Comparative study of electrical conduction and oxygen diffusion in the rhombohedral and bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) polymorphs

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dc.contributor.authorShlyakhtina, AVen_AU
dc.contributor.authorLyskov, NVen_AU
dc.contributor.authorAvdeev, Men_AU
dc.contributor.authorGoffman, VGen_AU
dc.contributor.authorGorshkov, NVen_AU
dc.contributor.authorKnotko, AVen_AU
dc.contributor.authorKolbanev, IVen_AU
dc.contributor.authorKaryagina, OKen_AU
dc.contributor.authorMaslakov, KIen_AU
dc.contributor.authorShcherbakova, LGen_AU
dc.contributor.authorSadovskaya, EMen_AU
dc.contributor.authorSadykov, VAen_AU
dc.contributor.authorEremeev, NFen_AU
dc.date.accessioned2021-06-10T03:52:25Zen_AU
dc.date.available2021-06-10T03:52:25Zen_AU
dc.date.issued2019-03-19en_AU
dc.date.statistics2021-04-29en_AU
dc.description.abstractElectrical conduction and oxygen diffusion mobility in the bixbyite (Ia3̅) and rhombohedral (R3̅) polymorphs of the Ln6MoO12−Δ (Ln = Er, Tm, Yb; Δ = δ, δ1, δ2; δ1 > δ2) heavy lanthanide molybdates, belonging to new, previously unexplored classes of potential mixed (ionic–electronic) conductors, have been studied in the range of 200–900 °C. The oxygen self-diffusion coefficient in bixbyite (Ia3̅) Yb6MoO12−δ phase estimated by the temperature-programmed heteroexchange with C18O2 was shown to be much higher than that for rhombohedral (R3̅) RI (with large oxygen deficiency) and (R3̅) RII (with small oxygen deficiency) Ln6MoO12−Δ (Ln = Tm, Yb; Δ = δ1; δ1 > δ2) oxides. According to the activation energy for total conduction in ambient air, 0.99, 0.93, and 1.01 eV in Er6MoO12−δ, Tm6MoO12−δ, and Yb6MoO12−δ bixbyites, respectively, oxygen ion conductivity prevails in the range ∼200–500 °C. Oxygen mobility data for the rhombohedral Ln6MoO12−Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) phases RI and RII indicate that the oxygen in these phases exhibits mobility at much higher temperatures, such as those above 600–700 °C. Accordingly, below 600–700 °C they have predominantly electronic conductivity. As shown by total conductivity study of Ln6MoO12−δ (Ln = Er, Tm, Yb) bixbyites (Ia3̅) and rhombohedral phases Ln6MoO12−Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) (R3̅) in dry and wet air, the proton conductivity contribution exists only in Ln6MoO12−δ (Ln = Er, Tm, Yb) bixbyites up to 450–600 °C and decreases with a decreasing of the lanthanide ionic radius. The obtained data on the mobility of oxygen and the presence of proton contribution in bixbyites in the 300–600 °C temperature range make it possible to confirm unequivocally that Ln6MoO12−δ (Ln = Er, Tm, Yb) bixbyites are mixed electron–proton conductors at these temperatures. © 2019 American Chemical Societyen_AU
dc.identifier.citationShlyakhtina, A. V., Lyskov, N. V., Avdeev, M., Goffman, V. G., Gorshkov, N. V., Knotko, A. V., Kolbanev, I. V., Karyagina, O. K., Maslakov, K. I., Shcherbakova, L. G., Sadovskaya, E. M., Sadykov, V. A., & Eremeev, N. F. (2019). Comparative study of electrical conduction and oxygen diffusion in the rhombohedral and bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) polymorphs. Inorganic chemistry, 58(7), 4275-4288. doi:10.1021/acs.inorgchem.8b03397en_AU
dc.identifier.issn1520-510Xen_AU
dc.identifier.issue7en_AU
dc.identifier.journaltitleInorganic chemistryen_AU
dc.identifier.pagination4275-4288en_AU
dc.identifier.urihttps://doi.org/10.1021/acs.inorgchem.8b03397en_AU
dc.identifier.urihttps://apo.ansto.gov.au/dspace/handle/10238/10853en_AU
dc.identifier.volume58en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectAtmospheric chemistryen_AU
dc.subjectOxygenen_AU
dc.subjectElectric conductivityen_AU
dc.subjectPhase transformationsen_AU
dc.subjectTrigonal latticesen_AU
dc.subjectRare earthsen_AU
dc.titleComparative study of electrical conduction and oxygen diffusion in the rhombohedral and bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) polymorphsen_AU
dc.typeJournal Articleen_AU
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