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.

The exploration of bifunctional electrocatalysts with high catalytic activity and long-term durability for low-temperature Zn-air batteries (ZABs) is an ongoing challenge. Here, quintet-shelled hollow spheres, P-doped multi-layer Co₃O₄ (PM-Co₃O₄), with enriched oxygen vacancies are prepared by thermally induced mass relocation and a simple phosphating process. Various advanced characterizations reveal P anion-induced effects on internal electronic structure and local coordination environment. The finite element method elucidates that the complex multi-layer spherical nanostructure is conducive to the transport and diffusion of OH^– and O₂. Benefiting from its unique structural features and abundant oxygen vacancies, the well-designed PM-Co₃O₄ presents small reversible oxygen overpotential for catalyzing oxygen reduction/evolution reactions. Accordingly, the fabricated low-temperature ZABs based on PM-Co₃O₄ as air-cathode exhibit high power density (20.8 mW·cm^–2) and long-term stability (over 600 cycles) at the ultra-low temperature of –40 °C, outperforming state-of-art Pt/C+IrO₂-based ZABs. Furthermore, the dynamic evolution mechanism of cobalt oxide catalysts during ZAB operation is elucidated. This work provides a guideline to design efficient electrocatalysts with regulated electronic configurations and exquisite nano-/microstructures for ZABs under extreme working conditions.