Fe-substituted Polyoxometalate-based Spherical Assemblies as Catalysts for Olefin Epoxidation

Abstract

Fe-substituted polyoxometalate(Na₁₅[(P₂W₁₅O₅₆)₂Fe₃])(Fe-POM)-based composite (C₁₉H₄₂N)₁₅[(P₂W₁₅O₅₆)₂Fe₃](CTAB-Fe-POM) was successfully synthesized through an ion-exchanged method. Then, it was self-assembly in a mixed solvent to form surfactant encapsulated complex nanosphere(SECN). The as-prepared SECN was employed as the catalyst for the epoxidation of olefins with H₂O₂. Compared with (C₁₉H₄₂N)₆[α-P₂W₁₈O₆₂](CTAB-P₂W₁₈), SECN shows a higher activity in the epoxidation of cis-cyclooctene with a high yield(97.3%). The extraordinary performance could be attributed to the amphiphilic module of cetyltrimethylammonium bromide(CTAB), which improves the dispersion of the catalyst in CH₃CN and accelerates the catalytic reaction. And Fe atom can rapidly activate H₂O₂, forming the active intermediate Fe-OOH to realize the transfer of active “O”. Furthermore, the catalyst could be reused five times without significant loss of activity.

Keywords

Polyoxometalate / Self-assembly / Epoxidation / Nanosphere / Mechanism

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