Surfactant-assisted sol–gel synthesis of zirconia supported phosphotungstates or Ti-substituted phosphotungstates for catalytic oxidation of cyclohexene

• Zirconia supported POM composites were synthesized by sol–gel technology.
• The POM clusters are highly dispersed in the composites.
• Strong interaction is built between POM units and ZrO2 framework.
• The composites show high catalytic activity in cyclohexene oxidation with H2O2.
• These catalysts are truly heterogeneous in nature, and easily recycled.

The Keggin-type polyoxometalates (POMs) including phosphotungstate and Ti-substituted phosphotungstates were supported on zirconia (ZrO2) matrix by a surfactant-assisted sol–gel copolymerization technique. The resultant ZrO2 supported POMs composite materials (ZrO2–POMs) were characterized by X-ray power diffraction, transmission electron microscopy, Fourier transform infrared spectra, diffuse reflectance ultraviolet–visible spectra, thermogravimetry-differential scanning calorimetry analysis, and 31P magic angle spinning (MAS) nuclear magnetic resonance (NMR) analysis. The results showed that the ZrO2–POMs materials have worm-like disordered mesoporous, and the primary structure of POMs is preserved after the formation of the composite materials. All the ZrO2–POMs materials are catalytically active for the H2O2-mediated oxidation of cyclohexene with relatively high selectivity to allylic oxidation products. Moreover, these materials exhibit high stability against leaching of active species, and can be easily recycled without obvious loss of activity and selectivity. The existence of relatively strong interaction between the POM units and the ZrO2 framework should play important role in fabricating the stable heterogeneous ZrO2–POMs catalysts.

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