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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). Finally, 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.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1570769
Alternate Identifier(s):
OSTI ID: 1581755
Grant/Contract Number:  
AC01-05CH11231; AC02-06CH11357; AC02-05CH11231; 0960140
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 44; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; montmorillonite; ion exchange; dynamic equilibrium; cryo-TEM

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.
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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.
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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.
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@article{osti_1570769,
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). Finally, 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},
number = 44,
volume = 116,
place = {United States},
year = {2019},
month = {10}
}
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DOI: 10.1073/pnas.1908086116
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