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Mesoporous Silicates with Spherical Morphology Modified with Vanadium Highly Active in Oxidation of Cyclohexene with H2O2

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Abstract

Vanadium-containing mesoporous molecular sieves have been prepared by hydrothermal treatment at 373 K. These materials showed spherical morphology with a narrow particle size distribution between 2 and 4 μm. The techniques used for their physicochemical characterization were: XRD, AAS, N2 physisorption, SEM, TEM and DR–UV–Vis spectroscopy. All the materials presented high specific surface area (>900 m2/g), characteristic of MCM-41 materials. A well-defined mesoporous structure was observed by TEM measures although there was no one-dimensional ordering of pores characteristic of such materials. Additionally, secondary mesoporosity domains were determined in the BJH size distribution. The sample synthesized with the highest content of V presented marked differences in their structural characteristics, which were attributed to the blockage of channels by the presence of nano-clusters and/or VxOy nano-oxides. From the DR–UV–Vis analysis, a successful incorporation of V ions to silica structure in tetrahedral coordination with oxygen of the network could be inferred. The catalytic activity of these materials was evaluated in the test reaction of cyclohexene oxidation using H2O2 as oxidizing agent, showing a high conversion of about 93% respect to the maximum, resulting dominant the radicalary mechanism over the direct oxidation mechanism. Apparently, the isolated V ions incorporated into the silica structure would be responsible for the high catalytic activity of these materials.

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Acknowledgment

G.A.E., K.S. and S.G.C are CONICET Researchers; C.M.Ch. and A.L.C received CONICET Doctoral Fellowship. This work was supported by the CONICET, the UTN-FRC and the UNSL of Argentina, and UdeC of Chile. We thank J. Bazán Aguirre (UTN-FRC Student) for valuable help on some experimental activities. Finally, C.M.Ch. acknowledge to Dra. M.E. Crivello for the participation in international cooperation project MINCYT–CONICYT, Code CH/08/03.

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Authors and Affiliations

  1. Facultad Regional Córdoba, Centro de Investigación y Tecnología Química (CITeQ), Universidad Tecnológica Nacional, Córdoba, 5016, Argentina

    Corina M. Chanquía, Analía L. Cánepa, Eduardo R. Herrero, Sandra G. Casuscelli & Griselda A. Eimer

  2. Laboratorio de Ciencias de Superficies y Medios Porosos (LaCSuMP), Departamento de Física, Instituto de Física Aplicada (INFAP), CONICET, Universidad Nacional de San Luis, San Luis, 5700, Argentina

    Karim Sapag

  3. Facultad de Ciencias Químicas, Universidad de Concepción, Casilla 3-C, Concepción, Chile

    Patricio Reyes

  4. CONICET, Avenida Rivadavia 1917, C1033AAJ, Buenos Aires, Argentina

    Corina M. Chanquía, Analía L. Cánepa, Karim Sapag, Sandra G. Casuscelli & Griselda A. Eimer

Authors
  1. Corina M. Chanquía
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  2. Analía L. Cánepa
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  3. Karim Sapag
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  4. Patricio Reyes
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  5. Eduardo R. Herrero
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  6. Sandra G. Casuscelli
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  7. Griselda A. Eimer
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Correspondence to Griselda A. Eimer.

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Chanquía, C.M., Cánepa, A.L., Sapag, K. et al. Mesoporous Silicates with Spherical Morphology Modified with Vanadium Highly Active in Oxidation of Cyclohexene with H2O2 . Top Catal 54, 160–169 (2011). https://doi.org/10.1007/s11244-011-9635-8

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  • DOI: https://doi.org/10.1007/s11244-011-9635-8

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