Engineering of oxoclusters-reinforced polymeric materials with application as heterogeneous oxydesulfurization catalysts

[Display omitted] •Polyacrylate polymers were reinforced upon cross-linking with Zr/Hf oxoclusters.•The hybrid polymers were used for the first time as catalysts for H2O2 activation.•The hybrid polymers enable the heterogeneous oxydesulfurization of a model fuel.•The polymeric environment fosters th...

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Bibliographic Details
Published in:Applied catalysis. B, Environmental Environmental, 2016-03, Vol.182, p.636-644
Main Authors: Vigolo, Marilisa, Borsacchi, Silvia, Sorarù, Antonio, Geppi, Marco, Smarsly, Bernd M., Dolcet, Paolo, Rizzato, Silvia, Carraro, Mauro, Gross, Silvia
Format: Article
Language:English
Subjects:
Activation
Catalysis
Catalysts
DBT oxidation
Displays
Fourier transforms
Hybrid materials
Magnetic resonance
Materials selection
Oxoclusters
Peroxides
Polymethyl methacrylates
Solid state NMR
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Summary:[Display omitted] •Polyacrylate polymers were reinforced upon cross-linking with Zr/Hf oxoclusters.•The hybrid polymers were used for the first time as catalysts for H2O2 activation.•The hybrid polymers enable the heterogeneous oxydesulfurization of a model fuel.•The polymeric environment fosters the oxidation of dibenzothiophene to its sulfone.•SS-NMR, XAS, SAXS demonstrate the high stability of the cross-linked oxoclusters. In this paper we report the first example of hybrid materials based on poly(methlymethacrylate) (PMMA) matrices covalently reinforced by MyOx(OH)w(O(O)CR)z oxoclusters (M=Zr or Hf), used as heterogeneous catalytic systems for hydrogen peroxide activation. The resulting hybrids were used to catalyze the oxidation of dibenzothiophene (DBT) to the corresponding sulfoxide (DBTO) and sulfone (DBTO2), in order to demonstrate their potential application for the oxydesulfurization (ODS) of a fuel. Thanks to catalyst confinement and to the higher affinity of the polymeric matrix towards polar substrates, the heterogeneous set-up displays improved performances with respect to the corresponding homogeneous systems. At 65°C, a DBT conversion higher than 84% was obtained in 24h, with a >94% selectivity for DBTO2. The stability of the hybrid materials under catalytic conditions was successfully assessed by a combined spectroscopic approach, based on FT-IR, resonance Raman, Solid State Nuclear Magnetic Resonance, X-ray Absorption and Small Angle X-ray scattering measurements.
ISSN:0926-3373
1873-3883
DOI:10.1016/j.apcatb.2015.10.008