Polyoxometalates (POMs) are molecular metal oxide clusters that feature a broad range of structures and functionalities, making them one of the most versatile classes of inorganic molecular materials. They have attracted widespread attention in homogeneous catalysis. Due to the challenges associated with their aggregation, precipitation, and degradation under operational conditions and to extend their scope of applications, various strategies of depositing POMs on heterogeneous substrates have been developed. Recent ground-breaking developments in the materials chemistry of supported POM composites are summarized and links between molecular-level understanding of POM-support interactions and macroscopic effects including new or optimized reactivities, improved stability, and novel function are established. Current limitations and future challenges in studying these complex composite materials are highlighted, and cutting-edge experimental and theoretical methods that will lead to an improved understanding of synergisms between POM and support material from the molecular through to the nano- and micrometer level are discussed. Future development in this fast-moving field is explored and emerging fields of research in POM heterogenization are identified.
Keywords: charge transfer; composites; heterogenization; molecular metal oxides; substrates.
© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.