Polyoxometalate‐Derived Photocatalysts Enabling Progress in Hydrogen Evolution Reactions

Abstract Photocatalytic water splitting is capable of converting abundant solar energy into environmentally friendly and renewable chemical energy, presenting a promising solution to alleviate the energy crisis and combat environmental pollution. The development of high‐performance photocatalysts is crucial for significantly improving the efficiency of the hydrogen evolution reaction (HER) involved. Polyoxometalate (POM)‐derived materials, known for their tunable compositions, diverse structures, electron storage/release capabilities, as well as quasi‐semiconductor photochemical properties, serve as highly efficient catalysts in sustainable photosynthesis. This comprehensive review navigates the latest advancements in the assembly strategies and HER performance of POM‐based crystalline materials. It also discusses the composite materials formed by infiltrating POM into metal‐organic frameworks (MOF) and examines the roles of transition metal compounds derived from polyoxometalates, such as sulfides and carbides, in photocatalytic HER. Emphasis is placed on the prospects for the future development of POM‐based compounds as photocatalysts, along with several strategies and outlooks that could facilitate their progress. POM‐derived materials are believed to have significant potential to enhance hydrogen production efficiency while maintaining thermal stability in HER processes.