Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO2 H at High Pressure
Abstract
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
- Authors:
-
[2];
- Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China)
- Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); Stanford Univ., CA (United States). Dept. of Geological Sciences
- Stanford Univ., CA (United States). Dept. of Geological Sciences
- Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
- Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); George Mason Univ., Fairfax, VA (United States). Dept. of Physics and Astronomy
- Publication Date:
- Research Org.:
- Carnegie Inst. of Washington, Washington, DC (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); NSAF
- OSTI Identifier:
- 1474063
- Grant/Contract Number:
- NA0001974; 21703004; U1530402
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 35; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 58 GEOSCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhu, Sheng-cai, Hu, Qingyang, Mao, Wendy L., Mao, Ho-kwang, and Sheng, Hongwei. Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO2 H at High Pressure. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b06528.
Zhu, Sheng-cai, Hu, Qingyang, Mao, Wendy L., Mao, Ho-kwang, & Sheng, Hongwei. Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO2 H at High Pressure. United States. https://doi.org/10.1021/jacs.7b06528
Zhu, Sheng-cai, Hu, Qingyang, Mao, Wendy L., Mao, Ho-kwang, and Sheng, Hongwei. Thu .
"Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO2 H at High Pressure". United States. https://doi.org/10.1021/jacs.7b06528. https://www.osti.gov/servlets/purl/1474063.
@article{osti_1474063,
title = {Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO2 H at High Pressure},
author = {Zhu, Sheng-cai and Hu, Qingyang and Mao, Wendy L. and Mao, Ho-kwang and Sheng, Hongwei},
abstractNote = {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},
doi = {10.1021/jacs.7b06528},
journal = {Journal of the American Chemical Society},
number = 35,
volume = 139,
place = {United States},
year = {Thu Aug 24 00:00:00 EDT 2017},
month = {Thu Aug 24 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 32 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Decomposition of phase D in the lower mantle and the fate of dense hydrous silicates in subducting slabs
journal, June 1998
- Shieh, Sean R.; Mao, Ho-kwang; Hemley, Russell J.
- Earth and Planetary Science Letters, Vol. 159, Issue 1-2
FeO2 and FeOOH under deep lower-mantle conditions and Earth’s oxygen–hydrogen cycles
journal, June 2016
- Hu, Qingyang; Kim, Duck Young; Yang, Wenge
- Nature, Vol. 534, Issue 7606
Hydrous minerals and the storage of water in the deep mantle
journal, December 2015
- Ohtani, Eiji
- Chemical Geology, Vol. 418
The Serpentinite Multisystem Revisited: Chrysotile Is Metastable
journal, June 2004
- Evans, Bernard W.
- International Geology Review, Vol. 46, Issue 6
Water transportation from the subducting slab into the mantle transition zone
journal, January 2007
- Maruyama, Shigenori; Okamoto, Kazuaki
- Gondwana Research, Vol. 11, Issue 1-2
Aluminous hydrous mineral δ -AlOOH as a carrier of hydrogen into the core-mantle boundary
journal, January 2008
- Sano, Asami; Ohtani, Eiji; Kondo, Tadashi
- Geophysical Research Letters, Vol. 35, Issue 3
First principles prediction of a new high-pressure phase of dense hydrous magnesium silicates in the lower mantle: PREDICTION OF A HIGH PRESSURE DHMS PHASE
journal, September 2013
- Tsuchiya, Jun
- Geophysical Research Letters, Vol. 40, Issue 17
Pressure-Induced Hydrogen Bond Symmetrization in Iron Oxyhydroxide
journal, October 2013
- Xu, Weiming; Greenberg, Eran; Rozenberg, Gregory Kh.
- Physical Review Letters, Vol. 111, Issue 17
Ultrahigh-pressure phases of H O ice predicted using an adaptive genetic algorithm
journal, December 2011
- Ji, Min; Umemoto, Koichiro; Wang, Cai-Zhuang
- Physical Review B, Vol. 84, Issue 22
High pressure ices
journal, December 2011
- Hermann, A.; Ashcroft, N. W.; Hoffmann, R.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 3
First-principles prediction of a high-pressure hydrous phase of AlOOH
journal, February 2011
- Tsuchiya, Jun; Tsuchiya, Taku
- Physical Review B, Vol. 83, Issue 5
Symmetrization driven spin transition in ε-FeOOH at high pressure
journal, October 2013
- Gleason, A. E.; Quiroga, C. E.; Suzuki, A.
- Earth and Planetary Science Letters, Vol. 379
Dehydrogenation of goethite in Earth’s deep lower mantle
journal, January 2017
- Hu, Qingyang; Kim, Duck Young; Liu, Jin
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 7
First principles calculation of a high-pressure hydrous phase, δ-AlOOH: FIRST PRINCIPLES CALCULATION OF δ-ALOOH
journal, October 2002
- Tsuchiya, Jun; Tsuchiya, Taku; Tsuneyuki, Shinji
- Geophysical Research Letters, Vol. 29, Issue 19
Stochastic Surface Walking Method for Structure Prediction and Pathway Searching
journal, February 2013
- Shang, Cheng; Liu, Zhi-Pan
- Journal of Chemical Theory and Computation, Vol. 9, Issue 3
Stochastic surface walking method for crystal structure and phase transition pathway prediction
journal, January 2014
- Shang, Cheng; Zhang, Xiao-Jie; Liu, Zhi-Pan
- Phys. Chem. Chem. Phys., Vol. 16, Issue 33
Variable-Cell Double-Ended Surface Walking Method for Fast Transition State Location of Solid Phase Transitions
journal, September 2015
- Zhang, Xiao-Jie; Liu, Zhi-Pan
- Journal of Chemical Theory and Computation, Vol. 11, Issue 10
A generalized solid-state nudged elastic band method
journal, February 2012
- Sheppard, Daniel; Xiao, Penghao; Chemelewski, William
- The Journal of Chemical Physics, Vol. 136, Issue 7
Design and Observation of Biphase TiO 2 Crystal with Perfect Junction
journal, September 2014
- Zhu, Sheng-Cai; Xie, Song-Hai; Liu, Zhi-Pan
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 18
Energy Landscape of Zirconia Phase Transitions
journal, June 2015
- Guan, Shu-Hui; Zhang, Xiao-Jie; Liu, Zhi-Pan
- Journal of the American Chemical Society, Vol. 137, Issue 25
Reaction Network of Layer-to-Tunnel Transition of MnO 2
journal, January 2016
- Li, Ye-Fei; Zhu, Sheng-Cai; Liu, Zhi-Pan
- Journal of the American Chemical Society, Vol. 138, Issue 16
Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition
journal, August 2015
- Zhu, Sheng-Cai; Xie, Song-Hai; Liu, Zhi-Pan
- Journal of the American Chemical Society, Vol. 137, Issue 35
Reaction sampling and reactivity prediction using the stochastic surface walking method
journal, January 2015
- Zhang, Xiao-Jie; Liu, Zhi-Pan
- Physical Chemistry Chemical Physics, Vol. 17, Issue 4
Pressure-temperature stability studies of FeOOH using X-ray diffraction
journal, November 2008
- Gleason, A. E.; Jeanloz, R.; Kunz, M.
- American Mineralogist, Vol. 93, Issue 11-12
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Three-phase junction for modulating electron–hole migration in anatase–rutile photocatalysts
journal, January 2015
- Zhao, Wei-Na; Zhu, Sheng-Cai; Li, Ye-Fei
- Chemical Science, Vol. 6, Issue 6
Stability limits and transformation pathways of α -quartz under high pressure
journal, March 2017
- Hu, Q. Y.; Shu, J. -F.; Yang, W. G.
- Physical Review B, Vol. 95, Issue 10
Dielectric properties and lattice dynamics of -PbO -type TiO : The role of soft phonon modes in pressure-induced phase transition to baddeleyite-type TiO
journal, September 2011
- Cai, Yongqing; Zhang, Chun; Feng, Yuan Ping
- Physical Review B, Vol. 84, Issue 9
Enhanced Electron Transport in Nb-Doped TiO 2 Nanoparticles via Pressure-Induced Phase Transitions
journal, December 2013
- Lü, Xujie; Yang, Wenge; Quan, Zewei
- Journal of the American Chemical Society, Vol. 136, Issue 1
Works referencing / citing this record:
Thermal equation of state of MgSiO4H2 phase H determined by in situ X-ray diffraction and a multianvil apparatus
journal, June 2018
- Nishi, Masayuki; Tsuchiya, Jun; Arimoto, Takeshi
- Physics and Chemistry of Minerals, Vol. 45, Issue 10
Novel phases in ammonia-water mixtures under pressure
journal, December 2018
- Naden Robinson, Victor; Marqués, Miriam; Wang, Yanchao
- The Journal of Chemical Physics, Vol. 149, Issue 23
Altered chemistry of oxygen and iron under deep Earth conditions
journal, January 2019
- Liu, Jin; Hu, Qingyang; Bi, Wenli
- Nature Communications, Vol. 10, Issue 1
Overall structural modification of a layered Ni-rich cathode for enhanced cycling stability and rate capability at high voltage
journal, January 2019
- Tang, Manjing; Yang, Jun; Chen, Nantao
- Journal of Materials Chemistry A, Vol. 7, Issue 11
Proton-transfer Ferroelectricity / Multiferroicity in Rutile Oxyhydroxides
text, January 2018
- Wu, Menghao; Duan, Tianci; Lu, Chengliang
- arXiv