Stabilization of Th{sup 3+} ions into mixed-valence thorium fluoride

Journal Article · Sat Jan 15 00:00:00 EST 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2010.10.010· OSTI ID:21494189

Dubois, Marc ^[1]; Dieudonne, Belto; Mesbah, Adel; Bonnet, Pierre; El-Ghozzi, Malika ^[1]; Renaudin, Guillaume ^[2]; Avignant, Daniel ^[1]

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1. Clermont Universite, Universite Blaise Pascal, Laboratoire des Materiaux Inorganiques, BP 10448, F-63000 Clermont-Ferrand (France)
2. Clermont Universite, ENSCCF, Laboratoire des Materiaux Inorganiques, BP 10448, F-63000 Clermont-Ferrand (France)

The unusual oxidation state +3 of the thorium has been stabilized into a lithium containing non-stoichiometric mixed-valence (III/IV) thorium fluorinated phase with formula Li{sub 2+x}Th{sub 12}F{sub 50} (0<x<1.8). This phase is closely related to the Li{sub 5.5}Ce{sub 12}F{sub 50} one, the structure of which has been determined from the combined single-crystal X-ray diffraction and high resolution synchrotron powder diffraction. In these phases, the Li{sup +} ions can be divided into two groups and are located either in locked positions or in open channels of the three dimensional framework. The amount of Li{sup +} ions in open channels can be variable, so that the afore mentioned single phase may be considered as an insertion compound. The Li{sup +} insertion is accompanied by the simultaneous reduction of a part of the Th{sup 4+} ions, resulting in a mixed-valence III/IV thorium fluoride. The electrochemical insertion of Li{sup +} ions into the open channels of the host matrix has been carried out at 60 {sup o}C, using an alkylcarbonate PC-LiClO{sub 4} 1 M electrolyte. The Li{sup +} and Th{sup 3+} contents, both in the starting composition and the Li{sup +} inserted ones, were investigated by high resolution solid state {sup 7}Li NMR and EPR, respectively. -- Graphical abstract: Electrochemical insertion of Li{sup +} ions into mixed-valence III/IV thorium fluoride and EPR spectra for the raw and inserted compounds. Display Omitted

• OSTI ID: 21494189
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 1; Other Information: DOI: 10.1016/j.jssc.2010.10.010; PII: S0022-4596(10)00464-0; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ELECTROCHEMISTRY
ELECTROLYTES
ELECTRON SPIN RESONANCE
LITHIUM
LITHIUM IONS
LITHIUM PERCHLORATES
MONOCRYSTALS
NUCLEAR MAGNETIC RESONANCE
REDUCTION
SPECTRA
STABILIZATION
TEMPERATURE RANGE 0273-0400 K
THORIUM FLUORIDES
THORIUM IONS
VALENCE
X-RAY DIFFRACTION
ACTINIDE COMPOUNDS
ALKALI METAL COMPOUNDS
ALKALI METALS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPOUNDS
COHERENT SCATTERING
CRYSTALS
DIFFRACTION
ELEMENTS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
IONS
LITHIUM COMPOUNDS
MAGNETIC RESONANCE
METALS
OXYGEN COMPOUNDS
PERCHLORATES
RESONANCE
SCATTERING
TEMPERATURE RANGE
THORIUM COMPOUNDS