One of challenges for industrial water electrolysis is to achieve large-sized electrodes with high structural uniformity and reaction stability. Here, catalyst electrodes of water electrolyzer with delicate nanostructures are fabricated through a facile corrosion engineering and ion regulation co-strategy. Herein the corrosion engineering is an energy efficient (60 °C, 10 min) and scalable route to transforming the commercial nickel foam into catalytic active materials, while the introduction of suitable anions in solutions induces the formation of ordered vanadium (V)-doped RuNi nanoparticles (denoted as V-RuNi) and tungsten (W)-doped NiFe nanowire arrays (denoted as W-NiFe) available to catalyze hydrogen/oxygen evolution reactions. The ion doping effect is proposed to explain the enhanced catalytic activity. Then an anion exchange membrane (AEM) water electrolyzer (electrode area: 19 cm × 19 cm) is assembled and operates stably for 200 h at a high current of 10 A with negligible degradation. This work provides a research paradigm to realize the large-area fabrication of low-cost catalyst electrodes for industrial hydrogen generation via water electrolysis.

In the pursuit of inexpensive and efficient oxygen reduction catalysts, Fe–N–C catalysts have garnered significant attention as a viable alternative to scarce platinum-based materials. Nevertheless, the intricate interaction between the carbon matrix and Fe active sites, along with the mechanism by which such synergies modulate catalytic activity, remains elusive. Herein, a programmed temperature pyrolysis strategy is developed to optimize both the carbon matrix properties and coordination environments of Fe sites. Systematic characterizations uncover the correlations between key parameters of Fe sites (the oxidation state, coordination number, and density of state), as well as the carbon matrix (the functional groups, nitrogen species and content, and the degree of graphitization), with the resultant catalytic activity. The optimized catalyst exhibits a high half-wave potential of 0.935 V and good stability, and the assembled zinc–air battery delivers a high peak power density and long-term cycling durability. Theoretical calculations reveal that Fe–N₄ coordination more effectively reduces the energy barrier for *OH release compared to Fe–N₃ coordination. Additionally, adjacent graphitic nitrogen species further lower the energy barrier of the rate-determining step, thereby accelerating oxygen reduction kinetics. This work highlights the critical role of the carbon support and Fe site properties in synergistically boosting the catalytic performance.