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Title: Molecular Dynamics Study of CO2 and H2O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite

Abstract

Grand Canonical Molecular Dynamics (GCMD) simulations were performed to investigate the intercalation of CO2 and H2O molecules in the interlayers of the smectite clay, Na-hectorite, at temperatures and pressures relevant to petroleum reservoir and geological carbon sequestration conditions and in equilibrium with H2O-saturated CO2. The computed adsorption isotherms indicate that CO2 molecules enter the interlayer space of Na-hectorite only when it is hydrated with approximately three H2O molecules per unit cell. The computed immersion energies show that the bilayer hydrate structure (2WL) contains less CO2 than the monolayer structure (1WL) but that the 2WL hydrate is the most thermodynamically stable state, consistent with experimental results for a similar Na-montmorillonite smectite. Under all T and P conditions examined (323–368 K and 90–150 bar), the CO2 molecules are adsorbed at the midplane of clay interlayers for the 1WL structure and closer to one of the basal surfaces for the 2WL structure. Interlayer CO2 molecules are dynamically less restricted in the 2WL structures. The CO2 molecules are preferentially located near basal surface oxygen atoms and H2O molecules rather than in coordination with Na+ ions. Accounting for the orientation and flexibility of the structural -OH groups of the clay layer has a significant effectmore » on the details of the computed structure and dynamics of H2O and CO2 molecules but does not affect the overall trends with changing basal spacing or the principal structural and dynamical conclusions. Temperature and pressure in the ranges examined have little effect on the principal structural and energetic conclusions, but the rates of dynamical processes increase with increasing temperature, as expected.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [5]
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  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
  2. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry; Univ. College London, London (United Kingdom). Dept. of Chemical Engineering
  3. St. Mary’s College of Maryland, St. Mary's City, MD (United States). Dept. of Chemistry and Biochemistry
  4. Subatomic Physics and Associated Technologies (SUBATECH) Lab., Nantes (France). Inst. Mines-Télécom Atlantique
  5. Michigan State Univ., East Lansing, MI (United States). College of Natural Science
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1482389
Grant/Contract Number:  
FG02-08ER15929; FG02-10ER16128
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 44; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Loganathan, Narasimhan, Yazaydin, A. Ozgur, Bowers, Geoffrey M., Kalinichev, Andrey G., and Kirkpatrick, R. James. Molecular Dynamics Study of CO2 and H2O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b06825.
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Loganathan, Narasimhan, Yazaydin, A. Ozgur, Bowers, Geoffrey M., Kalinichev, Andrey G., & Kirkpatrick, R. James. Molecular Dynamics Study of CO2 and H2O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite. United States. https://doi.org/10.1021/acs.jpcc.7b06825
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Loganathan, Narasimhan, Yazaydin, A. Ozgur, Bowers, Geoffrey M., Kalinichev, Andrey G., and Kirkpatrick, R. James. Wed . "Molecular Dynamics Study of CO2 and H2O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite". United States. https://doi.org/10.1021/acs.jpcc.7b06825. https://www.osti.gov/servlets/purl/1482389.
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@article{osti_1482389,
title = {Molecular Dynamics Study of CO2 and H2O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite},
author = {Loganathan, Narasimhan and Yazaydin, A. Ozgur and Bowers, Geoffrey M. and Kalinichev, Andrey G. and Kirkpatrick, R. James},
abstractNote = {Grand Canonical Molecular Dynamics (GCMD) simulations were performed to investigate the intercalation of CO2 and H2O molecules in the interlayers of the smectite clay, Na-hectorite, at temperatures and pressures relevant to petroleum reservoir and geological carbon sequestration conditions and in equilibrium with H2O-saturated CO2. The computed adsorption isotherms indicate that CO2 molecules enter the interlayer space of Na-hectorite only when it is hydrated with approximately three H2O molecules per unit cell. The computed immersion energies show that the bilayer hydrate structure (2WL) contains less CO2 than the monolayer structure (1WL) but that the 2WL hydrate is the most thermodynamically stable state, consistent with experimental results for a similar Na-montmorillonite smectite. Under all T and P conditions examined (323–368 K and 90–150 bar), the CO2 molecules are adsorbed at the midplane of clay interlayers for the 1WL structure and closer to one of the basal surfaces for the 2WL structure. Interlayer CO2 molecules are dynamically less restricted in the 2WL structures. The CO2 molecules are preferentially located near basal surface oxygen atoms and H2O molecules rather than in coordination with Na+ ions. Accounting for the orientation and flexibility of the structural -OH groups of the clay layer has a significant effect on the details of the computed structure and dynamics of H2O and CO2 molecules but does not affect the overall trends with changing basal spacing or the principal structural and dynamical conclusions. Temperature and pressure in the ranges examined have little effect on the principal structural and energetic conclusions, but the rates of dynamical processes increase with increasing temperature, as expected.},
doi = {10.1021/acs.jpcc.7b06825},
journal = {Journal of Physical Chemistry. C},
number = 44,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b06825
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Cited by: 16 works
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Figures / Tables:

Figure 1 Figure 1: Average number of intercalated CO2 and H2O molecules in the Na-hectorite interlayers per unit cell as functions of interlayer basal spacing at different combinations of simulated T and P. Note that the CO2 data are expanded (see the right hand y axis) since a small number of CO2more » are present in the interlayer relative to the interlayer H2O at most conditions. Color code: black – 323K; red – 348K; green – 368K. Figure d is for simulations at 90 bar using fixed structural -OH groups. The error bars show the 95% confidence level.« less
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Works referenced in this record:

A Guide to CO2 Sequestration
journal, June 2003

A Quantitative Model for Ion Diffusion in Compacted Bentonite
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An Integrated Experimental System for Solid-Gas-Liquid Environmental Cells
journal, December 2014

Water diffusion in a synthetic hectorite by neutron scattering—beyond the isotropic translational model
journal, February 2008

Multiscale Water Dynamics within Dense Clay Sediments Probed by 2 H Multiquantum NMR Relaxometry and Two-Time Stimulated Echo NMR Spectroscopy
journal, December 2013

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journal, March 2003

  • Breu, Josef; Seidl, Wolfgang; Stoll, Alexander
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  • DOI: 10.1002/zaac.200390083

Grand canonical molecular dynamics
journal, December 2003

  • Boinepalli, Sharada; Attard, Phil
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  • DOI: 10.1063/1.1629079

On the Hydrogen Bonding Structure at the Aqueous Interface of Ammonium-Substituted Mica: A Molecular Dynamics Simulation
journal, February 2013

  • Loganathan, Narasimhan; Kalinichev, Andrey G.
  • Zeitschrift für Naturforschung A, Vol. 68, Issue 1-2
  • DOI: 10.5560/zna.2012-0101

Hydrogen-bond kinetics in liquid water
journal, January 1996

  • Luzar, Alenka; Chandler, David
  • Nature, Vol. 379, Issue 6560
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Smectite fluorination and its impact on interlayer water content and structure: A way to fine tune the hydrophilicity of clay surfaces?
journal, November 2013

Structure and dynamics of hydrated ions
journal, May 1993

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    Understanding methane/carbon dioxide partitioning in clay nano- and meso-pores with constant reservoir composition molecular dynamics modeling
    journal, January 2019

    • Loganathan, Narasimhan; Bowers, Geoffrey M.; Ngouana Wakou, Brice F.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 13
    • DOI: 10.1039/c9cp00851a
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      Figures / Tables found in this record:

      Figure 1 (p. 43)figure
      Figure 2 (p. 44)figure
      Figure 3 (p. 45)figure
      Figure 4 (p. 46)figure
      Figure 5 (p. 47)figure
      Figure 6 (p. 48)figure
      Figure 7 (p. 49)figure
      Figure 8 (p. 53)figure
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