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Title: Temperature dependent structure and dynamics in smectite interlayers: 23 Na MAS NMR spectroscopy of Na-hectorite

Abstract

23Na MAS NMR spectroscopy of the smectite mineral hectorite acquired at temperatures from –120 °C to 40 °C in combination with the results from computational molecular dynamics (MD) simulations show the presence of complex dynamical processes in the interlayer galleries that depend significantly on their hydration state. The results indicate that site exchange occurs within individual interlayers that contain coexisting 1 and 2 water layer hydrates in different places. We suggest that the observed dynamical averaging may be due to motion of water volumes comparable to the dripplons recently proposed to occur in hydrated graphene interlayers (Yoshida et al. Nat. Commun., 2018, 9, 1496). Such motion would cause rippling of the T-O-T structure of the clay layers at frequencies greater than ~25 kHz. For samples exposed to 0% relative humidity (R.H.), the 23Na spectra show the presence of two Na+ sites (probably 6 and 9 coordinated by basal oxygen atoms) that do not undergo dynamical averaging at any temperature from –120 °C to 40 °C. For samples exposed to R.H.s from 29% to 100% the spectra show the presence of three hydrated Na+ sites that undergo dynamical averaging beginning at –60 °C. These sites have different numbers of H2O moleculesmore » coordinating the Na+, and diffusion calculations indicate that they probably occur within the same individual interlayer. The average hydration state of Na+ increases with increasing R.H. and water content of the clay.« less

Authors:
 [1];  [2];  [3];  [4];  [5]
+ Show Author Affiliations
  1. Department of Chemistry, Michigan State University, East Lansing, USA, Department of Chemistry
  2. Department of Chemistry and Biochemistry, St. Mary's College of Maryland, St. Mary's City, USA
  3. Department of Chemistry, Michigan State University, East Lansing, USA
  4. William R. Wiley Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, USA
  5. Department of Chemistry, Michigan State University, East Lansing, USA, Department 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); Battelle Memorial Institute, Columbus, OH (United States); Michigan State Univ., East Lansing, MI (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1508865
Alternate Identifier(s):
OSTI ID: 1543823; OSTI ID: 1617901
Report Number(s):
PNNL-SA-145048
Journal ID: ISSN 2046-2069; RSCACL
Grant/Contract Number:  
AC05-76RL01830; FG02-08ER15929
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 9 Journal Issue: 22; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Nanda, Raju, Bowers, Geoffrey M., Loganathan, Narasimhan, Burton, Sarah D., and Kirkpatrick, R. James. Temperature dependent structure and dynamics in smectite interlayers: 23 Na MAS NMR spectroscopy of Na-hectorite. United Kingdom: N. p., 2019. Web. doi:10.1039/C9RA01056D.
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Nanda, Raju, Bowers, Geoffrey M., Loganathan, Narasimhan, Burton, Sarah D., & Kirkpatrick, R. James. Temperature dependent structure and dynamics in smectite interlayers: 23 Na MAS NMR spectroscopy of Na-hectorite. United Kingdom. https://doi.org/10.1039/C9RA01056D
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Nanda, Raju, Bowers, Geoffrey M., Loganathan, Narasimhan, Burton, Sarah D., and Kirkpatrick, R. James. Thu . "Temperature dependent structure and dynamics in smectite interlayers: 23 Na MAS NMR spectroscopy of Na-hectorite". United Kingdom. https://doi.org/10.1039/C9RA01056D.
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@article{osti_1508865,
title = {Temperature dependent structure and dynamics in smectite interlayers: 23 Na MAS NMR spectroscopy of Na-hectorite},
author = {Nanda, Raju and Bowers, Geoffrey M. and Loganathan, Narasimhan and Burton, Sarah D. and Kirkpatrick, R. James},
abstractNote = {23Na MAS NMR spectroscopy of the smectite mineral hectorite acquired at temperatures from –120 °C to 40 °C in combination with the results from computational molecular dynamics (MD) simulations show the presence of complex dynamical processes in the interlayer galleries that depend significantly on their hydration state. The results indicate that site exchange occurs within individual interlayers that contain coexisting 1 and 2 water layer hydrates in different places. We suggest that the observed dynamical averaging may be due to motion of water volumes comparable to the dripplons recently proposed to occur in hydrated graphene interlayers (Yoshida et al. Nat. Commun., 2018, 9, 1496). Such motion would cause rippling of the T-O-T structure of the clay layers at frequencies greater than ~25 kHz. For samples exposed to 0% relative humidity (R.H.), the 23Na spectra show the presence of two Na+ sites (probably 6 and 9 coordinated by basal oxygen atoms) that do not undergo dynamical averaging at any temperature from –120 °C to 40 °C. For samples exposed to R.H.s from 29% to 100% the spectra show the presence of three hydrated Na+ sites that undergo dynamical averaging beginning at –60 °C. These sites have different numbers of H2O molecules coordinating the Na+, and diffusion calculations indicate that they probably occur within the same individual interlayer. The average hydration state of Na+ increases with increasing R.H. and water content of the clay.},
doi = {10.1039/C9RA01056D},
journal = {RSC Advances},
number = 22,
volume = 9,
place = {United Kingdom},
year = {Thu Apr 25 00:00:00 EDT 2019},
month = {Thu Apr 25 00:00:00 EDT 2019}
}
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https://doi.org/10.1039/C9RA01056D
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