Fluorination and reduction of CaCrO3 by topochemical methods

Juillerat, Christian A.; Tsujimoto, Yoshihiro; Chikamatsu, Akira; Masubuchi, Yuji; Hasegawa, Tetsuya; Yamaura, Kazunari

doi:10.1039/C9DT04321G

Fluorination and reduction of CaCrO₃ by topochemical methods

Journal Article · Tue Jan 21 23:00:00 EST 2020 · Dalton Transactions

DOI:https://doi.org/10.1039/C9DT04321G· OSTI ID:1767698

^[1]; ^[2]; ^[3]; ^[4]; Hasegawa, Tetsuya ^[3]; ^[2]

National Inst. for Materials Science (NIMS), Tsukuba (Japan); Univ. of South Carolina, Columbia, SC (United States); OSTI
National Inst. for Materials Science (NIMS), Tsukuba (Japan); Hokkaido Univ., Sapporo (Japan)
Univ. of Tokyo (Japan)
Hokkaido Univ., Sapporo (Japan)

Topochemical reactions between CaCrO₃ and polyvinylidene difluoride yield the new fluorinated phase CaCrO_2.5F_0.5, which was characterized by powder synchrotron X-ray diffraction, X-ray photoemission spectroscopy, and magnetic susceptibility measurements. The reaction proceeds via reduced oxide intermediates, CaCrO_2.67 and CaCrO_2.5, 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-C₃N_4. Both CaCrO₃ and CaCrO_2.5F_0.5 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, CaCrO_2.67 and CaCrO_2.5, a site preference for fluorine in the oxyfluoride phase cannot be confirmed. CaCrO₃ and CaCrO_2.5F_0.5 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 CaCrO_2.5F_0.5 structure.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Hierarchical Waste Form Materials (CHWM); Univ. of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); JSPS KAKENHI

Grant/Contract Number:: SC0016574

OSTI ID:: 1767698

Alternate ID(s):: OSTI ID: 1595494

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 6 Vol. 49; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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