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

Title: Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling

Abstract

Ion exchange in nanoporous clay-rich media plays an integral role in water, nutrient, and contaminant storage and transport. In montmorillonite (MMT), a common clay mineral in soils, sediments, and muds, the swelling and collapse of clay particles through the addition or removal of discrete molecular layers of water alters cation exchange selectivities in a poorly understood way. Here, we show that ion exchange is coupled to the dynamic delamination and restacking of clay layers, which creates a feedback between the hydration state of the exchanging cation and the composition of the clay interlayer. Particles with different hydration states are distinct phases with unique binding selectivities. Surprisingly, equilibrium achieved through thermal fluctuations in cation concentration and hydration state leads to the exchange of both ions and individual MMT layers between particles, a process we image directly with high-resolution transmission electron microscopy at cryogenic conditions (cryo-TEM). We introduce an exchange model that accounts for the binding selectivities of different phases, which is likely applicable to many charged colloidal or macromolecular systems in which the structural conformation is correlated with the activities of water and counterions within spatially confined compartments.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1575020
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 44; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Whittaker, Michael L., Lammers, Laura N., Carrero, Sergio, Gilbert, Benjamin, and Banfield, Jillian F. Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling. United States: N. p., 2019. Web. doi:10.1073/pnas.1908086116.
Whittaker, Michael L., Lammers, Laura N., Carrero, Sergio, Gilbert, Benjamin, & Banfield, Jillian F. Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling. United States. doi:10.1073/pnas.1908086116.
Whittaker, Michael L., Lammers, Laura N., Carrero, Sergio, Gilbert, Benjamin, and Banfield, Jillian F. Wed . "Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling". United States. doi:10.1073/pnas.1908086116.
@article{osti_1575020,
title = {Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling},
author = {Whittaker, Michael L. and Lammers, Laura N. and Carrero, Sergio and Gilbert, Benjamin and Banfield, Jillian F.},
abstractNote = {Ion exchange in nanoporous clay-rich media plays an integral role in water, nutrient, and contaminant storage and transport. In montmorillonite (MMT), a common clay mineral in soils, sediments, and muds, the swelling and collapse of clay particles through the addition or removal of discrete molecular layers of water alters cation exchange selectivities in a poorly understood way. Here, we show that ion exchange is coupled to the dynamic delamination and restacking of clay layers, which creates a feedback between the hydration state of the exchanging cation and the composition of the clay interlayer. Particles with different hydration states are distinct phases with unique binding selectivities. Surprisingly, equilibrium achieved through thermal fluctuations in cation concentration and hydration state leads to the exchange of both ions and individual MMT layers between particles, a process we image directly with high-resolution transmission electron microscopy at cryogenic conditions (cryo-TEM). We introduce an exchange model that accounts for the binding selectivities of different phases, which is likely applicable to many charged colloidal or macromolecular systems in which the structural conformation is correlated with the activities of water and counterions within spatially confined compartments.},
doi = {10.1073/pnas.1908086116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 44,
volume = 116,
place = {United States},
year = {2019},
month = {10}
}

Works referenced in this record:

Natural, incidental, and engineered nanomaterials and their impacts on the Earth system
journal, March 2019


Clay, Water, and Salt: Controls on the Permeability of Fine-Grained Sedimentary Rocks
journal, August 2017


Short- and Long-Range Attractive Forces That Influence the Structure of Montmorillonite Osmotic Hydrates
journal, November 2016


DND-CAT's new triple area detector system for simultaneous data collection at multiple length scales
journal, September 2011

  • Weigand, Steven J.; Keane, Denis T.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 649, Issue 1
  • DOI: 10.1016/j.nima.2010.12.045

A Thermodynamic Understanding of Clay-Swelling Inhibition by Potassium Ions
journal, September 2006

  • Liu, Xian-Dong; Lu, Xian-Cai
  • Angewandte Chemie International Edition, Vol. 45, Issue 38
  • DOI: 10.1002/anie.200601740

Monte Carlo and Molecular Dynamics Simulations of Electrical Double-Layer Structure in Potassium−Montmorillonite Hydrates
journal, March 1998

  • Chang, Fang-Ru Chou; Skipper, N. T.; Sposito, Garrison
  • Langmuir, Vol. 14, Issue 5
  • DOI: 10.1021/la9704720

K+–Na+ exchange in phlogopite on the scale of a single layer
journal, April 2010

  • Sánchez-Pastor, Nuria; Aldushin, Kirill; Jordan, Guntram
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 7
  • DOI: 10.1016/j.gca.2009.12.026

Connecting the Molecular Scale to the Continuum Scale for Diffusion Processes in Smectite-Rich Porous Media
journal, March 2010

  • Bourg, Ian C.; Sposito, Garrison
  • Environmental Science & Technology, Vol. 44, Issue 6
  • DOI: 10.1021/es903645a

Temperature effects on the diffusion of water and monovalent counterions in the hydrated montmorillonite
journal, December 2013


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

Revealing Transition States during the Hydration of Clay Minerals
journal, June 2019

  • Ho, Tuan A.; Criscenti, Louise J.; Greathouse, Jeffery A.
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 13
  • DOI: 10.1021/acs.jpclett.9b01565

Alkali Cation Selectivity and Fixation by Clay Minerals
journal, January 1980


X-ray-diffraction studies of hydration transitions in Na vermiculite
journal, June 1990


Hydration transitions in a nanolayered synthetic silicate:  A synchrotron x-ray scattering study
journal, March 2003


Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite. 1. The sodium-exchanged form
journal, November 1992


Hysteresis in the crystalline swelling of montmorillonite
journal, December 1966


Swelling Properties of Montmorillonite and Beidellite Clay Minerals from Molecular Simulation: Comparison of Temperature, Interlayer Cation, and Charge Location Effects
journal, August 2015

  • Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jové-Colón, Carlos F.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 36
  • DOI: 10.1021/acs.jpcc.5b03253

Molecular Dynamics Simulations of Water and Sodium Diffusion in Smectite Interlayer Nanopores as a Function of Pore Size and Temperature
journal, December 2013

  • Holmboe, Michael; Bourg, Ian C.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 2
  • DOI: 10.1021/jp408884g

Free energy, energy, and entropy of swelling in Cs–, Na–, and Sr–montmorillonite clays
journal, March 2004

  • Whitley, Heather D.; Smith, David E.
  • The Journal of Chemical Physics, Vol. 120, Issue 11
  • DOI: 10.1063/1.1648013

Hysteresis in Clay Swelling Induced by Hydrogen Bonding:  Accurate Prediction of Swelling States
journal, January 2006

  • Tambach, Tim J.; Bolhuis, Peter G.; Hensen, Emiel J. M.
  • Langmuir, Vol. 22, Issue 3
  • DOI: 10.1021/la051367q

Interaction energy and surface reconstruction between sheets of layered silicates
journal, June 2006

  • Heinz, Hendrik; Vaia, R. A.; Farmer, B. L.
  • The Journal of Chemical Physics, Vol. 124, Issue 22
  • DOI: 10.1063/1.2202330

Thermodynamics of Swelling Clay-Water Systems
journal, January 1972


On the driving force of cation exchange in clays: Insights from combined microcalorimetry experiments and molecular simulation
journal, July 2009

  • Rotenberg, Benjamin; Morel, Jean-Pierre; Marry, Virginie
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 14
  • DOI: 10.1016/j.gca.2009.04.012

Hydration Energy Determines Isovalent Cation Exchange Selectivity by Clay Minerals
journal, January 2006

  • Teppen, Brian J.; Miller, David M.
  • Soil Science Society of America Journal, Vol. 70, Issue 1
  • DOI: 10.2136/sssaj2004.0212

Direct Exchange Mechanism for Interlayer Ions in Non-Swelling Clays
journal, December 2016

  • Ruiz Pestana, Luis; Kolluri, Kedarnath; Head-Gordon, Teresa
  • Environmental Science & Technology, Vol. 51, Issue 1
  • DOI: 10.1021/acs.est.6b04747

Measurement of Swelling of Individual Smectite Tactoids In Situ Using Atomic Force Microscopy
journal, April 2017

  • Arndt, DianaS.; Mattei, Michael; Heist, ChristopherA.
  • Clays and Clay Minerals, Vol. 65, Issue 2
  • DOI: 10.1346/CCMN.2017.064053

Molecular Dynamics Simulations of Anion Exclusion in Clay Interlayer Nanopores
journal, August 2016

  • Tournassat, Christophe; Bourg, IanC.; Holmboe, Michael
  • Clays and Clay Minerals, Vol. 64, Issue 4
  • DOI: 10.1346/CCMN.2016.0640403

Non-Arrhenian Ionic dc Conductivity of Homoionic Alkali Exchanged Montmorillonites with Low Water Loadings
journal, May 2010

  • Balme, S.; Kharroubi, M.; Haouzi, A.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 20
  • DOI: 10.1021/jp101979t

A structural coarse-grained model for clays using simple iterative Boltzmann inversion
journal, June 2018

  • Schaettle, Karl; Ruiz Pestana, Luis; Head-Gordon, Teresa
  • The Journal of Chemical Physics, Vol. 148, Issue 22
  • DOI: 10.1063/1.5011817

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

Ionic transport in polymer electrolytes based on renewing environments
journal, March 1994

  • Druger, Stephen D.
  • The Journal of Chemical Physics, Vol. 100, Issue 5
  • DOI: 10.1063/1.466331

Flexibility of nanolayers and stacks: implications in the nanostructuration of clays
journal, January 2018

  • Honorio, Tulio; Brochard, Laurent; Vandamme, Matthieu
  • Soft Matter, Vol. 14, Issue 36
  • DOI: 10.1039/C8SM01359D