Transition Metal Phosphides in Electrocatalytic Alkaline Hydrogen Evolution: Rational Functional Design Principles and Strategies

ABSTRACT To address the global energy crisis and environmental pollution, developing efficient and sustainable hydrogen production technologies is of paramount importance. Electrochemical water splitting, particularly anion exchange membrane water electrolysis (AEMWE), offers a sustainable and efficient alternative for large‐scale hydrogen generation. The hydrogen evolution reaction (HER) in alkaline media exhibits sluggish kinetics owing to the additional Volmer step, which involves the adsorption of water molecules followed by their dissociation to generate active hydrogen (*H). Since single‐component catalysts rarely simultaneously optimize H 2 O adsorption, H 2 O dissociation, and the binding energies of active hydrogen (HBE) and active hydroxyl (OHBE), the development of multi‐component catalysts with tailored properties offers a promising strategy to enhance alkaline HER performance. This review provides a comprehensive summary and professional guidance on component regulation strategies for transition metal phosphide (TMP)‐based catalysts in alkaline HER. It begins by articulating the core design principles essential for developing highly efficient TMP catalysts, emphasizing the correlation between structural features and catalytic performance. Building on this foundation, the review systematically discusses key component regulation strategies, including doping, alloying, and heterostructures. Furthermore, it offers a forward‐looking perspective on the future design and functional regulation of TMPs for alkaline HER. Finally, the review addresses the current challenges facing TMPs in this context and explores promising directions for future research and development.