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Monovacant polyoxometalates incorporated into MIL-101(Cr): novel heterogeneous catalysts for liquid phase oxidation

Paper ID Volume ID Publish Year Pages File Format Full-Text
40411 45852 2013 11 PDF Available
Title
Monovacant polyoxometalates incorporated into MIL-101(Cr): novel heterogeneous catalysts for liquid phase oxidation
Abstract

Two novel hybrid composite materials, PW11@MIL-101 and SiW11@MIL-101, were prepared by the inclusion of the potassium salts of the monovacant polyoxotungstates, [PW11O39]7− (PW11) and [SiW11O39]8− (SiW11), into the porous Metal-Organic Framework MIL-101(Cr). Materials were characterized by a myriad of solid-state methods such as powder X-ray diffraction (XRD), vibrational (FT-IR and FT-Raman) and 31P solid-state NMR spectroscopies, elemental analysis, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX), and textural analysis confirming the incorporation of the POMs into MIL-101(Cr). PW11@MIL-101 and SiW11@MIL-101 revealed to be active, selective and recyclable catalysts for the oxidation of cis-cyclooctene, geraniol and R-(+)-limonene using the H2O2 as oxidant. Only one product was obtained from the epoxidation of cis-cyclooctene and geraniol: 1,2-epoxycylooctane and 2,3-epoxygeraniol, respectively. In the oxidation of R-(+)-limonene the main products were limonene-1,2-epoxide and limonene-1,2-diol, however the diepoxide was also formed. Both composite materials, PW11@MIL-101 and SiW11@MIL-101, are recyclable for, at least, three consecutive cycles without significant loss of activity. The stability of the composites after the catalytic cycles was confirmed by several techniques. Remarkably, the MOF framework was found to play an important role in the stability of the PW11 in the presence of H2O2.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (367 K)Download as PowerPoint slideHighlights► Novel composite materials, PW11@MIL-101 and SiW11@MIL-101, were isolated. ► Materials were characterized and investigated as heterogeneous catalysts. ► Sustainable oxidation of cis-cyclooctene, geraniol and R-(+)-limonene was studied. ► Both composite materials revealed to be active, selective and recyclable catalysts.

Keywords
Polyoxometalates; Metal organic-framework; Hybrid materials; Heterogeneous catalysis; Oxidation
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Monovacant polyoxometalates incorporated into MIL-101(Cr): novel heterogeneous catalysts for liquid phase oxidation
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Publisher
Database: Elsevier - ScienceDirect
Journal: Applied Catalysis A: General - Volume 453, 26 February 2013, Pages 316–326
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
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