnNi alloy electrode with hierarchical porous architecture is fabricated via dealloying. This metallic sponge-like material integrates macroscopic frameworks with microscopic channels, enabling electrolyte infiltration and rapid gas bubble release, while the catalytic performance of Co and Ni active sites is optimized through electronic modulation induced by Zn incorporation. The electrode exhibits exceptional activity and stability for both HER and OER at 1000 mA cm−2. In situ Raman spectroscopy reveals that Co sites facilitate water dissociation, Ni sites mediate the adsorption and desorption of hydrogen intermediates, and Co sites drive oxygen evolution via a direct O–O coupling pathway, thereby unraveling the synergistic mechanism. This work offers a promising non-noble bifunctional electrocatalyst design for scalable green hydrogen production.