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

Zhu, Sheng-cai; Hu, Qingyang; Mao, Wendy L.; Mao, Ho-kwang; Sheng, Hongwei

doi:10.1021/jacs.7b06528

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

Journal Article · Thu Aug 24 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b06528· OSTI ID:1474063

Zhu, Sheng-cai ^[1];

^[2]; Mao, Wendy L. ^[3]; Mao, Ho-kwang ^[4]; Sheng, Hongwei ^[5]

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

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

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Carnegie Inst. of Washington, Washington, DC (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); NSAF

Grant/Contract Number:: NA0001974; 21703004; U1530402

OSTI ID:: 1474063

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 35; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 32 works

Citation information provided by
Web of Science

References (31)

Decomposition of phase D in the lower mantle and the fate of dense hydrous silicates in subducting slabs Shieh, Sean R.; Mao, Ho-kwang; Hemley, Russell J. Earth and Planetary Science Letters, Vol. 159, Issue 1-2 https://doi.org/10.1016/S0012-821X(98)00062-4	journal	June 1998
FeO2 and FeOOH under deep lower-mantle conditions and Earth’s oxygen–hydrogen cycles Hu, Qingyang; Kim, Duck Young; Yang, Wenge Nature, Vol. 534, Issue 7606 https://doi.org/10.1038/nature18018	journal	June 2016
Hydrous minerals and the storage of water in the deep mantle Ohtani, Eiji Chemical Geology, Vol. 418 https://doi.org/10.1016/j.chemgeo.2015.05.005	journal	December 2015
The Serpentinite Multisystem Revisited: Chrysotile Is Metastable Evans, Bernard W. International Geology Review, Vol. 46, Issue 6 https://doi.org/10.2747/0020-6814.46.6.479	journal	June 2004
Water transportation from the subducting slab into the mantle transition zone Maruyama, Shigenori; Okamoto, Kazuaki Gondwana Research, Vol. 11, Issue 1-2 https://doi.org/10.1016/j.gr.2006.06.001	journal	January 2007
Aluminous hydrous mineral δ -AlOOH as a carrier of hydrogen into the core-mantle boundary Sano, Asami; Ohtani, Eiji; Kondo, Tadashi Geophysical Research Letters, Vol. 35, Issue 3 https://doi.org/10.1029/2007GL031718	journal	January 2008
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 Tsuchiya, Jun Geophysical Research Letters, Vol. 40, Issue 17 https://doi.org/10.1002/grl.50875	journal	September 2013
Pressure-Induced Hydrogen Bond Symmetrization in Iron Oxyhydroxide Xu, Weiming; Greenberg, Eran; Rozenberg, Gregory Kh. Physical Review Letters, Vol. 111, Issue 17 https://doi.org/10.1103/PhysRevLett.111.175501	journal	October 2013
Ultrahigh-pressure phases of H $_{2}$ O ice predicted using an adaptive genetic algorithm Ji, Min; Umemoto, Koichiro; Wang, Cai-Zhuang Physical Review B, Vol. 84, Issue 22 https://doi.org/10.1103/PhysRevB.84.220105	journal	December 2011
High pressure ices Hermann, A.; Ashcroft, N. W.; Hoffmann, R. Proceedings of the National Academy of Sciences, Vol. 109, Issue 3 https://doi.org/10.1073/pnas.1118694109	journal	December 2011
First-principles prediction of a high-pressure hydrous phase of AlOOH Tsuchiya, Jun; Tsuchiya, Taku Physical Review B, Vol. 83, Issue 5 https://doi.org/10.1103/PhysRevB.83.054115	journal	February 2011
Symmetrization driven spin transition in ε-FeOOH at high pressure Gleason, A. E.; Quiroga, C. E.; Suzuki, A. Earth and Planetary Science Letters, Vol. 379 https://doi.org/10.1016/j.epsl.2013.08.012	journal	October 2013
Dehydrogenation of goethite in Earth’s deep lower mantle Hu, Qingyang; Kim, Duck Young; Liu, Jin Proceedings of the National Academy of Sciences, Vol. 114, Issue 7 https://doi.org/10.1073/pnas.1620644114	journal	January 2017
First principles calculation of a high-pressure hydrous phase, δ-AlOOH: FIRST PRINCIPLES CALCULATION OF δ-ALOOH Tsuchiya, Jun; Tsuchiya, Taku; Tsuneyuki, Shinji Geophysical Research Letters, Vol. 29, Issue 19 https://doi.org/10.1029/2002GL015417	journal	October 2002
Stochastic Surface Walking Method for Structure Prediction and Pathway Searching Shang, Cheng; Liu, Zhi-Pan Journal of Chemical Theory and Computation, Vol. 9, Issue 3 https://doi.org/10.1021/ct301010b	journal	February 2013
Stochastic surface walking method for crystal structure and phase transition pathway prediction Shang, Cheng; Zhang, Xiao-Jie; Liu, Zhi-Pan Phys. Chem. Chem. Phys., Vol. 16, Issue 33 https://doi.org/10.1039/C4CP01485E	journal	January 2014
Variable-Cell Double-Ended Surface Walking Method for Fast Transition State Location of Solid Phase Transitions Zhang, Xiao-Jie; Liu, Zhi-Pan Journal of Chemical Theory and Computation, Vol. 11, Issue 10 https://doi.org/10.1021/acs.jctc.5b00641	journal	September 2015
A generalized solid-state nudged elastic band method Sheppard, Daniel; Xiao, Penghao; Chemelewski, William The Journal of Chemical Physics, Vol. 136, Issue 7 https://doi.org/10.1063/1.3684549	journal	February 2012
Design and Observation of Biphase TiO ₂ Crystal with Perfect Junction Zhu, Sheng-Cai; Xie, Song-Hai; Liu, Zhi-Pan The Journal of Physical Chemistry Letters, Vol. 5, Issue 18 https://doi.org/10.1021/jz5016247	journal	September 2014
Energy Landscape of Zirconia Phase Transitions Guan, Shu-Hui; Zhang, Xiao-Jie; Liu, Zhi-Pan Journal of the American Chemical Society, Vol. 137, Issue 25 https://doi.org/10.1021/jacs.5b04528	journal	June 2015
Reaction Network of Layer-to-Tunnel Transition of MnO ₂ Li, Ye-Fei; Zhu, Sheng-Cai; Liu, Zhi-Pan Journal of the American Chemical Society, Vol. 138, Issue 16 https://doi.org/10.1021/jacs.6b01768	journal	January 2016
Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition Zhu, Sheng-Cai; Xie, Song-Hai; Liu, Zhi-Pan Journal of the American Chemical Society, Vol. 137, Issue 35 https://doi.org/10.1021/jacs.5b07734	journal	August 2015
Reaction sampling and reactivity prediction using the stochastic surface walking method Zhang, Xiao-Jie; Liu, Zhi-Pan Physical Chemistry Chemical Physics, Vol. 17, Issue 4 https://doi.org/10.1039/C4CP04456H	journal	January 2015
Pressure-temperature stability studies of FeOOH using X-ray diffraction Gleason, A. E.; Jeanloz, R.; Kunz, M. American Mineralogist, Vol. 93, Issue 11-12 https://doi.org/10.2138/am.2008.2942	journal	November 2008
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Three-phase junction for modulating electron–hole migration in anatase–rutile photocatalysts Zhao, Wei-Na; Zhu, Sheng-Cai; Li, Ye-Fei Chemical Science, Vol. 6, Issue 6 https://doi.org/10.1039/C5SC00621J	journal	January 2015
Stability limits and transformation pathways of α -quartz under high pressure Hu, Q. Y.; Shu, J. -F.; Yang, W. G. Physical Review B, Vol. 95, Issue 10 https://doi.org/10.1103/PhysRevB.95.104112	journal	March 2017
Dielectric properties and lattice dynamics of $α$ -PbO $_{2}$ -type TiO $_{2}$ : The role of soft phonon modes in pressure-induced phase transition to baddeleyite-type TiO $_{2}$ Cai, Yongqing; Zhang, Chun; Feng, Yuan Ping Physical Review B, Vol. 84, Issue 9 https://doi.org/10.1103/PhysRevB.84.094107	journal	September 2011
Enhanced Electron Transport in Nb-Doped TiO ₂ Nanoparticles via Pressure-Induced Phase Transitions Lü, Xujie; Yang, Wenge; Quan, Zewei Journal of the American Chemical Society, Vol. 136, Issue 1 https://doi.org/10.1021/ja410810w	journal	December 2013

Cited By (5)

Thermal equation of state of MgSiO4H2 phase H determined by in situ X-ray diffraction and a multianvil apparatus Nishi, Masayuki; Tsuchiya, Jun; Arimoto, Takeshi Physics and Chemistry of Minerals, Vol. 45, Issue 10 https://doi.org/10.1007/s00269-018-0980-z	journal	June 2018
Novel phases in ammonia-water mixtures under pressure Naden Robinson, Victor; Marqués, Miriam; Wang, Yanchao The Journal of Chemical Physics, Vol. 149, Issue 23 https://doi.org/10.1063/1.5063569	journal	December 2018
Altered chemistry of oxygen and iron under deep Earth conditions Liu, Jin; Hu, Qingyang; Bi, Wenli Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-08071-3	journal	January 2019
Overall structural modification of a layered Ni-rich cathode for enhanced cycling stability and rate capability at high voltage Tang, Manjing; Yang, Jun; Chen, Nantao Journal of Materials Chemistry A, Vol. 7, Issue 11 https://doi.org/10.1039/c8ta12494a	journal	January 2019
Proton-transfer Ferroelectricity / Multiferroicity in Rutile Oxyhydroxides Wu, Menghao; Duan, Tianci; Lu, Chengliang arXiv https://doi.org/10.48550/arxiv.1811.00091	text	January 2018

Similar Records

Experimental Evidence for Partially Dehydrogenated ε-FeOOH

Journal Article · Sat Jul 13 00:00:00 EDT 2019 · Crystals · OSTI ID:1474063

Zhuang, Yukai; Cui, Zhongxun; Zhang, Dongzhou; +3 more

Superionic iron oxide–hydroxide in Earth’s deep mantle

Journal Article · Mon Mar 08 00:00:00 EST 2021 · Nature Geoscience · OSTI ID:1474063

Hou, Mingqiang; He, Yu; Jang, Bo Gyu; +16 more

Dehydrogenation of goethite in Earth’s deep lower mantle

Journal Article · Tue Jan 31 00:00:00 EST 2017 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1474063

Hu, Qingyang; Kim, Duck Young; Liu, Jin; +5 more

Related Subjects

58 GEOSCIENCES
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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

Citation Formats

References (31)

Cited By (5)

Similar Records

Related Subjects

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