The embedding of molecular metal oxides, or polyoxometalates (POMs), in metal–organic frameworks (MOFs) opens new research avenues in catalysis and beyond. This review explores the host–guest chemistry of POMs embedded in MOF hosts and discusses the synergism of the resulting composites for heterogeneous catalysis. The review focuses on well-established and well-studied classes of POMs, such as Keggin and Wells–Dawson anions, and well-researched MOFs, including the MIL, UiO, and NENU families. Outstanding examples of synergistic catalytic activity between the POM and MOF are described, and key performance parameters, including POM localization, pore size and pore structure, as well as particle size effects are described for technologically important catalytic processes. In addition to thermal catalysis, we discuss the use of POM@MOF composites for electro- and photocatalysis with an emphasis on energy conversion systems. Finally, we provide an outlook on emerging areas where POM@MOF composites could lead to new catalytic reactivity.

One of the most attractive areas in inorganic chemistry is the synthesis of polyoxometalates (POMs) exhibiting new properties and applications. Since the impact of POMs in biochemistry and related fields of research has increased in the last few years, there has been a special interest in this topic. Significant progress in biological applications has been made where the interaction of POMs with amino acids, peptides and proteins is relevant. Versatile POMs play a series of different roles in the interaction with these biomolecules as described in this review. Various types of interactions are established, depending on the POM shape and charge, the amino acid side chain, peptide sequence or protein structure. Experimental conditions such as temperature, acidity, solvent, etc. are also important factors that influence the binding/reactivity of POM with biomolecules, as described herein. This understanding allows the adequate design of the POM-biomolecule couple for tailoring and controlling mechanisms of action such as catalysis, inhibition, and aggregation, or the crystallising agent.

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