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Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO2 H at High Pressure

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b06528· OSTI ID:1474063
 [1];  [2];  [3];  [4];  [5]
  1. Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai 201203, People’s Republic of China; Department of Geological Sciences, Stanford University, Stanford, Californi
  2. Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); Stanford Univ., CA (United States). Dept. of Geological Sciences
  3. Stanford Univ., CA (United States). Dept. of Geological Sciences
  4. Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  5. Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); George Mason Univ., Fairfax, VA (United States). Dept. of Physics and Astronomy
+ Show Author Affiliations
The cycling of hydrogen plays an important role in the geochemical evolution of our planet. Under high-pressure conditions, asymmetric hydroxyl bonds tend to form a symmetric O–H–O configuration in which H is positioned at the center of two O atoms. The symmetrization of O–H bonds improves their thermal stability and as such, water-bearing minerals can be present deeper in the Earth’s lower mantle. However, how exactly H is recycled from the deep mantle remains unclear. Here, we employ first-principles free-energy landscape sampling methods together with high pressure-high temperature experiments to reveal the dehydrogenation mechanism of a water-bearing mineral, FeO2H, at deep mantle conditions. Experimentally, we show that ~50% H is released from symmetrically hydrogen-bonded ε-FeO2H upon transforming to a pyrite-type phase (Py-phase). By resolving the lowest-energy transition pathway from ε-FeO2H to the Py-phase, we demonstrate that half of the O–H bonds in the mineral rupture during the structural transition, leading toward the breakdown of symmetrized hydrogen bonds and eventual dehydrogenation. In conclusion, our study sheds new light on the stability of symmetric hydrogen bonds during structural transitions and provides a dehydrogenation mechanism for hydrous minerals existing in the deep mantle
Research Organization:
Carnegie Inst. of Washington, Washington, DC (United States)
Sponsoring Organization:
NSAF; National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
NA0001974
OSTI ID:
1474063
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 35 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (9)

Chemical Reactions Between Fe and H 2 O up to Megabar Pressures and Implications for Water Storage in the Earth's Mantle and Core journal February 2018
Thermal equation of state of MgSiO4H2 phase H determined by in situ X-ray diffraction and a multianvil apparatus journal June 2018
Ferrous Iron Under Oxygen‐Rich Conditions in the Deep Mantle journal February 2019
Altered chemistry of oxygen and iron under deep Earth conditions journal January 2019
Proton transfer ferroelectricity/multiferroicity in rutile oxyhydroxides journal January 2018
Overall structural modification of a layered Ni-rich cathode for enhanced cycling stability and rate capability at high voltage journal January 2019
Novel phases in ammonia-water mixtures under pressure journal December 2018
The role of H-bond in the high-pressure chemistry of model molecules journal February 2018
Proton-transfer Ferroelectricity / Multiferroicity in Rutile Oxyhydroxides text January 2018

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