Unique Structural Features of Polyoxometalates for Efficient Alkaline Hydrogen‐Evolution Reaction

The alkaline hydrogen evolution reaction (HER) is a key technology for hydrogen production, and polyoxometalates (POMs) have emerged as promising high-performance catalysts owing to their unique structural and physicochemical properties. This review summarizes the mechanism of alkaline HER, the structural features, HER-relevant properties, synthesis methods, and characterization techniques of POMs and places particular emphasis on recent advances in the application of POMs and POM-derived materials (e.g., nitrides, sulfides) to alkaline HER. We provide an in-depth analysis of structure-activity relationships and mechanisms of catalytic enhancement and present an outlook on future research directions to guide the design and industrial implementation of POM-based alkaline HER catalysts.