Multiscale Study on the Formation and Evolution of the Crystal and Local Structures in Lanthanide Tungstates Ln2(WO4)3 Full article
| Journal |
Journal of Alloys and Compounds
ISSN: 0925-8388 , E-ISSN: 1873-4669 |
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| Output data | Year: 2022, Volume: 910, Article number : 164922, Pages count : 13 DOI: 10.1016/j.jallcom.2022.164922 | ||||||||||||
| Tags | Lanthanide tungstates, Crystal and local structure, Synchrotron XRD, X-ray absorption fine structure (XAFS), Raman spectroscopy, FT-IR spectroscopy | ||||||||||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Ministry of Science and Higher Education of the Russian Federation | 0718-2020-0037 |
| 2 | Ministry of Science and Higher Education of the Russian Federation | 075-15-2021-1352 |
Abstract:
The influence exerted by the specific type of the lanthanide cation and calcination temperature on the crystal and local structures of Ln2(WO4)3 tungstates (Ln = La–Dy) prepared by a coprecipitation is studied using synchrotron X-ray diffraction, X-ray absorption fine structure (XAFS) spectroscopy, Fourier transform infrared (FT-IR) and Raman spectroscopies, photoluminescence, simultaneous thermal analysis, and inductively coupled plasma atomic emission spectroscopy. The combination of these experimental techniques enabled a structural insight into Ln tungstates at multiple characteristic scales, i.e. short-range of metal atom coordination (XAFS), medium-range of the network of chemical bonds (FT-IR and Raman spectroscopies), and long-range or 3D periodicity within crystallites (XRD). It is found that the onset of amorphous precursor crystallization is observed at 575–600 ∘C/3 h and leads to the formation of Ln2(WO4)3 nanocrystalline powders with a monoclinic (sp. gr. C12/c1 (15)) structure. An increase in the calcination temperature leads to the growth of crystallite size and a decrease in microstrains. In the case of Dy2(WO4)3 an additional orthorhombic phase emerges (sp. gr. Pbcn(60)) at 1000 ∘C. It is shown that the local structure of all well-crystallized compounds being studied contains lanthanide ions in the form of Ln3+ and tungsten ions in the form of WO tetrahedra. The local structure in the monoclinic phase can be represented as a superposition of two non-equivalent tungstate tetrahedra: W(1)O4 (C2 site symmetry) and W(2)O4 (C1 site symmetry). The LnO8 polyhedra are strongly irregular, and the Ln3+ cations occupy low-symmetry sites.
Cite:
Popov V.V.
, Menushenkov A.P.
, Yastrebtsev A.A.
, Rudakov S.G.
, Ivanov A.A.
, Gaynanov B.R.
, Svetogorov R.D.
, Khramov E.V.
, Zubavichus Y.V.
, Molokova A.Y.
, Tsarenko N.A.
, Ognevskaya N.V.
, Seregina O.N.
, Rachenok I.G.
, Shchetinin I.V.
, Ponkratov K.V.
Multiscale Study on the Formation and Evolution of the Crystal and Local Structures in Lanthanide Tungstates Ln2(WO4)3
Journal of Alloys and Compounds. 2022. V.910. 164922 :1-13. DOI: 10.1016/j.jallcom.2022.164922 WOS Scopus РИНЦ ANCAN OpenAlex publication_identifier_short.sciact_skif_identifier_type
Multiscale Study on the Formation and Evolution of the Crystal and Local Structures in Lanthanide Tungstates Ln2(WO4)3
Journal of Alloys and Compounds. 2022. V.910. 164922 :1-13. DOI: 10.1016/j.jallcom.2022.164922 WOS Scopus РИНЦ ANCAN OpenAlex publication_identifier_short.sciact_skif_identifier_type
Dates:
| Submitted: | Nov 18, 2021 |
| Accepted: | Apr 5, 2022 |
| Published online: | Apr 8, 2022 |
| Published print: | Jul 25, 2022 |
Identifiers:
| Web of science: | WOS:000797885700005 |
| Scopus: | 2-s2.0-85128206208 |
| Elibrary: | 48428480 |
| Chemical Abstracts: | 2022:1026672 |
| Chemical Abstracts (print): | 179:18487 |
| OpenAlex: | W4224903323 |
| publication_identifier.sciact_skif_identifier_type: | 527 |