Fluorination and reduction of CaCrO3 by topochemical methods
Abstract
Topochemical reactions between CaCrO3 and polyvinylidene difluoride yield the new fluorinated phase CaCrO2.5F0.5, which was characterized by powder synchrotron X-ray diffraction, X-ray photoemission spectroscopy, and magnetic susceptibility measurements. The reaction proceeds via reduced oxide intermediates, CaCrO2.67 and CaCrO2.5, in which CrO6 octahedral and CrO4 tetrahedral layers are stacked in a different manner along the c axis of CaCrO3. These two intermediate phases can be selectively synthesized by the carbothermal reduction with g-C3N4. Both CaCrO3 and CaCrO2.5F0.5 adopt the same orthorhombic space group, Pbnm; however, the fluorinated phase has decreased Cr–O–Cr bond angles as compared to the parent compound in both the ab plane and along the c-direction, which indicates an increased orthorhombic distortion due to the fluorination. Overall, while the oxygen vacancies are ordered in both intermediate phases, CaCrO2.67 and CaCrO2.5, a site preference for fluorine in the oxyfluoride phase cannot be confirmed. CaCrO3 and CaCrO2.5F0.5 undergo antiferromagnetic phase transitions involving spin canting, where the fluorination causes the transition temperature to increase from 90 K to 110 K, as a result of the competition between the increased octahedral tilting and the enhancement of superexchange interactions involving Cr3+ ions in the CaCrO2.5F0.5 structure.
- Authors:
-
[1];
[2];
[3];
[4];
[2]
- National Inst. for Materials Science (NIMS), Tsukuba (Japan); Univ. of South Carolina, Columbia, SC (United States)
- National Inst. for Materials Science (NIMS), Tsukuba (Japan); Hokkaido Univ., Sapporo (Japan)
- Univ. of Tokyo (Japan)
- Hokkaido Univ., Sapporo (Japan)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Hierarchical Waste Form Materials (CHWM); Univ. of South Carolina, Columbia, SC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); JSPS KAKENHI
- OSTI Identifier:
- 1767698
- Alternate Identifier(s):
- OSTI ID: 1595494
- Grant/Contract Number:
- SC0016574; 1250052; P15H02024, JP16H06438; JP16H06441; JP19H02594; 19H04711; 16H06439; 16K21724; SC00116574
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 49; Journal Issue: 6; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear; materials and chemistry by design; synthesis (novel materials); synthesis (predictive)
Citation Formats
Juillerat, Christian A., Tsujimoto, Yoshihiro, Chikamatsu, Akira, Masubuchi, Yuji, Hasegawa, Tetsuya, and Yamaura, Kazunari. Fluorination and reduction of CaCrO3 by topochemical methods. United States: N. p., 2020.
Web. doi:10.1039/C9DT04321G.
Juillerat, Christian A., Tsujimoto, Yoshihiro, Chikamatsu, Akira, Masubuchi, Yuji, Hasegawa, Tetsuya, & Yamaura, Kazunari. Fluorination and reduction of CaCrO3 by topochemical methods. United States. https://doi.org/10.1039/C9DT04321G
Juillerat, Christian A., Tsujimoto, Yoshihiro, Chikamatsu, Akira, Masubuchi, Yuji, Hasegawa, Tetsuya, and Yamaura, Kazunari. Wed .
"Fluorination and reduction of CaCrO3 by topochemical methods". United States. https://doi.org/10.1039/C9DT04321G. https://www.osti.gov/servlets/purl/1767698.
@article{osti_1767698,
title = {Fluorination and reduction of CaCrO3 by topochemical methods},
author = {Juillerat, Christian A. and Tsujimoto, Yoshihiro and Chikamatsu, Akira and Masubuchi, Yuji and Hasegawa, Tetsuya and Yamaura, Kazunari},
abstractNote = {Topochemical reactions between CaCrO3 and polyvinylidene difluoride yield the new fluorinated phase CaCrO2.5F0.5, which was characterized by powder synchrotron X-ray diffraction, X-ray photoemission spectroscopy, and magnetic susceptibility measurements. The reaction proceeds via reduced oxide intermediates, CaCrO2.67 and CaCrO2.5, in which CrO6 octahedral and CrO4 tetrahedral layers are stacked in a different manner along the c axis of CaCrO3. These two intermediate phases can be selectively synthesized by the carbothermal reduction with g-C3N4. Both CaCrO3 and CaCrO2.5F0.5 adopt the same orthorhombic space group, Pbnm; however, the fluorinated phase has decreased Cr–O–Cr bond angles as compared to the parent compound in both the ab plane and along the c-direction, which indicates an increased orthorhombic distortion due to the fluorination. Overall, while the oxygen vacancies are ordered in both intermediate phases, CaCrO2.67 and CaCrO2.5, a site preference for fluorine in the oxyfluoride phase cannot be confirmed. CaCrO3 and CaCrO2.5F0.5 undergo antiferromagnetic phase transitions involving spin canting, where the fluorination causes the transition temperature to increase from 90 K to 110 K, as a result of the competition between the increased octahedral tilting and the enhancement of superexchange interactions involving Cr3+ ions in the CaCrO2.5F0.5 structure.},
doi = {10.1039/C9DT04321G},
journal = {Dalton Transactions},
number = 6,
volume = 49,
place = {United States},
year = {Wed Jan 22 00:00:00 EST 2020},
month = {Wed Jan 22 00:00:00 EST 2020}
}
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