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

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [5]
  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
+ Show Author Affiliations
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.
Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-08ER15929
OSTI ID:
1543652
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 41 Vol. 122; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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