Advances in Bridging Homogeneous and Heterogeneous Water Oxidation Catalysis by Insolubilized Polyoxometalate Clusters

The water oxidation half-reaction is vital in numerous alternative-energy blueprints and technologies since it can provide four protons and four electrons necessary for transforming renewable energy into chemicals and fuels. Significant progress has been made in recent decades in regard to the development of heterogeneous and homogeneous water oxidation catalysts (WOCs). However, homogeneous and heterogeneous catalysts are two parallel frontiers in catalysis science, each possessing their individual advantages and disadvantages. It is urgently required to construct desirable catalysts combining the merits and overcoming the natural shortcomings of homogeneous and heterogeneous WOCs. This Perspective demonstrates an overview of recent progress in utilizing insoluble polyoxometalate (POM) clusters as a promising bridge between homogeneous and heterogeneous WOCs and discusses the characterization methods for the stability, the origin of enhanced activities, electron transfer dynamics, and structure–property correlation of insoluble POM cluster WOCs. This Perspective not only guides the design of robust and efficient insoluble POM cluster catalysts applied for energy transformation but also provides important insights into the design of POM-based heterogeneous catalysts applied in other important fields.