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Issue 35, 2013
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Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor

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Abstract

The oxidative dehydrogenation (ODH) of propane to propylene by supported vanadia catalysts has received much attention in recent years, but different reactivity trends have been reported for this catalytic reaction system. In the present investigation, the origin of these differing trends are investigated with synthesis of supported V/SiO2, V/TiO2, and V/Al2O3 catalysts prepared with three different vanadium oxide precursors (2-propanol/vanadyl triisopropoxide [VO(O-Pri)3] (VTI), oxalic acid/ammonium metavanadate [NH4VO3] (AMV), and toluene/vanadyl acetylacetonate [VO(C5H7O2)2] (VAA)) in order to elucidate the influence of the precursor on supported vanadia phase and propane ODH activity. In situ Raman spectroscopy revealed that the choice of vanadium precursor does not affect the dispersion of the supported vanadium oxide phase below 4 V nm−2 (0.5 monolayer coverage), where only isolated and oligomeric surface VO4 species are present, and only the AMV precursor favors crystalline V2O5 nanoparticle (NP) formation below monolayer coverage (8 V nm−2). The propane ODH specific reactivity trend demonstrated that there is no significant difference in TOF for the isolated and oligomeric surface VO4 sites. Surprisingly, V2O5 NPs in the ∼1–2 nm range exhibit anomalously high propane ODH TOF values for the supported vanadia catalysts. This was found for all supported vanadium oxide catalysts examined. This comparative study with different V-precursors and synthesis methods and oxide supports finally resolves the debate in the catalysis literature about the dependence of TOF on the surface vanadium density that is related to the unusually high reactivity of small V2O5 NPs.

Graphical abstract: Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor

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Publication details

The article was received on 05 Mar 2013, accepted on 25 Apr 2013, published on 08 May 2013 and first published online on 08 May 2013


Article type: Paper
DOI: 10.1039/C3DT50611H
Citation: Dalton Trans., 2013,42, 12644-12653
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    Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor

    C. A. Carrero, C. J. Keturakis, A. Orrego, R. Schomäcker and I. E. Wachs, Dalton Trans., 2013, 42, 12644
    DOI: 10.1039/C3DT50611H

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