Rational Design Strategies Toward Efficient and Stable Electrocatalysts for Hydrogen Production via Water Electrolysis: A Comprehensive Review

Abstract

Active and stable electrocatalysts are critical for sustainable hydrogen production, particularly for high‐current‐density water electrolysis and specialized applications like seawater splitting. However, most water‐splitting electrocatalysts show limited activity at high current densities and poor long‐term stability, making it difficult to meet the stringent performance and durability requirements of industrial‐scale applications (operation at high current density (≥500 mA/cm) and long‐term stability (>1,000 h). This review emphasizes the need to rationally design efficient, stable, earth‐abundant, non‐noble‐metal electrocatalysts for scalable, cost‐effective hydrogen production. We discuss progress in developing earth‐abundant transition‐metal oxides, oxyhydroxides, phosphides, nitrides, carbides, and dichalcogenides. We also present an in‐depth analysis of key strategies to enhance the electrocatalytic activity and stability of transition‐metal‐based materials, focusing on hydrogen evolution reactions via water electrolysis. Practical strategies—including heteroatom doping, heterostructure formation, defect engineering, and phase and strain engineering—are discussed within a synergistic experimental and theoretical framework, highlighting their ability to tune electronic structure, enhance surface properties, and improve overall catalytic efficiency. This unique approach is a key feature of this review and guides rational electrocatalyst design. Finally, we provide perspectives on the challenges and opportunities for advancing robust and highly active electrocatalysts for practical hydrogen production via water electrolysis.