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Issue 32, 2015
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Novel La3Fe(MoO4)6 phase: magnetic properties and ethanol reactivity

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Single crystals of a new oxide, La3Fe(MoO4)6, were grown from fluxes of oxide precursors, and a polycrystalline sample was also prepared by a standard solid state reaction. La3Fe(MoO4)6 crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 19.3164(11), b = 10.4143(5) and c = 22.0594(12) Å. This crystal structure exhibits a singular architectural type built on infinite chains of Fe(MoO4)4, each of them being surrounded by two isolated MoO4 tetrahedra and three isolated La3+ cations. Fe3+ ions in La3Fe(MoO4)6 are antiferromagnetically ordered below TN = 6.6 K in chains and between chains, as refined from neutron diffraction data. Further the redox stability of this compound – pure powder – was checked using temperature-programmed X-ray diffraction under a controlled atmosphere; under air, we observed a reversible phase transition above 523 K. The same phenomenon was observed under a reductive atmosphere, followed by a destruction of the as-formed phase above 923 K owing to iron III to II reduction. Reactivity of ethanol was then evaluated to get insights into the redox properties of the material under working conditions. After 4 hours of reaction at 648 K, the ethanol conversion was 97% with a selectivity to acetaldehyde of ∼60%, the other products being formaldehyde (∼10%) and CO2 (∼30%), underlining a better acetaldehyde selectivity than that of the La-free conventional Fe2(MoO4)3 catalytic formulation.

Graphical abstract: Novel La3Fe(MoO4)6 phase: magnetic properties and ethanol reactivity

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The article was received on 16 Apr 2015, accepted on 01 Jul 2015 and first published on 02 Jul 2015

Article type: Paper
DOI: 10.1039/C5DT01444A
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Citation: Dalton Trans., 2015,44, 14444-14452
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    Novel La3Fe(MoO4)6 phase: magnetic properties and ethanol reactivity

    M. Colmont, G. Bucataru, A. Borowiec, M. Capron, F. Dumeignil, M. Huvé, F. Capet, F. Damay, O. Mentré and P. Roussel, Dalton Trans., 2015, 44, 14444
    DOI: 10.1039/C5DT01444A

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