Polyoxometalate Chemistry and Catalytic Applications

Polyoxometalates (POMs) are discrete, anionic metal-oxide clusters characterised by remarkable structural diversity and tunable redox, acid–base and photochemical properties. Archetypal frameworks such as the Keggin, Dawson and Lindqvist structures serve as platforms for precise control of nuclearity and electronic configuration. The intrinsic redox flexibility of POMs enables multiple, reversible electron transfers, making them powerful mediators in oxidation and reduction catalysis. Their strong Brønsted acidity and Lewis acidity further broaden their utility in acid-catalysed transformations, including hydrolysis, isomerisation and polymerisation. In heterogeneous systems, POMs can be immobilised on solid supports—such as metal oxides, zeolites or carbon materials—to deliver high surface area catalysts that combine molecular-level activity with robust recyclability. In homogeneous or biphasic arrangements, POMs excel in selective oxidation of organic substrates under mild conditions, oxidative desulfurisation of fuels, water-splitting and electrocatalytic energy conversion. Advances in speciation control, organic functionalisation and hybrid nanocomposite design continue to enhance stability, selectivity and turnover efficiency. These developments underpin the global significance of POM chemistry in sustainable processes, green energy storage and environmental remediation.

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Polyoxometalate Chemistry and Catalytic Applications publication trend

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Technical terms

Polyoxometalate (POM): A discrete anionic metal-oxide cluster composed of early transition-metal centres bridged by oxide ligands, notable for multi-electron redox behaviour and strong acidity.

Keggin structure: A common POM architecture comprising a central tetrahedral heteroatom surrounded by twelve edge-sharing octahedral metal-oxo units, renowned for thermal stability and catalytic versatility.

Proton-coupled electron transfer (PCET): A mechanism in which an electron and a proton are transferred in a concerted or sequential fashion, critical to many redox and catalytic processes.

Oxidative desulfurisation (ODS): A catalytic approach for sulphur removal from fossil fuels involving oxidation of sulphur compounds to more polar sulphoxides or sulphones, followed by extraction.

References

1. Aqueous solutions of super reduced polyoxotungstates as electron storage systems. Energy & Environmental Science (2023).
2. Proton-Coupled Electron Transfer at the Surface of Polyoxovanadate-Alkoxide Clusters. Accounts of Chemical Research (2023).
3. A Comprehensive Review on Catalytic Oxidative Desulfurization of Liquid Fuel Oil. Catalysts (2019).