Stability of montmorillonite edge faces studied using firstprinciples calculations

Hiroshi Sakuma, Yukio Tachi, Kenji Yotsuji, Shigeru Suehara, Tatsumi Arima, Naoki Fujii, Katsuyuki Kawamura, Akira Honda

Research output: Contribution to journalArticle

Abstract

The reactivity and stability of the edge faces of swelling clay minerals can be altered by layer charge and the stacking structure; however, these effects are poorly understood due to experimental limitations. The structure and stability of the montmorillonite {110}, {010}, {100}, and {130} edge faces with a layer charge of either y = 0.50 or y = 0.33 (e-/Si4O10) were investigated using first-principles calculations based on density functional theory. Stacked- and single-layer models were tested and compared to understand the effect of stacking on the stability of montmorillonite edge faces. Most stacked layers stabilize the edge faces by creating hydrogen bonds between the layers; therefore, the surface energy of the layers in the stacked-layer model is lower than in the single-layer model. This indicates that the estimates of edge face surface energy should consider the swelling conditions. Negative surface energies were calculated for these edge faces in the presence of chemisorbed water molecules. A high layer charge of 0.50 reduced the surface energy relative to that of the low layer charge of 0.33. The isomorphic substitution of Mg for Al increased the stability of interlayer Na ion positions, which were stable in the trigonal ring next to the Mg ions. The lowest surface energies of the {010} and {130} edge faces were characterized by the presence of Mg ions on edge faces, which had a strong cation adsorption site due to the local negative charge of the edges. The coordination numbers of O atoms around cations adsorbed to these edge faces were small in comparison to interlayers without water.

Original languageEnglish
Pages (from-to)252-272
Number of pages21
JournalClays and Clay Minerals
Volume65
Issue number4
DOIs
Publication statusPublished - Aug 1 2017

Fingerprint

Bentonite
montmorillonite
Interfacial energy
surface energy
energy
Ions
Swelling
Cations
ions
cations
Water
Clay minerals
stacking
swelling
Density functional theory
clay minerals
ion
Hydrogen bonds
Substitution reactions
cation

All Science Journal Classification (ASJC) codes

  • Water Science and Technology
  • Soil Science
  • Geochemistry and Petrology
  • Earth and Planetary Sciences (miscellaneous)

Cite this

Stability of montmorillonite edge faces studied using firstprinciples calculations. / Sakuma, Hiroshi; Tachi, Yukio; Yotsuji, Kenji; Suehara, Shigeru; Arima, Tatsumi; Fujii, Naoki; Kawamura, Katsuyuki; Honda, Akira.

In: Clays and Clay Minerals, Vol. 65, No. 4, 01.08.2017, p. 252-272.

Research output: Contribution to journalArticle

Sakuma, H, Tachi, Y, Yotsuji, K, Suehara, S, Arima, T, Fujii, N, Kawamura, K & Honda, A 2017, 'Stability of montmorillonite edge faces studied using firstprinciples calculations', Clays and Clay Minerals, vol. 65, no. 4, pp. 252-272. https://doi.org/10.1346/CCMN.2017.064062
Sakuma, Hiroshi ; Tachi, Yukio ; Yotsuji, Kenji ; Suehara, Shigeru ; Arima, Tatsumi ; Fujii, Naoki ; Kawamura, Katsuyuki ; Honda, Akira. / Stability of montmorillonite edge faces studied using firstprinciples calculations. In: Clays and Clay Minerals. 2017 ; Vol. 65, No. 4. pp. 252-272.
@article{f4cb4f0fadef4900afd2a07db9efd609,
title = "Stability of montmorillonite edge faces studied using firstprinciples calculations",
abstract = "The reactivity and stability of the edge faces of swelling clay minerals can be altered by layer charge and the stacking structure; however, these effects are poorly understood due to experimental limitations. The structure and stability of the montmorillonite {110}, {010}, {100}, and {130} edge faces with a layer charge of either y = 0.50 or y = 0.33 (e-/Si4O10) were investigated using first-principles calculations based on density functional theory. Stacked- and single-layer models were tested and compared to understand the effect of stacking on the stability of montmorillonite edge faces. Most stacked layers stabilize the edge faces by creating hydrogen bonds between the layers; therefore, the surface energy of the layers in the stacked-layer model is lower than in the single-layer model. This indicates that the estimates of edge face surface energy should consider the swelling conditions. Negative surface energies were calculated for these edge faces in the presence of chemisorbed water molecules. A high layer charge of 0.50 reduced the surface energy relative to that of the low layer charge of 0.33. The isomorphic substitution of Mg for Al increased the stability of interlayer Na ion positions, which were stable in the trigonal ring next to the Mg ions. The lowest surface energies of the {010} and {130} edge faces were characterized by the presence of Mg ions on edge faces, which had a strong cation adsorption site due to the local negative charge of the edges. The coordination numbers of O atoms around cations adsorbed to these edge faces were small in comparison to interlayers without water.",
author = "Hiroshi Sakuma and Yukio Tachi and Kenji Yotsuji and Shigeru Suehara and Tatsumi Arima and Naoki Fujii and Katsuyuki Kawamura and Akira Honda",
year = "2017",
month = "8",
day = "1",
doi = "10.1346/CCMN.2017.064062",
language = "English",
volume = "65",
pages = "252--272",
journal = "Clays and Clay Minerals",
issn = "0009-8604",
publisher = "Clay Minerals Society",
number = "4",

}

TY - JOUR

T1 - Stability of montmorillonite edge faces studied using firstprinciples calculations

AU - Sakuma, Hiroshi

AU - Tachi, Yukio

AU - Yotsuji, Kenji

AU - Suehara, Shigeru

AU - Arima, Tatsumi

AU - Fujii, Naoki

AU - Kawamura, Katsuyuki

AU - Honda, Akira

PY - 2017/8/1

Y1 - 2017/8/1

N2 - The reactivity and stability of the edge faces of swelling clay minerals can be altered by layer charge and the stacking structure; however, these effects are poorly understood due to experimental limitations. The structure and stability of the montmorillonite {110}, {010}, {100}, and {130} edge faces with a layer charge of either y = 0.50 or y = 0.33 (e-/Si4O10) were investigated using first-principles calculations based on density functional theory. Stacked- and single-layer models were tested and compared to understand the effect of stacking on the stability of montmorillonite edge faces. Most stacked layers stabilize the edge faces by creating hydrogen bonds between the layers; therefore, the surface energy of the layers in the stacked-layer model is lower than in the single-layer model. This indicates that the estimates of edge face surface energy should consider the swelling conditions. Negative surface energies were calculated for these edge faces in the presence of chemisorbed water molecules. A high layer charge of 0.50 reduced the surface energy relative to that of the low layer charge of 0.33. The isomorphic substitution of Mg for Al increased the stability of interlayer Na ion positions, which were stable in the trigonal ring next to the Mg ions. The lowest surface energies of the {010} and {130} edge faces were characterized by the presence of Mg ions on edge faces, which had a strong cation adsorption site due to the local negative charge of the edges. The coordination numbers of O atoms around cations adsorbed to these edge faces were small in comparison to interlayers without water.

AB - The reactivity and stability of the edge faces of swelling clay minerals can be altered by layer charge and the stacking structure; however, these effects are poorly understood due to experimental limitations. The structure and stability of the montmorillonite {110}, {010}, {100}, and {130} edge faces with a layer charge of either y = 0.50 or y = 0.33 (e-/Si4O10) were investigated using first-principles calculations based on density functional theory. Stacked- and single-layer models were tested and compared to understand the effect of stacking on the stability of montmorillonite edge faces. Most stacked layers stabilize the edge faces by creating hydrogen bonds between the layers; therefore, the surface energy of the layers in the stacked-layer model is lower than in the single-layer model. This indicates that the estimates of edge face surface energy should consider the swelling conditions. Negative surface energies were calculated for these edge faces in the presence of chemisorbed water molecules. A high layer charge of 0.50 reduced the surface energy relative to that of the low layer charge of 0.33. The isomorphic substitution of Mg for Al increased the stability of interlayer Na ion positions, which were stable in the trigonal ring next to the Mg ions. The lowest surface energies of the {010} and {130} edge faces were characterized by the presence of Mg ions on edge faces, which had a strong cation adsorption site due to the local negative charge of the edges. The coordination numbers of O atoms around cations adsorbed to these edge faces were small in comparison to interlayers without water.

UR - http://www.scopus.com/inward/record.url?scp=85037680786&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85037680786&partnerID=8YFLogxK

U2 - 10.1346/CCMN.2017.064062

DO - 10.1346/CCMN.2017.064062

M3 - Article

AN - SCOPUS:85037680786

VL - 65

SP - 252

EP - 272

JO - Clays and Clay Minerals

JF - Clays and Clay Minerals

SN - 0009-8604

IS - 4

ER -