Synthesis and structural characterization of the hexagonal anti-perovskite Na{sub 2}CaVO{sub 4}F
Abstract
The structural details of the ordered hexagonal oxyfluoride Na{sub 2}CaVO{sub 4}F prepared by solid-state synthesis using stoichiometric amounts of V{sub 2}O{sub 5}, CaCO{sub 3}, Na{sub 2}CO{sub 3} and NaF were characterized using high-resolution neutron powder diffraction. The structural changes between 25 °C and 750 °C revealed that the two structural subunits in this material behave different when heated: there is an expansion of the face-shared FNa{sub 4}Ca{sub 2} octahedra while the VO{sub 4} tetrahedra due to increased thermal disorder reveal marginal bond contractions. Bond valences and the global instability index point to significant structural disorder at 750 °C. - Graphical abstract: The structure of the novel oxyfluoride Na{sub 2}CaVO{sub 4}F is studied at room temperature and high-temperatures. The structure can be viewed as layers of compression and elongation of polyhedral subunits, which change as a function of temperature. - Highlights: • The novel oxyfluoride, Na{sub 2}CaVO{sub 4}F, is synthesized via solid-state method. • High-resolution neutron diffraction data is used to analyze the structure of Na{sub 2}CaVO{sub 4}F. • Structural subunits exhibit expansion and contraction with increasing temperature. • Higher temperatures increase instability within the structure of Na{sub 2}CaVO{sub 4}F.
- Authors:
-
- Australian Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia)
- NanoCenter and Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208 (United States)
- Publication Date:
- OSTI Identifier:
- 22658297
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Solid State Chemistry
- Additional Journal Information:
- Journal Volume: 250; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CALCIUM CARBONATES; CARBON IONS; NEUTRON DIFFRACTION; OXYFLUORIDES; SODIUM CARBONATES; SODIUM FLUORIDES; SYNTHESIS; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 0273-0400 K; TEMPERATURE RANGE 0400-1000 K; VANADIUM OXIDES
Citation Formats
Green, Robert L., E-mail: rgreen@flpoly.org, Avdeev, Maxim, School of Chemistry, The University of Sydney, Sydney, NSW 2006, and Vogt, Thomas. Synthesis and structural characterization of the hexagonal anti-perovskite Na{sub 2}CaVO{sub 4}F. United States: N. p., 2017.
Web. doi:10.1016/J.JSSC.2017.03.027.
Green, Robert L., E-mail: rgreen@flpoly.org, Avdeev, Maxim, School of Chemistry, The University of Sydney, Sydney, NSW 2006, & Vogt, Thomas. Synthesis and structural characterization of the hexagonal anti-perovskite Na{sub 2}CaVO{sub 4}F. United States. https://doi.org/10.1016/J.JSSC.2017.03.027
Green, Robert L., E-mail: rgreen@flpoly.org, Avdeev, Maxim, School of Chemistry, The University of Sydney, Sydney, NSW 2006, and Vogt, Thomas. 2017.
"Synthesis and structural characterization of the hexagonal anti-perovskite Na{sub 2}CaVO{sub 4}F". United States. https://doi.org/10.1016/J.JSSC.2017.03.027.
@article{osti_22658297,
title = {Synthesis and structural characterization of the hexagonal anti-perovskite Na{sub 2}CaVO{sub 4}F},
author = {Green, Robert L., E-mail: rgreen@flpoly.org and Avdeev, Maxim and School of Chemistry, The University of Sydney, Sydney, NSW 2006 and Vogt, Thomas},
abstractNote = {The structural details of the ordered hexagonal oxyfluoride Na{sub 2}CaVO{sub 4}F prepared by solid-state synthesis using stoichiometric amounts of V{sub 2}O{sub 5}, CaCO{sub 3}, Na{sub 2}CO{sub 3} and NaF were characterized using high-resolution neutron powder diffraction. The structural changes between 25 °C and 750 °C revealed that the two structural subunits in this material behave different when heated: there is an expansion of the face-shared FNa{sub 4}Ca{sub 2} octahedra while the VO{sub 4} tetrahedra due to increased thermal disorder reveal marginal bond contractions. Bond valences and the global instability index point to significant structural disorder at 750 °C. - Graphical abstract: The structure of the novel oxyfluoride Na{sub 2}CaVO{sub 4}F is studied at room temperature and high-temperatures. The structure can be viewed as layers of compression and elongation of polyhedral subunits, which change as a function of temperature. - Highlights: • The novel oxyfluoride, Na{sub 2}CaVO{sub 4}F, is synthesized via solid-state method. • High-resolution neutron diffraction data is used to analyze the structure of Na{sub 2}CaVO{sub 4}F. • Structural subunits exhibit expansion and contraction with increasing temperature. • Higher temperatures increase instability within the structure of Na{sub 2}CaVO{sub 4}F.},
doi = {10.1016/J.JSSC.2017.03.027},
url = {https://www.osti.gov/biblio/22658297},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 250,
place = {United States},
year = {Thu Jun 15 00:00:00 EDT 2017},
month = {Thu Jun 15 00:00:00 EDT 2017}
}