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Order and Disorder: Toward the Thermodynamically Stable α-BaMoO2F4 from the Metastable Polymorph

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Abstract
A fully ordered noncentrosymmetric barium molybdenum oxyfluoride, α-BaMoO2F4, has been synthesized by a hydrothermal reaction at 200 °C in a concentrated hydrofluoric acid solution. A centrosymmetric polymorph with O/F disorder, β-BaMoO2F4, has been obtained in several minutes when the reaction mixture was stirred at room temperature in the same medium. Interestingly, we found that the metastable β-BaMoO2F4 transforms into the thermodynamically stable α-BaMoO2F4 in an ambient condition. More detailed kinetic studies using powder X-ray diffraction indicate that the MoO2F4 octahedra in the kinetic phase, β-BaMoO2F4, rearrange through the constant dissolution/precipitation process to find a more stable orientation and form the fully ordered α-BaMoO2F4. Density functional theory (DFT)calculations suggest that the formation of the thermodynamically stable α-BaMoO2F4 is driven by the strong Mo?O π-interactions induced by Ba2+ cations. The new finding on the understanding of the kinetics of solid-state reactions suggests a novel way toward an effective discovery of functional materials with asymmetric structures.
Author(s)
조홍일이민형옥강민
Issued Date
2021
Type
Article
Keyword
orderdisorderα?BaMoO2F4metastablepolymorph
DOI
10.1021/acs.chemmater.1c00074
URI
https://oak.ulsan.ac.kr/handle/2021.oak/9626
https://ulsan-primo.hosted.exlibrisgroup.com/primo-explore/fulldisplay?docid=TN_cdi_crossref_primary_10_1021_acs_chemmater_1c00074&context=PC&vid=ULSAN&lang=ko_KR&search_scope=default_scope&adaptor=primo_central_multiple_fe&tab=default_tab&query=any,contains,Order%20and%20Disorder:%20Toward%20the%20Thermodynamically%20Stable%20%CE%B1-BaMoO2F4%20from%20the%20Metastable%20Polymorph&offset=0&pcAvailability=true
Publisher
CHEMISTRY OF MATERIALS
Location
미국
Language
영어
ISSN
0897-4756
Citation Volume
33
Citation Number
5
Citation Start Page
1875
Citation End Page
1882
Appears in Collections:
Natural Science > Chemistry
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