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Structure-Controlled Oxygen Concentration in Fe2O3 and FeO2

  • Sheng-cai Zhu
    Sheng-cai Zhu
    Department of Physics and Astronomy, High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States
    Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai 201203, P. R. China
  • Jin Liu
    Jin Liu
    Department of Geological Sciences, Stanford University, Stanford, California 94305, United States
    More by Jin Liu
  • Qingyang Hu*
    Qingyang Hu
    Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai 201203, P. R. China
    *E-mail: [email protected] (Q.H.).
    More by Qingyang Hu
  • Wendy L. Mao
    Wendy L. Mao
    Department of Geological Sciences, Stanford University, Stanford, California 94305, United States
    More by Wendy L. Mao
  • Yue Meng
    Yue Meng
    High Pressure Collaborative Access Team, X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
    More by Yue Meng
  • Dongzhou Zhang
    Dongzhou Zhang
    Hawai’i Institute of Geophysics and Planetology, School of Ocean and Earth Science and Technology, University of Hawai’i at Manoa, Honolulu, Hawaii 96822, United States
  • Ho-kwang Mao
    Ho-kwang Mao
    Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai 201203, P. R. China
    Geophysical Laboratory, Carnegie Institution of Washington, Washington, D.C. 20015, United States
    More by Ho-kwang Mao
  • , and 
  • Qiang Zhu*
    Qiang Zhu
    Department of Physics and Astronomy, High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States
    *E-mail: [email protected] (Q.Z.).
    More by Qiang Zhu
Cite this: Inorg. Chem. 2019, 58, 9, 5476–5482
Publication Date (Web):December 17, 2018
https://doi.org/10.1021/acs.inorgchem.8b02764
Copyright © 2018 American Chemical Society

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    Abstract

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    Solid–solid reaction, particularly in the Fe–O binary system, has been extensively studied in the past decades because of its various applications in chemistry and materials and earth sciences. The recently synthesized pyrite-FeO2 at high pressure suggested a novel oxygen-rich stoichiometry that extends the achievable O–Fe ratio in iron oxides by 33%. Although FeO2 was synthesized from Fe2O3 and O2, the underlying solid reaction mechanism remains unclear. Herein, combining in situ X-ray diffraction experiments and first-principles calculations, we identified that two competing phase transitions starting from Fe2O3: (1) without O2, perovskite-Fe2O3 transits to the post-perovskite structure above 50 GPa; (2) if free oxygen is present, O diffuses into the perovskite-type lattice of Fe2O3 leading to the pyrite-type FeO2 phase. We found the O–O bonds in FeO2 are formed by the insertion of oxygen into the Pv lattice via the external stress and such O–O bonding is only kinetically stable under high pressure. This may provide a general mechanism of adding extra oxygen to previous known O saturated oxides to produce unconventional stoichiometries. Our results also shed light on how O is enriched in mantle minerals under pressure.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b02764.

    • High-pressure in situ XRD experiment method; the calculation detail of SSW sampling method, the interface energy and O diffusion; the atomic structure of Py-FeO2 and Fe2O3 polymorphs; the electron localization function of MgO2, pyrite-type FeO2, and PdF2-type SiO2 at 75 GPa; XRD pattern of reaction products of Pv-Fe2O3 and oxygen at 75 GPa; and the Py-FeO2 and Pv-Fe2O3 interface and Py-FeO2 and Rh2O3-II-type Fe2O3 interface module (PDF)

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    Cited By

    This article is cited by 9 publications.

    1. Gu-wen Chen, Bin Wen, Jiang-Sheng Xie, Li-Kai Chen, Sheng-Cai Zhu. Resolving the Perovskite Degradation Mechanism by Machine Learning Potential: The Case of CsPbI3. The Journal of Physical Chemistry C 2023, 127 (24) , 11692-11699. https://doi.org/10.1021/acs.jpcc.3c01589
    2. Haibo Liu, Lei Liu, Cunlin Xin, Longxing Yang, Xiaoyu Gu. A first-principles study of the structural, electronic and elastic properties of the FeO 2 –FeO 2 He system under high pressure. Physical Chemistry Chemical Physics 2023, 25 (30) , 20225-20234. https://doi.org/10.1039/D3CP02315J
    3. Shengxuan Huang, Qingyang Hu. Medium-range structure motifs of complex iron oxides. Journal of Applied Physics 2022, 131 (7) https://doi.org/10.1063/5.0082503
    4. Hongzhan Fei, Zhaodong Liu, Rong Huang, Seiji Kamada, Naohisa Hirao, Saori Kawaguchi, Catherine McCammon, Tomoo Katsura. Pressure Destabilizes Oxygen Vacancies in Bridgmanite. Journal of Geophysical Research: Solid Earth 2021, 126 (12) https://doi.org/10.1029/2021JB022437
    5. Qingyang Hu, Jin Liu. Deep mantle hydrogen in the pyrite-type FeO2–FeO2H system. Geoscience Frontiers 2021, 12 (2) , 975-981. https://doi.org/10.1016/j.gsf.2020.04.006
    6. Bingyun Ao. Quantum-mechanical oxidation states of metal ions in the solid-state binary sulfides. Acta Materialia 2020, 186 , 597-608. https://doi.org/10.1016/j.actamat.2020.01.036
    7. Qian Ding, Ruizhi Qiu, Bingyun Ao. Dependency of f states in fluorite-type XO 2 (X = Ce, Th, U) on the stability and electronic state of doped transition metals. Physical Chemistry Chemical Physics 2019, 21 (47) , 25962-25975. https://doi.org/10.1039/C9CP04371C
    8. Wei Jian, Ran Jia, Jian Wang, Hong-Xing Zhang, Fu-Quan Bai. Iron oxides with a reverse spinel structure: impact of active sites on molecule adsorption. Inorganic Chemistry Frontiers 2019, 6 (10) , 2810-2816. https://doi.org/10.1039/C9QI00790C
    9. Yukai Zhuang, Zhongxun Cui, Dongzhou Zhang, Jin Liu, Renbiao Tao, Qingyang Hu. Experimental Evidence for Partially Dehydrogenated ε-FeOOH. Crystals 2019, 9 (7) , 356. https://doi.org/10.3390/cryst9070356

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