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Title: High-pressure phase transformation of carbonate malachite Cu2(CO3)(OH)2 driven by [CuO6] regularization and [CO3] rotation

Abstract

High-pressure synchrotronX-ray diffraction and infrared absorption spectroscopy have been employed to studythe crystal chemistry and phase transitions in an [OH]-bearing carbonate, malachite Cu2(CO3)(OH)2, to determine the effect of [OH] on the stability of carbonate. We found that the crystal structure of malachite is stabilized by a high degree of [CuO6]-octahedron distortion, as is manifested by large variations in Cu-O bond lengths resulting from oxygen atoms that connect to hydrogen at crystallographically different sites. External pressure offsets the effect of hydrogen bond, promotes [CuO6] compression and regularization and accordingly [CO3] rotation. Rotation of [CO3]-triangles, in turn, assists in a conversion in the crystal orientation of the [CuO6] structural unit. During compression to above ~6 GPa, malachite begins to turn into the rosasite lattice, accompanied with a jump in density of 3.3%. Rosasite is characterized with a hardened lattice and preserves to the maximum pressure (18.2 GPa) of the present study. Phase transformation mechanism of malachite to rosasite is different from that of carbonates, with the latter being driven by an almost uniform compression of [MO6]-octahedron (M = Ca, Cd, Mn, Fe, Zn, Mg, etc.) and rotation/translation of [CO3]-triangle under pressure.

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [1]
+ Show Author Affiliations
  1. Chinese Academy of Sciences (CAS), Beijing (China)
  2. Chinese Academy of Geological Sciences, Beijing (China)
  3. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  4. Univ. of Illinois, Chicago, IL (United States)
Publication Date:
Research Org.:
Univ. of Illinois, Chicago, IL (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP); National Science Foundation (NSF); National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; China Postdoctoral Science Foundation
OSTI Identifier:
1820160
Grant/Contract Number:  
NA0003975; EAR-1555388; EAR-1565708; EAR-1829273; EAR-1157758; 41902035; 41490614; 41822202; 2018M640179; 2019T120132; AC98-06CH10886; FC03-03N00144
Resource Type:
Accepted Manuscript
Journal Name:
Geoscience Frontiers
Additional Journal Information:
Journal Volume: 12; Journal Issue: 2; Journal ID: ISSN 1674-9871
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray diffraction; Infrared spectroscopy; Hydrogen bond; Carbonates; Phase transformation

Citation Formats

Gao, Jing, Yuan, Xueyin, Chen, Bin, Liu, Zhenxian, and Su, Wen. High-pressure phase transformation of carbonate malachite Cu2(CO3)(OH)2 driven by [CuO6] regularization and [CO3] rotation. United States: N. p., 2020. Web. doi:10.1016/j.gsf.2020.07.006.
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Gao, Jing, Yuan, Xueyin, Chen, Bin, Liu, Zhenxian, & Su, Wen. High-pressure phase transformation of carbonate malachite Cu2(CO3)(OH)2 driven by [CuO6] regularization and [CO3] rotation. United States. https://doi.org/10.1016/j.gsf.2020.07.006
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Gao, Jing, Yuan, Xueyin, Chen, Bin, Liu, Zhenxian, and Su, Wen. Fri . "High-pressure phase transformation of carbonate malachite Cu2(CO3)(OH)2 driven by [CuO6] regularization and [CO3] rotation". United States. https://doi.org/10.1016/j.gsf.2020.07.006. https://www.osti.gov/servlets/purl/1820160.
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@article{osti_1820160,
title = {High-pressure phase transformation of carbonate malachite Cu2(CO3)(OH)2 driven by [CuO6] regularization and [CO3] rotation},
author = {Gao, Jing and Yuan, Xueyin and Chen, Bin and Liu, Zhenxian and Su, Wen},
abstractNote = {High-pressure synchrotronX-ray diffraction and infrared absorption spectroscopy have been employed to studythe crystal chemistry and phase transitions in an [OH]-bearing carbonate, malachite Cu2(CO3)(OH)2, to determine the effect of [OH] on the stability of carbonate. We found that the crystal structure of malachite is stabilized by a high degree of [CuO6]-octahedron distortion, as is manifested by large variations in Cu-O bond lengths resulting from oxygen atoms that connect to hydrogen at crystallographically different sites. External pressure offsets the effect of hydrogen bond, promotes [CuO6] compression and regularization and accordingly [CO3] rotation. Rotation of [CO3]-triangles, in turn, assists in a conversion in the crystal orientation of the [CuO6] structural unit. During compression to above ~6 GPa, malachite begins to turn into the rosasite lattice, accompanied with a jump in density of 3.3%. Rosasite is characterized with a hardened lattice and preserves to the maximum pressure (18.2 GPa) of the present study. Phase transformation mechanism of malachite to rosasite is different from that of carbonates, with the latter being driven by an almost uniform compression of [MO6]-octahedron (M = Ca, Cd, Mn, Fe, Zn, Mg, etc.) and rotation/translation of [CO3]-triangle under pressure.},
doi = {10.1016/j.gsf.2020.07.006},
journal = {Geoscience Frontiers},
number = 2,
volume = 12,
place = {United States},
year = {Fri Aug 07 00:00:00 EDT 2020},
month = {Fri Aug 07 00:00:00 EDT 2020}
}
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