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Title: Structural complexity of simple Fe 2O 3 at high pressures and temperatures

Abstract

Although chemically very simple, Fe 2O 3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe 2O 3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe 2O 3. Decomposition of Fe 2O 3 and Fe 3O 4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe 5O 7 and Fe 25O 32 phases with release of oxygen. Lastly, our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [3];  [4];  [4];  [4];  [5]
  1. Univ. of Bayreuth, Bayreuth (Germany)
  2. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  3. Univ. of Bayreuth, Bayreuth (Germany); European Synchrotron Radiation Facility, Grenoble (France)
  4. European Synchrotron Radiation Facility, Grenoble (France)
  5. Univ. of Chicago, Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1238292
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal Issue: 02, 2016; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical physics; structural properties

Citation Formats

Bykova, Elena, Dubrovinsky, L., Dubrovinskaia, N., Bykov, M., McCammon, C., Ovsyannikov, S. V., Liermann, H. -P., Kupenko, I., Chumakov, A. I., Ruffer, R., Hanfland, M., and Prakapenka, V. Structural complexity of simple Fe2O3 at high pressures and temperatures. United States: N. p., 2016. Web. doi:10.1038/ncomms10661.
Bykova, Elena, Dubrovinsky, L., Dubrovinskaia, N., Bykov, M., McCammon, C., Ovsyannikov, S. V., Liermann, H. -P., Kupenko, I., Chumakov, A. I., Ruffer, R., Hanfland, M., & Prakapenka, V. Structural complexity of simple Fe2O3 at high pressures and temperatures. United States. doi:10.1038/ncomms10661.
Bykova, Elena, Dubrovinsky, L., Dubrovinskaia, N., Bykov, M., McCammon, C., Ovsyannikov, S. V., Liermann, H. -P., Kupenko, I., Chumakov, A. I., Ruffer, R., Hanfland, M., and Prakapenka, V. Thu . "Structural complexity of simple Fe2O3 at high pressures and temperatures". United States. doi:10.1038/ncomms10661. https://www.osti.gov/servlets/purl/1238292.
@article{osti_1238292,
title = {Structural complexity of simple Fe2O3 at high pressures and temperatures},
author = {Bykova, Elena and Dubrovinsky, L. and Dubrovinskaia, N. and Bykov, M. and McCammon, C. and Ovsyannikov, S. V. and Liermann, H. -P. and Kupenko, I. and Chumakov, A. I. and Ruffer, R. and Hanfland, M. and Prakapenka, V.},
abstractNote = {Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Lastly, our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.},
doi = {10.1038/ncomms10661},
journal = {Nature Communications},
number = 02, 2016,
volume = 7,
place = {United States},
year = {2016},
month = {2}
}

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    Works referencing / citing this record:

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    High-Pressure Phase Transformations in TiPO 4 : A Route to Pentacoordinated Phosphorus
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    Preliminary reference Earth model
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    Nonstoichiometry of the perovskite-type oxide La1−xSrxCrO3−δ
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    Magnesium silicate perovskite and effect of iron oxidation state on its bulk sound velocity at the conditions of the lower mantle
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    High-pressure phase transition of hematite, Fe2O3
    journal, August 2004

    • Ono, Shigeaki; Kikegawa, Takumi; Ohishi, Yasuo
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    • DOI: 10.1016/j.jpcs.2003.11.042

    In situ X-ray observation of phase transformation in Fe2O3 at high pressures and high temperatures
    journal, October 2005


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    • DOI: 10.1016/j.pepi.2009.11.005

    Adiabatic temperature profile in the mantle
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    • Katsura, Tomoo; Yoneda, Akira; Yamazaki, Daisuke
    • Physics of the Earth and Planetary Interiors, Vol. 183, Issue 1-2
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    Solid oxygen
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    Evidence for deep mantle circulation from global tomography
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    • Tuček, Jiří; Machala, Libor; Ono, Shigeaki
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    BX90: A new diamond anvil cell design for X-ray diffraction and optical measurements
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    Portable double-sided laser-heating system for Mössbauer spectroscopy and X-ray diffraction experiments at synchrotron facilities with diamond anvil cells
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    • Kupenko, I.; Dubrovinsky, L.; Dubrovinskaia, N.
    • Review of Scientific Instruments, Vol. 83, Issue 12
    • DOI: 10.1063/1.4772458

    Electronic and magnetic structures of the postperovskite-type Fe2O3 and implications for planetary magnetic records and deep interiors
    journal, March 2009

    • Shim, S. -H.; Bengtson, A.; Morgan, D.
    • Proceedings of the National Academy of Sciences, Vol. 106, Issue 14
    • DOI: 10.1073/pnas.0808549106

    Discovery of the recoverable high-pressure iron oxide Fe4O5
    journal, October 2011

    • Lavina, B.; Dera, P.; Kim, E.
    • Proceedings of the National Academy of Sciences, Vol. 108, Issue 42
    • DOI: 10.1073/pnas.1107573108

    Single-crystal X-ray diffraction at megabar pressures and temperatures of thousands of degrees
    journal, December 2010


    Novel high pressure monoclinic Fe 2 O 3 polymorph revealed by single-crystal synchrotron X-ray diffraction studies
    journal, August 2013


    A study of the crystal structure of Fe 2 O 3 in the pressure range up to 65 GPa using synchrotron radiation
    journal, March 1991


    The structure of the metallic high-pressure Fe 3 O 4 polymorph: experimental and theoretical study
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    • Dubrovinsky, L. S.; Dubrovinskaia, N. A.; McCammon, C.
    • Journal of Physics: Condensed Matter, Vol. 15, Issue 45
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    Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6
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    • Lavina, Barbara; Meng, Yue
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    • DOI: 10.1126/sciadv.1400260

    Determination of high-pressure phase equilibria of Fe2O3 using the Kawai-type apparatus equipped with sintered diamond anvils
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    • Ito, E.; Fukui, H.; Katsura, T.
    • American Mineralogist, Vol. 94, Issue 2-3
    • DOI: 10.2138/am.2009.2913

    High-pressure structural behavior of  -Fe2O3 studied by single-crystal X-ray diffraction and synchrotron radiation up to 25 GPa
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    • Schouwink, P.; Dubrovinsky, L.; Glazyrin, K.
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    • DOI: 10.2138/am.2011.3775

    Effect of high pressure on the crystal structure and electronic properties of magnetite below 25 GPa
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