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Mixed-valence iron dumortierite Fe13.52.22+(As5+O4-x)8(OH)6 and its intricate topotactic exsolution at mild temperature

hal.structure.identifierUnité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
dc.contributor.authorMENTRÉ, Olivier
hal.structure.identifierUnité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
dc.contributor.authorBLAZQUEZ-ALCOVER, Ignacio
hal.structure.identifierDepartemento Química Inorgánica
dc.contributor.authorGARCÍA-MARTÍN, Susana
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDUTTINE, Mathieu
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorWATTIAUX, Alain
hal.structure.identifierUnité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
dc.contributor.authorPARDIS, Simon
hal.structure.identifierUnité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
dc.contributor.authorHUVÉ, Marielle
hal.structure.identifierUnité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
dc.contributor.authorDAVIERO-MINAUD, Sylvie
dc.date.issued2018-12-04
dc.identifier.issn0020-1669
dc.description.abstractEnThe mixed-valent iron arsenate hydroxide Fe13.52.22+(AsO4–x)8(OH)6, x = 0.25, was prepared using the reaction of iron metal with arsenate in aqueous solution and autogenous pressure. Its crystal structure reveals a dumortierite-like framework with mixed-valent Fe2+/Fe3+ in double chains creating channel walls. Remarkably, hexagonal channels consist of chains of face-sharing Fe2+O6 octahedra, 3/4th occupied, whereas AsO4 tetrahedra occupy triangular ones with a single “up” orientation according to the polar P63mc symmetry. We have analyzed the transformation of this phase upon heating, in which several chemical processes interact, including dehydroxylation, arsenate to arsenite reduction, and oxidative exsolution of a significant part of iron (ca. 15%) found at the surface as hematite and amorphous Fe-rich surficial layer. It leaves a strongly disordered composite structure between several Fe3+-based subunits, in which ∼80% of them is ordered in a complex supercell. Because of the high degree of disorder, the crystal chemistry of the individual subunits and their plausible imbrication were considered to unravel the most plausible ideal 3D model.
dc.description.sponsorshipCouplages Magnéto-Electriques exacerbés dans des matériaux à unités ferromagnétiques - ANR-16-CE08-0023
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enMixed-valence iron dumortierite Fe13.52.22+(As5+O4-x)8(OH)6 and its intricate topotactic exsolution at mild temperature
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.inorgchem.8b02122
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page15093-15104
bordeaux.volume57
bordeaux.issue24
bordeaux.peerReviewedoui
hal.identifierhal-01963530
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01963530v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Inorganic%20Chemistry&rft.date=2018-12-04&rft.volume=57&rft.issue=24&rft.spage=15093-15104&rft.epage=15093-15104&rft.eissn=0020-1669&rft.issn=0020-1669&rft.au=MENTR%C3%89,%20Olivier&BLAZQUEZ-ALCOVER,%20Ignacio&GARC%C3%8DA-MART%C3%8DN,%20Susana&DUTTINE,%20Mathieu&WATTIAUX,%20Alain&rft.genre=article


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