skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Temperature dependent structure and dynamics in smectite interlayers: 23Na 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 Hmore » 2O 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.« less

Authors:
 [1];  [2];  [3];  [4];  [3]
  1. Michigan State Univ., East Lansing, MI (United States); Bar-Ilan Univ., Ramat Gan (Israel)
  2. St. Mary's College of Maryland; St. Mary's City, MD (United States)
  3. Michigan State Univ., East Lansing, MI (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
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)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1508865
Alternate Identifier(s):
OSTI ID: 1543823
Grant/Contract Number:  
AC05-76RL01830; FG02-08ER15929
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Volume: 9; Journal Issue: 22; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Chemistry

Citation Formats

Nanda, Raju, Bowers, Geoffrey M., Loganathan, Narasimhan, Burton, Sarah D., and Kirkpatrick, R. James. Temperature dependent structure and dynamics in smectite interlayers: 23Na MAS NMR spectroscopy of Na-hectorite. United States: N. p., 2019. Web. doi:10.1039/c9ra01056d.
Nanda, Raju, Bowers, Geoffrey M., Loganathan, Narasimhan, Burton, Sarah D., & Kirkpatrick, R. James. Temperature dependent structure and dynamics in smectite interlayers: 23Na MAS NMR spectroscopy of Na-hectorite. United States. doi:10.1039/c9ra01056d.
Nanda, Raju, Bowers, Geoffrey M., Loganathan, Narasimhan, Burton, Sarah D., and Kirkpatrick, R. James. Thu . "Temperature dependent structure and dynamics in smectite interlayers: 23Na MAS NMR spectroscopy of Na-hectorite". United States. doi:10.1039/c9ra01056d.
@article{osti_1508865,
title = {Temperature dependent structure and dynamics in smectite interlayers: 23Na 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 States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/c9ra01056d

Save / Share:

Works referenced in this record:

Competitive Adsorption of H 2 O and CO 2 in 2-Dimensional Nanoconfinement: GCMD Simulations of Cs- and Ca-Hectorites
journal, June 2018

  • Loganathan, Narasimhan; Bowers, Geoffrey M.; Yazaydin, A. Ozgur
  • The Journal of Physical Chemistry C, Vol. 122, Issue 41
  • DOI: 10.1021/acs.jpcc.8b06602

Influence of Confinement on the Long-Range Mobility of Water Molecules within Clay Aggregates:  A 2 H NMR Analysis Using Spin-Locking Relaxation Rates
journal, September 2007

  • Porion, Patrice; Michot, Laurent J.; Faugère, Anne Marie
  • The Journal of Physical Chemistry C, Vol. 111, Issue 35
  • DOI: 10.1021/jp073393y

Water Structure and Dynamics in Smectites: X-ray Diffraction and 2 H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite
journal, April 2016

  • Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan
  • The Journal of Physical Chemistry C, Vol. 120, Issue 16
  • DOI: 10.1021/acs.jpcc.6b03431

Sequences of charged sheets in rectorite
journal, April 1995

  • Jakobsen, Hans J.; Nielsen, Niels C.; Lindgreen, Holger
  • American Mineralogist, Vol. 80, Issue 3-4
  • DOI: 10.2138/am-1995-3-406

Modelling one- and two-dimensional solid-state NMR spectra: Modelling 1D and 2D solid-state NMR spectra
journal, December 2001

  • Massiot, Dominique; Fayon, Franck; Capron, Mickael
  • Magnetic Resonance in Chemistry, Vol. 40, Issue 1
  • DOI: 10.1002/mrc.984

Geometry and Dynamics of Intercalated Water in Na-Fluorhectorite Clay Hydrates
journal, January 2008

  • Tenório, Rômulo P.; Alme, Lars Ramstad; Engelsberg, Mario
  • The Journal of Physical Chemistry C, Vol. 112, Issue 2
  • DOI: 10.1021/jp0766407

Water and ions in clays: Unraveling the interlayer/micropore exchange using molecular dynamics
journal, November 2007

  • Rotenberg, Benjamin; Marry, Virginie; Vuilleumier, Rodolphe
  • Geochimica et Cosmochimica Acta, Vol. 71, Issue 21
  • DOI: 10.1016/j.gca.2007.08.018

Signature of Low-Dimensional Diffusion in Complex Systems
journal, December 2008


Structure, Energetics, and Dynamics of Cs + and H 2 O in Hectorite: Molecular Dynamics Simulations with an Unconstrained Substrate Surface
journal, May 2016

  • Loganathan, Narasimhan; Yazaydin, A. Ozgur; Bowers, Geoffrey M.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 19
  • DOI: 10.1021/acs.jpcc.6b01016

Structural and dynamical relationships of Ca2+ and H2O in smectite/2H2O systems
journal, February 2014

  • Bowers, G. M.; Singer, J. W.; Bish, D. L.
  • American Mineralogist, Vol. 99, Issue 2-3
  • DOI: 10.2138/am.2014.4499

In Situ 13 C and 23 Na Magic Angle Spinning NMR Investigation of Supercritical CO 2 Incorporation in Smectite–Natural Organic Matter Composites
journal, February 2014

  • Bowers, Geoffrey M.; Hoyt, David W.; Burton, Sarah D.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 7
  • DOI: 10.1021/jp410535d

The structural environments of cations adsorbed onto clays: 133Cs variable-temperature MAS NMR spectroscopic study of hectorite
journal, June 1990

  • Weiss, Charles Arthur; Kirkpatrick, R. James; Altaner, Stephen P.
  • Geochimica et Cosmochimica Acta, Vol. 54, Issue 6
  • DOI: 10.1016/0016-7037(90)90398-5

X-ray absorption spectroscopy investigation of aqueous Co(II) and Sr(II) sorption at clay–water interfaces
journal, October 1999


Lanthanide sorption on smectitic clays in presence of cement leachates
journal, February 2010

  • Galunin, Evgeny; Alba, María D.; Santos, Maria J.
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 3
  • DOI: 10.1016/j.gca.2009.11.003

Emergence of Undulations and Determination of Materials Properties in Large-Scale Molecular Dynamics Simulation of Layered Double Hydroxides
journal, November 2007

  • Thyveetil, Mary-Ann; Coveney, Peter V.; Suter, James L.
  • Chemistry of Materials, Vol. 19, Issue 23
  • DOI: 10.1021/cm070923u

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Charge location effect on the hydration properties of synthetic saponite and hectorite saturated by Na+, Ca2+ cations: XRD investigation
journal, September 2009


Molecular Simulation for Flexibility of a Single Clay Layer
journal, August 2001

  • Sato, Hisako; Yamagishi, Akihiko; Kawamura, Katsuyuki
  • The Journal of Physical Chemistry B, Vol. 105, Issue 33
  • DOI: 10.1021/jp004491l

23 Na and 133 Cs NMR study of cation adsorption on mineral surfaces: Local environments, dynamics, and effects of mixed cations
journal, December 1997


YUCCA MOUNTAIN: Earth-Science Issues at a Geologic Repository for High-Level Nuclear Waste
journal, May 2004


133Cs NMR and XPS investigation of cesium adsorbed on clay minerals and related phases
journal, March 1996

  • Kim, Yeongkyoo; Cygan, Randall T.; Kirkpatrick, R. James
  • Geochimica et Cosmochimica Acta, Vol. 60, Issue 6
  • DOI: 10.1016/0016-7037(95)00452-1

Correlation of exfoliation performance with interlayer cations of montmorillonite in the preparation of two‐dimensional nanosheets
journal, January 2019

  • Bai, Haoyu; Zhao, Yunliang; Zhang, Xian
  • Journal of the American Ceramic Society, Vol. 102, Issue 7
  • DOI: 10.1111/jace.16285

23Na NMR chemical shifts and local Na coordination environments in silicate crystals, melts and glasses
journal, October 1993

  • Xue, Xianyu; Stebbins, JonathanF.
  • Physics and Chemistry of Minerals, Vol. 20, Issue 5
  • DOI: 10.1007/BF00215100

Materials properties of clay nanocomposites: onset of negative Poisson ratio in large-scale molecular dynamics simulation
journal, January 2009

  • Suter, James L.; Coveney, Peter V.
  • Soft Matter, Vol. 5, Issue 20
  • DOI: 10.1039/b907590a

Dehydration of Cu−Hectorite:  Water Isotherm, XRD, and EPR Studies
journal, January 1996

  • Annabi-Bergaya, Faïza; Estrade-Szwarckopf, Henriette; Van Damme, Henri
  • The Journal of Physical Chemistry, Vol. 100, Issue 10
  • DOI: 10.1021/jp950283v

Intercalated Water in Synthetic Fluorhectorite Clay
journal, June 2010

  • Tenório, Rômulo P.; Engelsberg, M.; Fossum, Jon Otto
  • Langmuir, Vol. 26, Issue 12
  • DOI: 10.1021/la100377s

Dynamics in Clays - Combining Neutron Scattering and Microscopic Simulation
journal, February 2010

  • Malikova, Natalie; Dubois, Emmanuelle; Marry, Virginie
  • Zeitschrift für Physikalische Chemie, Vol. 224, Issue 1-2
  • DOI: 10.1524/zpch.2010.6097

High-Resolution Electron Microscopy of Montmorillonite and Montmorillonite/Epoxy Nanocomposites
journal, September 2005

  • Drummy, Lawrence F.; Koerner, Hilmar; Farmer, Karen
  • The Journal of Physical Chemistry B, Vol. 109, Issue 38
  • DOI: 10.1021/jp053133l

Deformation Measurements on Thin Clay Tactoids
journal, August 2009


Water Diffusion in a Synthetic Hectorite Clay Studied by Quasi-elastic Neutron Scattering
journal, November 2007

  • Malikova, N.; Cadène, A.; Dubois, E.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 47
  • DOI: 10.1021/jp0748009

Interaction of water with clay minerals as studied by 2H nuclear magnetic resonance spectroscopy
journal, January 1996


Large-Scale Molecular Dynamics Study of Montmorillonite Clay:  Emergence of Undulatory Fluctuations and Determination of Material Properties
journal, June 2007

  • Suter, James L.; Coveney, Peter V.; Greenwell, H. Chris
  • The Journal of Physical Chemistry C, Vol. 111, Issue 23
  • DOI: 10.1021/jp070294b

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers
journal, September 2002


Linking Cesium and Strontium Uptake to Kaolinite Weathering in Simulated Tank Waste Leachate
journal, May 2003

  • Chorover, Jon; Choi, Sunkyung; Amistadi, Mary Kay
  • Environmental Science & Technology, Vol. 37, Issue 10
  • DOI: 10.1021/es025980x

Hydration of Na + , Ni 2+ , and Sm 3+ in the Interlayer of Hectorite: A Quasielastic Neutron Scattering Study
journal, July 2009

  • Sobolev, Oleg; Le Forestier, Lydie; González, Miguel A.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 31
  • DOI: 10.1021/jp903179g

Molecular Dynamics Study of CO 2 and H 2 O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite
journal, October 2017

  • Loganathan, Narasimhan; Yazaydin, A. Ozgur; Bowers, Geoffrey M.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 44
  • DOI: 10.1021/acs.jpcc.7b06825

Formation and Restacking of Disordered Smectite Osmotic Hydrates
journal, December 2015

  • Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M.
  • Clays and Clay Minerals, Vol. 63, Issue 6
  • DOI: 10.1346/CCMN.2015.0630602

Bending of Layered Silicates on the Nanometer Scale: Mechanism, Stored Energy, and Curvature Limits
journal, October 2011

  • Fu, Yao-Tsung; Zartman, Gregory D.; Yoonessi, Mitra
  • The Journal of Physical Chemistry C, Vol. 115, Issue 45
  • DOI: 10.1021/jp208383f

Alkali Metal and H 2 O Dynamics at the Smectite/Water Interface
journal, October 2011

  • Bowers, Geoffrey M.; Singer, Jared W.; Bish, David L.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 47
  • DOI: 10.1021/jp2072167

2 H and 27 Al Solid-State NMR Study of the Local Environments in Al-Doped 2-Line Ferrihydrite, Goethite, and Lepidocrocite
journal, May 2015


Montmorillonite−Poly(ethylene oxide) Nanocomposites:  Interlayer Alkali Metal Behavior
journal, September 2005

  • Reinholdt, Marc X.; Kirkpatrick, R. James; Pinnavaia, Thomas J.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 34
  • DOI: 10.1021/jp052601o

Structural and Dynamical Properties of the Water Molecules Confined in Dense Clay Sediments:  a Study Combining 2 H NMR Spectroscopy and Multiscale Numerical Modeling
journal, March 2007

  • Porion, Patrice; Michot, Laurent J.; Faugère, Anne Marie
  • The Journal of Physical Chemistry C, Vol. 111, Issue 14
  • DOI: 10.1021/jp067907p

Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state 1H and 71Ga NMR spectroscopy
journal, November 2014

  • Petersen, Line Boisen; Lipton, Andrew S.; Zorin, Vadim
  • Journal of Solid State Chemistry, Vol. 219
  • DOI: 10.1016/j.jssc.2014.07.023

Molecular Dynamics Simulation of Water Mobility in Magnesium-Smectite Hydrates
journal, November 2000

  • Greathouse, Jeffery A.; Refson, Keith; Sposito, Garrison
  • Journal of the American Chemical Society, Vol. 122, Issue 46
  • DOI: 10.1021/ja0018769

Surface geochemistry of the clay minerals
journal, March 1999

  • Sposito, G.; Skipper, N. T.; Sutton, R.
  • Proceedings of the National Academy of Sciences, Vol. 96, Issue 7
  • DOI: 10.1073/pnas.96.7.3358

Overview of scientific investigations at Yucca Mountain—the potential repository for high-level nuclear waste
journal, May 1999


Exploiting NMR spectroscopy for the study of disorder in solids
journal, February 2017

  • Moran, Robert F.; Dawson, Daniel M.; Ashbrook, Sharon E.
  • International Reviews in Physical Chemistry, Vol. 36, Issue 1
  • DOI: 10.1080/0144235X.2017.1256604

Molecular Simulation of Structure and Diffusion at Smectite–Water Interfaces: Using Expanded Clay Interlayers as Model Nanopores
journal, July 2015

  • Greathouse, Jeffery A.; Hart, David B.; Bowers, Geoffrey M.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 30
  • DOI: 10.1021/acs.jpcc.5b03314

Water Self-Diffusion within Nematic Dispersions of Nanocomposites:  A Multiscale Analysis of 1 H Pulsed Gradient Spin−Echo NMR Measurements
journal, May 2003

  • Porion, P.; Mukhtar, M. Al; Faugère, A. M.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 17
  • DOI: 10.1021/jp022161q

Single crystal structure refinement of one- and two-layer hydrates of sodium fluorohectorite
journal, January 2012

  • Kalo, Hussein; Milius, Wolfgang; Breu, Josef
  • RSC Advances, Vol. 2, Issue 22
  • DOI: 10.1039/c2ra20457f

Structure and dynamics of hydrated ions
journal, May 1993


Structure, Energetics, and Dynamics of Smectite Clay Interlayer Hydration: Molecular Dynamics and Metadynamics Investigation of Na-Hectorite
journal, March 2013

  • Morrow, Christin P.; Yazaydin, A. Özgür; Krishnan, Marimuthu
  • The Journal of Physical Chemistry C, Vol. 117, Issue 10
  • DOI: 10.1021/jp312286g

Cation Exchange at the Mineral−Water Interface: H 3 O + /K + Competition at the Surface of Nano-Muscovite
journal, September 2008

  • Bowers, Geoffrey M.; Bish, David L.; Kirkpatrick, R. James
  • Langmuir, Vol. 24, Issue 18
  • DOI: 10.1021/la8021112

Solid-state NMR and short-range order in crystalline oxides and silicates: a new tool in paramagnetic resonances
journal, February 2017

  • Stebbins, Jonathan F.; McCarty, Ryan J.; Palke, Aaron C.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 73, Issue 3
  • DOI: 10.1107/S2053229616015606

Dielectric properties of smectite clays
journal, December 1996

  • Kaviratna, P. D.; Pinnavaia, Thomas J.; Schroeder, P. A.
  • Journal of Physics and Chemistry of Solids, Vol. 57, Issue 12
  • DOI: 10.1016/S0022-3697(96)00076-5

Dripplons as localized and superfast ripples of water confined between graphene sheets
journal, April 2018


The structure and dynamics of 2-dimensional fluids in swelling clays
journal, June 2006


Water Sites at a Clay Interface
journal, January 1997


H 2 O and Cation Structure and Dynamics in Expandable Clays:  2 H and 39 K NMR Investigations of Hectorite
journal, March 2008

  • Bowers, Geoffrey M.; Bish, David L.; Kirkpatrick, R. James
  • The Journal of Physical Chemistry C, Vol. 112, Issue 16
  • DOI: 10.1021/jp7119087

Cation and Water Structure, Dynamics, and Energetics in Smectite Clays: A Molecular Dynamics Study of Ca–Hectorite
journal, June 2016

  • Loganathan, Narasimhan; Yazaydin, A. Ozgur; Bowers, Geoffrey M.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 23
  • DOI: 10.1021/acs.jpcc.6b00230

Water Dynamics in Hectorite Clays: Infuence of Temperature Studied by Coupling Neutron Spin Echo and Molecular Dynamics
journal, April 2011

  • Marry, Virginie; Dubois, Emmanuelle; Malikova, Natalie
  • Environmental Science & Technology, Vol. 45, Issue 7
  • DOI: 10.1021/es1031932

Molecular Simulation of Interlayer Structure and Dynamics in 12.4 Å Cs-Smectite Hydrates
journal, May 2001

  • Sutton, Rebecca; Sposito, Garrison
  • Journal of Colloid and Interface Science, Vol. 237, Issue 2
  • DOI: 10.1006/jcis.2000.7416