A novel hybrid containing two kinds of polyoxometalates for catalyzing olefin epoxidation

Abstract

Vanadium-substituted Keggin-type polyoxometalates exhibit a higher negative charge compared to parent polyoxometalates, which not only enhances their ability to coordinate with metals but also endows them with significant potential for oxidative catalysis due to the intrinsic high oxidative catalytic capacity of vanadium. In this study, by incorporating vanadium-substituted Keggin-type polyoxometalates and sodium molybdate, an inorganic-organic hybrid compound, [Cu₆(phen)₆(Mo₆O₂₂)(HPMo₁₀V₂O₄₀)·H₂O] (phen = 1,10-phenanthroline), was successfully constructed under hydrothermal conditions. This compound is composed of two kinds of polyoxometalates, [PMo₁₀V₂O₄₀]⁵⁻ and [Mo₆O₂₂]⁸⁻, in which {PMo₁₀V₂} and {Mo₆} represent [PMo₁₀V₂O₄₀]⁵⁻ and [Mo₆O₂₂]⁸⁻, respectively. In the catalytic epoxidation of olefins, this hybrid efficiently oxidized cyclooctene to 1,2-epoxycyclooctane within 4 hours at 35 °C using oxygen as the oxidant (conversion rate of 98.6% and a selectivity greater than 99%). Moreover, it retained high catalytic activity after five successive cycles and demonstrated broad substrate scope, effectively catalyzing the epoxidation of various olefins.

Keywords

vanadium-substituted Keggin-type polyoxometalates / inorganic-organic hybrids / olefin epoxidation

Acknowledgements

This research was financially supported by the National Natural Science Foundation of China (22371034).

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