Comparative Study of Electrical Conduction and Oxygen Diffusion in the Rhombohedral and Bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) Polymorphs Научная публикация
| Журнал |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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| Вых. Данные | Год: 2019, Том: 58, Номер: 7, Страницы: 4275-4288 Страниц : 14 DOI: 10.1021/acs.inorgchem.8b03397 | ||||||||||||||||
| Ключевые слова | FLUORITE-RELATED SUPERSTRUCTURE; RARE-EARTH; TRANSPORT-PROPERTIES; Ln(6-X)MoO(12-δ) Ln; CRYSTAL-CHEMISTRY; PHASE-EQUILIBRIA; SYSTEM; ION; X=0; ELECTROLYTES | ||||||||||||||||
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| Организации |
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Информация о финансировании (4)
| 1 | Российский фонд фундаментальных исследований | 16-03-00143 (АААА-А16-116031050045-0) |
| 2 | Федеральное агентство научных организаций России | 0082-2014-0011 (АААА-А17-117111600093-8) |
| 3 | Российский фонд фундаментальных исследований | 19-03-00358 (АААА-А19-119031290055-2) |
| 4 | Российский научный фонд | 16-13-00112 |
Реферат:
Electrical 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.
Библиографическая ссылка:
Shlyakhtina 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.
Comparative Study of Electrical Conduction and Oxygen Diffusion in the Rhombohedral and Bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) Polymorphs
Inorganic Chemistry. 2019. V.58. N7. P.4275-4288. DOI: 10.1021/acs.inorgchem.8b03397 WOS Scopus РИНЦ CAPlus OpenAlex
Comparative Study of Electrical Conduction and Oxygen Diffusion in the Rhombohedral and Bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) Polymorphs
Inorganic Chemistry. 2019. V.58. N7. P.4275-4288. DOI: 10.1021/acs.inorgchem.8b03397 WOS Scopus РИНЦ CAPlus OpenAlex
Даты:
| Поступила в редакцию: | 5 дек. 2018 г. |
| Опубликована online: | 19 мар. 2019 г. |
| Опубликована в печати: | 1 апр. 2019 г. |
Идентификаторы БД:
| Web of science: | WOS:000463462200031 |
| Scopus: | 2-s2.0-85063667686 |
| РИНЦ: | 38719466 |
| Chemical Abstracts: | 2019:501851 |
| OpenAlex: | W2924266316 |