Research Progress of Polyoxometalate‐Integrated Frameworks: Syntheses, Properties, and Applications

Standalone applications of polyoxometalates (POMs) are hindered by issues such as solubility and difficult recovery, while other porous frameworks also face their own challenges: covalent organic frameworks (COFs) have limited catalytic sites, metal–organic frameworks (MOFs) suffer from stability issues, and hydrogen‐bonded organic frameworks (HOFs) exhibit dynamic porosity. Integrating POMs with these frameworks effectively overcomes these drawbacks and generates significant synergistic effects: the frameworks provide a confined environment and stability, suppressing POM leaching and aggregation, while POMs contribute rich redox activity and catalytic functionality. This review systematically summarizes the research scope of POMs‐based composite materials, covering classical platforms such as COFs, MOFs, and HOFs, as well as emerging platforms including cyclodextrin‐based supramolecular frameworks relying on host–guest recognition, ionic porous aromatic frameworks with inherent ionic sites, and water cluster‐templated POM‐based hydrogen‐bonded supramolecular frameworks. These composites exhibit outstanding performance in various fields, such as (photo)electrocatalysis, energy storage, (bio)sensing, biomedicine, and proton conduction. The field still faces challenges like harsh synthesis conditions and insufficient long‐term stability. Future research should focus on developing mild and scalable synthesis methods and gaining deeper insights into stability mechanisms, providing a blueprint for designing next‐generation POMs‐based functional materials and their applications in sustainable energy and precision medicine.