On the Role of Fe and Co Dopants during the Activation of the VO(HPO4), 0.5 H2O Precursor of the Vanadium Phosphorus Catalyst as Studied by in Situ Laser Raman Spectroscopy
Identifieur interne : 001059 ( Main/Curation ); précédent : 001058; suivant : 001060On the Role of Fe and Co Dopants during the Activation of the VO(HPO4), 0.5 H2O Precursor of the Vanadium Phosphorus Catalyst as Studied by in Situ Laser Raman Spectroscopy
Auteurs : M. T. Sananés-Schulz [France] ; F. Ben Abdelouahab [Maroc] ; G. J. Hutchings [Royaume-Uni] ; J. C. Volta [France]Source :
- Journal of Catalysis [ 0021-9517 ] ; 1996.
Descripteurs français
- Pascal (Inist)
- Wicri :
English descriptors
- KwdEn :
Abstract
Two vanadium phosphorus oxide precursors doped by Co and Fe have been prepared by a new route consisting of a reduction of VOPO4, 2H2O by isobutanol which is known to give a particular morphology of VOHPO4, 0.5H2O, developing crystallites in the [110] direction. Their activation undern-butane/air catalytic atmosphere (1.5%) has been compared to the corresponding undoped precursor prepared under the same conditions and used as a reference. The modification of the structure of the VPO materials has been followed on-line byin situlaser Raman spectroscopy. In a first period of the activation, the nucleation of αI-VOPO4is favoured for the undoped VPO precursor, while (VO)2P2O7appears in a second period. For the Co-doped VPO precursor, αI- and αII-VOPO4first appear, and then (VO)2P2O7appears. At variance, the Fe-doped VPO precursor promotes the only nucleation of αI-VOPO4. When comparing with the classical organic route, catalytic performances are markedly improved when the VOHPO4, 0.5H2O precursor is prepared via this new route both for the undoped and the Co-doped VPO catalysts. At variance, the Fe-doped catalyst gives poorer performances which have been explained by a high oxidation state for this catalyst (almost (V5+) as αI-VOPO4). This is confirmed by an analysis of the bulk and surface composition of the final catalysts by XRD and XPS spectroscopy. The role of the two dopants on this new morphology of VOHPO4, 0.5H2O is then quite different at variance with what was observed on the same precursor prepared by the classical route of reduction of V2O5by isobutanol (see B. Abdelouahabet al., 1995,J. Catal.,157, 687. The present study demonstrates that the preparative route for the formation of doped VPO precursors is most important in controlling the VOPO4/(VO)2P2O7dispersion and catalytic performance of the final catalyst.
Url:
DOI: 10.1006/jcat.1996.0336
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<front><div type="abstract" xml:lang="en">Two vanadium phosphorus oxide precursors doped by Co and Fe have been prepared by a new route consisting of a reduction of VOPO4, 2H2O by isobutanol which is known to give a particular morphology of VOHPO4, 0.5H2O, developing crystallites in the [110] direction. Their activation undern-butane/air catalytic atmosphere (1.5%) has been compared to the corresponding undoped precursor prepared under the same conditions and used as a reference. The modification of the structure of the VPO materials has been followed on-line byin situlaser Raman spectroscopy. In a first period of the activation, the nucleation of αI-VOPO4is favoured for the undoped VPO precursor, while (VO)2P2O7appears in a second period. For the Co-doped VPO precursor, αI- and αII-VOPO4first appear, and then (VO)2P2O7appears. At variance, the Fe-doped VPO precursor promotes the only nucleation of αI-VOPO4. When comparing with the classical organic route, catalytic performances are markedly improved when the VOHPO4, 0.5H2O precursor is prepared via this new route both for the undoped and the Co-doped VPO catalysts. At variance, the Fe-doped catalyst gives poorer performances which have been explained by a high oxidation state for this catalyst (almost (V5+) as αI-VOPO4). This is confirmed by an analysis of the bulk and surface composition of the final catalysts by XRD and XPS spectroscopy. The role of the two dopants on this new morphology of VOHPO4, 0.5H2O is then quite different at variance with what was observed on the same precursor prepared by the classical route of reduction of V2O5by isobutanol (see B. Abdelouahabet al., 1995,J. Catal.,157, 687. The present study demonstrates that the preparative route for the formation of doped VPO precursors is most important in controlling the VOPO4/(VO)2P2O7dispersion and catalytic performance of the final catalyst.</div>
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), O.5H<sub>2</sub>
O precursor of the vanadium phosphorus catalyst as studied by in situ laser Raman spectroscopy. II. Study of VO(HPO<sub>4</sub>
), 0.5H<sub>2</sub>
O precursors prepared by reduction of VOPO<sub>4</sub>
, 2 H<sub>2</sub>
O by isobutanol</title>
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<term>Iron</term>
<term>Modified material</term>
<term>Phosphorus Oxides</term>
<term>Precursor</term>
<term>Preparation</term>
<term>Quaternary compound</term>
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<term>Fer</term>
<term>Cobalt</term>
<term>Spectrométrie Raman</term>
<term>Vanadyle Hydrogénophosphate</term>
<term>Composé quaternaire</term>
<term>Diffraction RX</term>
<term>Catalyse hétérogène</term>
<term>O P V</term>
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<front><div type="abstract" xml:lang="en">Two vanadium phosphorus oxide precursors doped by Co and Fe have been prepared by a new route consisting of a reduction of VOPO<sub>4</sub>
, 2H<sub>2</sub>
O by isobutanol which is known to give a particular morphology of VOHPO<sub>4</sub>
, 0.5H<sub>2</sub>
O, developing crystallites in the [110] direction. Their activation under n-butane/air catalytic atmosphere (1.5%) has been compared to the corresponding undoped precursor prepared under the same conditions and used as a reference. The modification of the structure of the VPO materials has been followed on-line by in situ laser Raman spectroscopy. In a first period of the activation, the nucleation of α<sub>1</sub>
-VOPO<sub>4</sub>
is favoured for the undoped VPO precursor, while (VO)<sub>2</sub>
P<sub>2</sub>
O<sub>7</sub>
appears in a second period. For the Co-doped VPO precursor, α<sub>I</sub>
- and α<sub>II</sub>
-VOPO<sub>4</sub>
first appear, and then (VO)<sub>2</sub>
P<sub>2</sub>
O<sub>7</sub>
appears. At variance, the Fe-doped VPO precursor promotes the only nucleation of α<sub>I</sub>
-VOPO<sub>4</sub>
. When comparing with the classical organic route, catalytic performances are markedly improved when the VOHPO<sub>4</sub>
, 0.5H<sub>2</sub>
O precursor is prepared via this new route both for the undoped and the Co-doped VPO catalysts. At variance, the Fe-doped catalyst gives poorer performances which have been explained by a high oxidation state for this catalyst (almost (V<sup>5+</sup>
) as α<sub>I</sub>
-VOPO<sub>4</sub>
). This is confirmed by an analysis of the bulk and surface composition of the final catalysts by XRD and XPS spectroscopy. The role of the two dopants on this new morphology of VOHPO<sub>4</sub>
, 0.5H<sub>2</sub>
O is then quite different at variance with what was observed on the same precursor prepared by the classical route of reduction of V<sub>2</sub>
O<sub>5</sub>
by isobutanol (see B. Abdelouahab et al., 1995, J. Catal., 157, 687. The present study demonstrates that the preparative route for the formation of doped VPO precursors is most important in controlling the VOPO<sub>4</sub>
/(VO)<sub>2</sub>
P<sub>2</sub>
O<sub>7</sub>
dispersion and catalytic performance of the final catalyst.</div>
</front>
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<author><name sortKey="Sananes Schulz, M T" sort="Sananes Schulz, M T" uniqKey="Sananes Schulz M" first="M. T." last="Sananés-Schulz">M. T. Sananés-Schulz</name>
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<author><name sortKey="Abdelouahab, F Ben" sort="Abdelouahab, F Ben" uniqKey="Abdelouahab F" first="F. Ben" last="Abdelouahab">F. Ben Abdelouahab</name>
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<author><name sortKey="Hutchings, G J" sort="Hutchings, G J" uniqKey="Hutchings G" first="G. J." last="Hutchings">G. J. Hutchings</name>
</author>
<author><name sortKey="Volta, J C" sort="Volta, J C" uniqKey="Volta J" first="J. C." last="Volta">J. C. Volta</name>
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<sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">On the Role of Fe and Co Dopants during the Activation of the VO(HPO4), 0.5 H2O Precursor of the Vanadium Phosphorus Catalyst as Studied by in Situ Laser Raman Spectroscopy</title>
<author><name sortKey="Sananes Schulz, M T" sort="Sananes Schulz, M T" uniqKey="Sananes Schulz M" first="M. T." last="Sananés-Schulz">M. T. Sananés-Schulz</name>
<affiliation wicri:level="3"><country xml:lang="fr">France</country>
<wicri:regionArea>Institut de Recherches sur la Catalyse, CNRS, 2 Avenue A. Einstein, 69626, Villeurbanne Cédex</wicri:regionArea>
<placeName><region type="region" nuts="2">Auvergne-Rhône-Alpes</region>
<region type="old region" nuts="2">Rhône-Alpes</region>
<settlement type="city">Villeurbanne Cédex</settlement>
</placeName>
</affiliation>
</author>
<author><name sortKey="Abdelouahab, F Ben" sort="Abdelouahab, F Ben" uniqKey="Abdelouahab F" first="F. Ben" last="Abdelouahab">F. Ben Abdelouahab</name>
<affiliation wicri:level="1"><country xml:lang="fr">Maroc</country>
<wicri:regionArea>Faculté des Sciences, Université Abdelmalek Essaadi, BP 2121, Tétouan</wicri:regionArea>
<wicri:noRegion>Tétouan</wicri:noRegion>
</affiliation>
</author>
<author><name sortKey="Hutchings, G J" sort="Hutchings, G J" uniqKey="Hutchings G" first="G. J." last="Hutchings">G. J. Hutchings</name>
<affiliation wicri:level="1"><country xml:lang="fr">Royaume-Uni</country>
<wicri:regionArea>Leverhulme Centre for Innovative Catalysis, Department of Chemistry, University of Liverpool, P.O. Box 147, Liverpool, L69 3BX</wicri:regionArea>
<wicri:noRegion>L69 3BX</wicri:noRegion>
</affiliation>
</author>
<author><name sortKey="Volta, J C" sort="Volta, J C" uniqKey="Volta J" first="J. C." last="Volta">J. C. Volta</name>
<affiliation wicri:level="3"><country xml:lang="fr">France</country>
<wicri:regionArea>Institut de Recherches sur la Catalyse, CNRS, 2 Avenue A. Einstein, 69626, Villeurbanne Cédex</wicri:regionArea>
<placeName><region type="region" nuts="2">Auvergne-Rhône-Alpes</region>
<region type="old region" nuts="2">Rhône-Alpes</region>
<settlement type="city">Villeurbanne Cédex</settlement>
</placeName>
</affiliation>
</author>
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<series><title level="j">Journal of Catalysis</title>
<title level="j" type="abbrev">YJCAT</title>
<idno type="ISSN">0021-9517</idno>
<imprint><publisher>ELSEVIER</publisher>
<date type="published" when="1996">1996</date>
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<front><div type="abstract" xml:lang="en">Two vanadium phosphorus oxide precursors doped by Co and Fe have been prepared by a new route consisting of a reduction of VOPO4, 2H2O by isobutanol which is known to give a particular morphology of VOHPO4, 0.5H2O, developing crystallites in the [110] direction. Their activation undern-butane/air catalytic atmosphere (1.5%) has been compared to the corresponding undoped precursor prepared under the same conditions and used as a reference. The modification of the structure of the VPO materials has been followed on-line byin situlaser Raman spectroscopy. In a first period of the activation, the nucleation of αI-VOPO4is favoured for the undoped VPO precursor, while (VO)2P2O7appears in a second period. For the Co-doped VPO precursor, αI- and αII-VOPO4first appear, and then (VO)2P2O7appears. At variance, the Fe-doped VPO precursor promotes the only nucleation of αI-VOPO4. When comparing with the classical organic route, catalytic performances are markedly improved when the VOHPO4, 0.5H2O precursor is prepared via this new route both for the undoped and the Co-doped VPO catalysts. At variance, the Fe-doped catalyst gives poorer performances which have been explained by a high oxidation state for this catalyst (almost (V5+) as αI-VOPO4). This is confirmed by an analysis of the bulk and surface composition of the final catalysts by XRD and XPS spectroscopy. The role of the two dopants on this new morphology of VOHPO4, 0.5H2O is then quite different at variance with what was observed on the same precursor prepared by the classical route of reduction of V2O5by isobutanol (see B. Abdelouahabet al., 1995,J. Catal.,157, 687. The present study demonstrates that the preparative route for the formation of doped VPO precursors is most important in controlling the VOPO4/(VO)2P2O7dispersion and catalytic performance of the final catalyst.</div>
</front>
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