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Title: Competitive Adsorption of H 2 O and CO 2 in 2-Dimensional Nanoconfinement: GCMD Simulations of Cs- and Ca-Hectorites

Abstract

The intercalation of H2O, CO2, and other fluid species in expandable clay minerals (smectites) may play a significant role in controlling the behavior of these species in geological carbon sequestration and enhanced petroleum production and has been the subject of intensive study in recent years. This paper reports the results of a computational study of the effects of the properties of the charge-balancing, exchangeable cations on H2O and CO2 intercalation in the smectite mineral, hectorite, in equilibrium with an H2O-saturated supercritical CO2 fluid under reservoir conditions using grand canonical molecular dynamics methods. The results show that the intercalation behavior is greatly different for the cations with relatively low hydration energies and high affinities for CO2 (here Cs+) than for cations with higher hydration energies (here Ca2+). With Cs+, CO2 intercalation occurs in a 1-layer structure and does not require H2O intercalation, whereas with Ca2+, the presence of a sub-monolayer of H2O is required for CO2 intercalation. The computational results provide a detailed structural, dynamical, and energetic insight into the differences in the intercalation behavior and are in excellent agreement with in situ experimental X-ray diffraction, infrared, quartz crystal microbalance, and nuclear magnetic resonance results for smectite materials obtained under reservoirmore » conditions.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [5]
+ Show Author Affiliations
  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
  2. St. Mary’s College of Maryland, St. Mary’s City, MD (United States). Dept. of Chemistry and Biochemistry
  3. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry; Univ. College London, London (United Kingdom). Dept. of Chemical Engineering
  4. Laboratoire SUBATECH, UMR 6457—Institut Mines-Télécom Atlantique, Université de Nantes, CNRS/IN2P3, 44307 Nantes, France
  5. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry, and Dept of Earth and Environmental Sciences
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Michigan State Univ., East Lansing, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1543652
Grant/Contract Number:  
FG02-08ER15929
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 41; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Science & Technology - Other Topics; Materials Science

Citation Formats

Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Kalinichev, Andrey G., and Kirkpatrick, R. James. Competitive Adsorption of H 2 O and CO 2 in 2-Dimensional Nanoconfinement: GCMD Simulations of Cs- and Ca-Hectorites. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b06602.
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Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Kalinichev, Andrey G., & Kirkpatrick, R. James. Competitive Adsorption of H 2 O and CO 2 in 2-Dimensional Nanoconfinement: GCMD Simulations of Cs- and Ca-Hectorites. United States. https://doi.org/10.1021/acs.jpcc.8b06602
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Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Kalinichev, Andrey G., and Kirkpatrick, R. James. Fri . "Competitive Adsorption of H 2 O and CO 2 in 2-Dimensional Nanoconfinement: GCMD Simulations of Cs- and Ca-Hectorites". United States. https://doi.org/10.1021/acs.jpcc.8b06602. https://www.osti.gov/servlets/purl/1543652.
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@article{osti_1543652,
title = {Competitive Adsorption of H 2 O and CO 2 in 2-Dimensional Nanoconfinement: GCMD Simulations of Cs- and Ca-Hectorites},
author = {Loganathan, Narasimhan and Bowers, Geoffrey M. and Yazaydin, A. Ozgur and Kalinichev, Andrey G. and Kirkpatrick, R. James},
abstractNote = {The intercalation of H2O, CO2, and other fluid species in expandable clay minerals (smectites) may play a significant role in controlling the behavior of these species in geological carbon sequestration and enhanced petroleum production and has been the subject of intensive study in recent years. This paper reports the results of a computational study of the effects of the properties of the charge-balancing, exchangeable cations on H2O and CO2 intercalation in the smectite mineral, hectorite, in equilibrium with an H2O-saturated supercritical CO2 fluid under reservoir conditions using grand canonical molecular dynamics methods. The results show that the intercalation behavior is greatly different for the cations with relatively low hydration energies and high affinities for CO2 (here Cs+) than for cations with higher hydration energies (here Ca2+). With Cs+, CO2 intercalation occurs in a 1-layer structure and does not require H2O intercalation, whereas with Ca2+, the presence of a sub-monolayer of H2O is required for CO2 intercalation. The computational results provide a detailed structural, dynamical, and energetic insight into the differences in the intercalation behavior and are in excellent agreement with in situ experimental X-ray diffraction, infrared, quartz crystal microbalance, and nuclear magnetic resonance results for smectite materials obtained under reservoir conditions.},
doi = {10.1021/acs.jpcc.8b06602},
journal = {Journal of Physical Chemistry. C},
number = 41,
volume = 122,
place = {United States},
year = {Fri Jun 01 00:00:00 EDT 2018},
month = {Fri Jun 01 00:00:00 EDT 2018}
}
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