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Cobalt speciation in cobalt oxide-apatite materials : structure-properties relationship in catalytic oxidative dehydrogenation of ethane and butan-2-ol conversion

Identifieur interne : 000893 ( Main/Merge ); précédent : 000892; suivant : 000894

Cobalt speciation in cobalt oxide-apatite materials : structure-properties relationship in catalytic oxidative dehydrogenation of ethane and butan-2-ol conversion

Auteurs : KAOUTAR EL KABOUSS [Maroc, France] ; Mohamed Kacimi [Maroc] ; Mahfoud Ziyad [Maroc] ; Souad Ammar [France] ; Alain Ensuque [France] ; Jean-Yves Piquemal [France] ; Francois Bozon-Verduraz [France]

Source :

RBID : Pascal:07-0089131

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English descriptors

Abstract

Impregnation of calcium hydroxyapatite by a solution of Co(II) nitrate followed by calcination at 823 K gives rise to various species, depending on the cobalt content. At low cobalt content (0.2 wt%), the cobalt species are isolated six-coordinated Co2+ ions. For Co content >0.4 wt%, the presence of tetrahedral Co2+ and octahedral Co3+ species is attested by UV-visible-NIR spectroscopy, magnetic measurements and XPS data. Magnetic data at low temperature suggest the formation of clustered CoxOy entities. For Co content ≥1.7 wt%, Co3O4 nanocrystals are generated, as evidenced by XRD and magnetic measurements. In the presence of oxygen, the butan-2-ol conversion produces only butan-2-one. The most active catalysts are the cobalt poorest samples which contain only isolated Co2+ ions. Oxidative dehydrogenation of ethane gives a similar trend. Upon increasing the cobalt loading above 0.9 wt%, the specific dehydrogenation activity of Co2+ ions decreases because the nature of the sites changes and the basic properties are lowered. Relationships between the nature of the sites and the catalytic performances are proposed.

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<term>Activation energy</term>
<term>Calcium</term>
<term>Catalysis</term>
<term>Chemical analysis</term>
<term>Cobalt oxides</term>
<term>Experimental study</term>
<term>Hydroxyapatite</term>
<term>Low temperature</term>
<term>Magnetic susceptibility</term>
<term>Nanocrystal</term>
<term>Nanostructured materials</term>
<term>Near infrared spectrum</term>
<term>Performance</term>
<term>Property structure relationship</term>
<term>Ultraviolet visible spectrum</term>
<term>X-ray photoelectron spectra</term>
<term>XRD</term>
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<term>Cobalt oxyde</term>
<term>Etude expérimentale</term>
<term>Relation structure propriété</term>
<term>Calcium</term>
<term>Apatite hydroxylée</term>
<term>Spectre UV visible</term>
<term>Analyse chimique</term>
<term>Spectre IR proche</term>
<term>Susceptibilité magnétique</term>
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<term>Basse température</term>
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<term>Nanomatériau</term>
<term>Diffraction RX</term>
<term>Catalyse</term>
<term>Performance</term>
<term>Energie activation</term>
<term>Ca10(PO4)6(OH)2</term>
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<term>7530C</term>
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<div type="abstract" xml:lang="en">Impregnation of calcium hydroxyapatite by a solution of Co(II) nitrate followed by calcination at 823 K gives rise to various species, depending on the cobalt content. At low cobalt content (0.2 wt%), the cobalt species are isolated six-coordinated Co
<sup>2+</sup>
ions. For Co content >0.4 wt%, the presence of tetrahedral Co
<sup>2+</sup>
and octahedral Co
<sup>3+</sup>
species is attested by UV-visible-NIR spectroscopy, magnetic measurements and XPS data. Magnetic data at low temperature suggest the formation of clustered Co
<sub>x</sub>
O
<sub>y</sub>
entities. For Co content ≥1.7 wt%, Co
<sub>3</sub>
O
<sub>4</sub>
nanocrystals are generated, as evidenced by XRD and magnetic measurements. In the presence of oxygen, the butan-2-ol conversion produces only butan-2-one. The most active catalysts are the cobalt poorest samples which contain only isolated Co
<sup>2+</sup>
ions. Oxidative dehydrogenation of ethane gives a similar trend. Upon increasing the cobalt loading above 0.9 wt%, the specific dehydrogenation activity of Co
<sup>2+</sup>
ions decreases because the nature of the sites changes and the basic properties are lowered. Relationships between the nature of the sites and the catalytic performances are proposed.</div>
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