Abstract
The activation of hydrogen peroxide (H2O2) as a terminal oxidant holds great promise for catalytic oxidation processes. However, developing an efficient catalyst for the epoxidation of bulky organic molecules with H2O2, including cyclic alkenes, remains challenging. In this research, a lacunary polyoxometalate (POM)‐based tetrakaidecahedron nanodices (NDs) are synthesized by [PW11O39]7− (PW11) clusters with tetrabutylammonium bromide (TBAB). The NDs exhibit significantly enhanced catalytic activity in the epoxidation of cyclooctene, with a yield 55.4 times greater than that of the raw PW11. Conversely, nanospheres (NSs) assembled from non‐lacunary POM clusters of [PW12O40]3− (PW12) under the same conditions achieve only a 2.9% yield, highlighting the essential role of the lacunary PW11 structure in NDs. Raman spectroscopy and density functional theory calculations confirm that the active hydroperoxo species from H2O2 activation serves as the effective epoxidizing agent. The reduced energy barrier for H2O2 activation on PW11, relative to PW12, corroborates the superior activity of the NDs. Furthermore, the intermediate generated post‐H2O2 activation shows stronger adsorption of cyclooctene, increasing oxygen transfer to cyclooctene during the epoxidation process. This study demonstrates the exceptional performance of an assembly structure utilizing lacunary POMs for the activation of H2O2 and subsequent oxidation reactions.
Published Version
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