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Cationic distribution and oxidation mechanism of trivalent manganese ions in submicrometer MnxCoFe2-xO4 spinel ferrites

Identifieur interne : 000348 ( PascalFrancis/Checkpoint ); précédent : 000347; suivant : 000349

Cationic distribution and oxidation mechanism of trivalent manganese ions in submicrometer MnxCoFe2-xO4 spinel ferrites

Auteurs : M. Laarj [Maroc] ; S. Kacim [Maroc] ; B. Gillot [France]

Source :

RBID : Pascal:96-0377530

Descripteurs français

English descriptors

Abstract

Submicrometer MnXCoFe2-xO4 (0 ≤ x < 1) spinel particles with a spherical shape were prepared at low temperature from oxalic precursors. Because of their small crystallite size (about 50 nm), these ferrite particles can be oxidized below 400°C giving cubic deficient spinels having both Mn3+ and Mn4+ ions because of oxido-reduction phenomena. Information about the valence state of the manganese and cobalt ions and cation distribution between tetrahedral (A) and octahedral (B) sites are derived from lattice parameter variation, IR spectroscopy, thermogravimetric analysis, and electrical conductivity. A kinetics study of the oxidation of Mn3+ ions shows that oxidation proceeds by cation diffusion through a topotactic reaction with a constant chemical diffusion coefficient for x < 0.60 and variable above x = 0.80 and an activation energy close to 115 kJ mol-1 but, however, depending on manganese substitution content.


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Pascal:96-0377530

Le document en format XML

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<title xml:lang="en" level="a">Cationic distribution and oxidation mechanism of trivalent manganese ions in submicrometer Mn
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CoFe
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O
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spinel ferrites</title>
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<title xml:lang="en" level="a">Cationic distribution and oxidation mechanism of trivalent manganese ions in submicrometer Mn
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CoFe
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O
<sub>4</sub>
spinel ferrites</title>
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<country>France</country>
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<region type="region" nuts="2">Bourgogne-Franche-Comté</region>
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<title level="j" type="main">Journal of solid state chemistry</title>
<title level="j" type="abbreviated">J. solid state chem.</title>
<idno type="ISSN">0022-4596</idno>
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<term>Cobalt oxides</term>
<term>Crystal chemistry</term>
<term>Electric conductivity</term>
<term>Experimental study</term>
<term>Ferrites spinels</term>
<term>Fine particle</term>
<term>Infrared spectra</term>
<term>Ion distribution</term>
<term>Iron oxides</term>
<term>Lattice parameters</term>
<term>Manganese oxides</term>
<term>Oxidation</term>
<term>Quaternary compounds</term>
<term>Reaction mechanism</term>
<term>Solid solutions</term>
<term>Spherical shape</term>
<term>TGA</term>
<term>Topotactic reaction</term>
<term>Valence</term>
<term>XRD</term>
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<keywords scheme="Pascal" xml:lang="fr">
<term>Etude expérimentale</term>
<term>Cristallochimie</term>
<term>Oxydation</term>
<term>Mécanisme réaction</term>
<term>Distribution ion</term>
<term>Particule fine</term>
<term>Composé quaternaire</term>
<term>Ferrites spinelles</term>
<term>Solution solide</term>
<term>Composition chimique</term>
<term>Manganèse oxyde</term>
<term>Cobalt oxyde</term>
<term>Fer oxyde</term>
<term>Forme sphérique</term>
<term>Valence</term>
<term>Paramètre cristallin</term>
<term>XRD</term>
<term>Conductivité électrique</term>
<term>Spectre IR</term>
<term>TGA</term>
<term>Réaction topotactique</term>
<term>6166F</term>
<term>MnxCoFe2-xO4</term>
<term>Co Fe Mn O</term>
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<div type="abstract" xml:lang="en">Submicrometer Mn
<sub>X</sub>
CoFe
<sub>2</sub>
-
<sub>x</sub>
O
<sub>4</sub>
(0 ≤ x < 1) spinel particles with a spherical shape were prepared at low temperature from oxalic precursors. Because of their small crystallite size (about 50 nm), these ferrite particles can be oxidized below 400°C giving cubic deficient spinels having both Mn
<sup>3+</sup>
and Mn
<sup>4+</sup>
ions because of oxido-reduction phenomena. Information about the valence state of the manganese and cobalt ions and cation distribution between tetrahedral (A) and octahedral (B) sites are derived from lattice parameter variation, IR spectroscopy, thermogravimetric analysis, and electrical conductivity. A kinetics study of the oxidation of Mn
<sup>3+</sup>
ions shows that oxidation proceeds by cation diffusion through a topotactic reaction with a constant chemical diffusion coefficient for x < 0.60 and variable above x = 0.80 and an activation energy close to 115 kJ mol
<sup>-1</sup>
but, however, depending on manganese substitution content.</div>
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<s0>Submicrometer Mn
<sub>X</sub>
CoFe
<sub>2</sub>
-
<sub>x</sub>
O
<sub>4</sub>
(0 ≤ x < 1) spinel particles with a spherical shape were prepared at low temperature from oxalic precursors. Because of their small crystallite size (about 50 nm), these ferrite particles can be oxidized below 400°C giving cubic deficient spinels having both Mn
<sup>3+</sup>
and Mn
<sup>4+</sup>
ions because of oxido-reduction phenomena. Information about the valence state of the manganese and cobalt ions and cation distribution between tetrahedral (A) and octahedral (B) sites are derived from lattice parameter variation, IR spectroscopy, thermogravimetric analysis, and electrical conductivity. A kinetics study of the oxidation of Mn
<sup>3+</sup>
ions shows that oxidation proceeds by cation diffusion through a topotactic reaction with a constant chemical diffusion coefficient for x < 0.60 and variable above x = 0.80 and an activation energy close to 115 kJ mol
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<s5>03</s5>
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<s5>04</s5>
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<s5>08</s5>
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<s5>08</s5>
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<s5>09</s5>
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<s5>09</s5>
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<s0>Chemical composition</s0>
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<s0>Manganèse oxyde</s0>
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<s5>13</s5>
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<s0>Valence</s0>
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<s5>18</s5>
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<s0>Lattice parameters</s0>
<s5>18</s5>
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<s5>19</s5>
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<s0>Topotactic reaction</s0>
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<s0>6166F</s0>
<s2>PAC</s2>
<s4>INC</s4>
<s5>56</s5>
</fC03>
<fC03 i1="23" i2="3" l="FRE">
<s0>MnxCoFe2-xO4</s0>
<s4>INC</s4>
<s5>92</s5>
</fC03>
<fC03 i1="24" i2="3" l="FRE">
<s0>Co Fe Mn O</s0>
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<name sortKey="Kacim, S" sort="Kacim, S" uniqKey="Kacim S" first="S." last="Kacim">S. Kacim</name>
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