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Introduction of vanadium species in β zeolite by solid-state reaction: spectroscopic study of V speciation and molecular mechanism

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V-containing β zeolites were prepared by solid-state reaction between V2O5 and β zeolite. The zeolite structure was analysed by XRD and N2 physisorption. The V speciation was studied by chemical analysis and different spectroscopies (FT-IR, 27Al-NMR, UV-Vis, EPR, photoluminescence). After calcination of V2O5β zeolite mechanical mixtures at 500°C, three kinds of V species were identified: (i) oligomeric vanadates with octahedral V5+ easily removed by treatment with NH4OAc, (ii) isolated vanadyl (V=O)2+ ions in axially distorted octahedral or square pyramidal environment, interacting with framework and/or extraframework Al nuclei and (iii) isolated V5+ in tetrahedral and octahedral environments, localized in framework defect sites. The amount of the latter species is higher when water vapor is present during calcination and when parent β zeolite contains a high concentration of defect sites generated by a strong acid pretreatment. Isolated V5+ are easily reduced to tetrahedral V4+ or to square pyramidal (V=O)2+. Possible models of the mechanism of formation of V species by solid-state reaction and further reduction are proposed.

Affiliations: 1: Laboratoire de Réactivité de Surface, UMR 7609 CNRS, Université Pierre et Marie Curie, casier 178, 4 place Jussieu, 75252 Paris Cedex 05, France; Exxon Mobil Research and Engineering Company 1545 Route 22 East, Clinton Township, Annandale, NJ 08801, USA; 2: Laboratoire de Réactivité de Surface, UMR 7609 CNRS, Université Pierre et Marie Curie, casier 178, 4 place Jussieu, 75252 Paris Cedex 05, France; 3: Institut Universitaire de France, Paris, France

10.1163/156856707782169327
/content/journals/10.1163/156856707782169327
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/content/journals/10.1163/156856707782169327
2007-09-01
2016-12-02

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