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Effects of Mg, Ca, and Fe(II) Doping on the Kaolinite (001) Surface with H2O Adsorption

Published online by Cambridge University Press:  01 January 2024

Man-Chao He  and
Jian Zhao
Man-Chao He
Affiliation:
State Key Laboratory for Geomechanics and Deep Underground Engineering, China University of Mining and Technology, Beijing 100083, China
Jian Zhao*
Affiliation:
State Key Laboratory for Geomechanics and Deep Underground Engineering, China University of Mining and Technology, Beijing 100083, China
*
*E-mail address of corresponding author: [email protected]
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Abstract

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Kaolinite is often a cause of deformation in soft-rock tunnel engineering, leading to safety problems. The mechanism of the deformation is closely related to the interaction between kaolinite and water molecules. Because kaolinite has multiple defects, the effects of Mg, Ca, and Fe(II) doping on the atomic structure of the kaolinite (001) surface, and the subsequent adsorption and penetration of H2O into the interlayer, were studied systematically using density-functional theory. The results showed that for the Mg-, Ca-, and Fe(II)-doped kaolinites (001), the surface relaxation around the doping layer changed from contraction to expansion, due to the redistribution of electrons. The adsorption energies of the H2O monomer on Mg-, Ca-, and Fe(II)-doped kaolinites (001) were less than on undoped kaolinite (001). The results further revealed that the H2O molecule can also adsorb on the hollow site on the second-layer O surface of the Mg-, Ca-, and Fe(II)-doped kaolinites (001). For the undoped kaolinite, however, the H2O molecule adsorbs on the surface only. The energetic barriers for penetration of H2O from the adsorption site on the surface to the adsorption site on the O surface of Mg-, Ca-, and Fe(II)-doped kaolinites were also calculated: 1.18 eV, 1.07 eV, and 1.41 eV, respectively. The results imply that the influences of Mg, Ca, and Fe(II) doping on kaolinite allow the adsorbed water molecules to penetrate from the on-surface adsorption site to the O-surface site.

Keywords

AdsorptionFirst-principles CalculationsKaolinitePenetrationPoint Defect
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 3 , June 2012 , pp. 330 - 337
Copyright
Copyright © Clay Minerals Society 2012

References

Adams, J.M., 1983 Hydrogen ion position in kaolinite by neutron profile refinement Clays and Clay Minerals 31 352–358.CrossRefGoogle Scholar
Benco, L. Tunega, D. Hafner, J. and Lischka, H., 2001 Orientation of OH groups in kaolinite and dickite: ab initio molecular dynamics study American Mineralogist 86 1057–1065.CrossRefGoogle Scholar
Bish, D.L., 1993 Rietveld refinement of the kaolinite structure at 1.5 K Clays and Clay Minerals 41 738–744.CrossRefGoogle Scholar
Blöchl, P.E., 1994 Projector augmented-wave method Physical Review B 50 17953–17979.CrossRefGoogle ScholarPubMed
Chen, J. and Wang, H.N. (2004) Pp. 35–60 in: Geochemistry (Xie, H.Y. and Liu, P., editors). Science Press, Beijing.Google Scholar
Croteau, T. Bertram, A.K. and Patey, G.N., 2009 Simulation of water adsorption on kaolinite under atmospheric conditions The Journal of Physical Chemistry A 113 7826–7833.CrossRefGoogle ScholarPubMed
Frost, R.L. Horváth, E. Makó, E. and Kristóf, J., 2004 Modification of low- and high-defect kaolinite surfaces: implications for kaolinite mineral processing Journal of Colloid and Interface Science 270 337–346.CrossRefGoogle ScholarPubMed
Gupta, V. and Miller, J.D., 2010 Surface force measurements at the basal planes of ordered kaolinite particles Journal of Colloid and Interface Science 344 362–371.CrossRefGoogle ScholarPubMed
Hayashi, S., 1997 NMR study of dynamics and evolution of guest molecules in kaolinite/dimethyl sulfoxide intercalation compound Clays and Clay Minerals 45 724–732.CrossRefGoogle Scholar
He, M.C. Jing, H.H. and Yao, A.J., 2000 Research progress of soft rock engineering geomechanics in China coal mine Journal of Engineering Geology 1 46–62.Google Scholar
He, M.C. Fang, Z.J. and Zhang, P., 2009 Theoretical studies on the defects of kaolinite in clays Chinese Physics Letters 26 059101–059104.Google Scholar
Hess, A.C. and Saunders, V.R., 1992 Periodic ab initio Hartree-Fock calculation of the low-symmetry mineral kaolinite The Journal of Physical Chemistry 11 4367–4374.CrossRefGoogle Scholar
Hobbs, J.D. Cygan, R.T. Nagy, K.L. Schultz, P.A. and Sears, M.P., 1997 All-atom ab initio energy minimization of the kaolinite crystal structure American Mineralogist 82 657–662.CrossRefGoogle Scholar
Hu, X.L. and Angelos, M., 2008 Water on the hydroxylated (001) surface of kaolinite: from monomer adsorption to a flat 2D wetting layer Surface Science 602 960–974.CrossRefGoogle Scholar
Jiang, M.Q. Jin, X.Y. Lu, X.Q. and Chen, Z.L., 2010 Adsorption of Pb(II), Cd(II), Ni(II), and Cu(II) onto natural kaolinite clay Desalination 252 33–39.CrossRefGoogle Scholar
Kresse, G. and Furthmuller, J., 1996 Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Physical Review B 54 11,169–11,173.CrossRefGoogle ScholarPubMed
Kresse, G. and Joubert, J., 1999 From ultrasoft pseudopotentials to the projector augmented-wave method Physical Review B 59 1758–1762.CrossRefGoogle Scholar
Masel, R.L., 1996 Principles of Adsorption and Reaction on Solid Surfaces New York Wiley 22–24.Google Scholar
Michaelides, A. Ranea, V.A. de Andres, P.L. and King, D.A., 2004 First-principles study of H2O diffusion on a metal surface: H2O on Al{100} Physical Review B 69 075409–075413.CrossRefGoogle Scholar
Monkhorst, H.J. and Pack, J.D., 1976 Special points for Brillouin-zone integrations Physical Review B 13 5188–5192.CrossRefGoogle Scholar
Park, S.H. Sposito, G., Dutta, P.K. Auerbach, S.M. and Carrado, K.A., 2004 Molecular modeling of clay mineral structure and surface chemistry Handbook of Layered Materials Boca Raton, Florida, USA CRC Press 39–90.Google Scholar
Plançon, A. Giese, R.F. Jr. Snyder, R. Drits, V.A. and Bookin, A.S., 1997 Stacking faults in the kaolinite-group minerals: defect structures of kaolinite Clays and Clay Minerals 37 195–198.Google Scholar
Roehl, J.L. Kolagatla, A. Ganguri, V.K.K. Khare, S.V. and Phaneuf, R.J., 2010 Binding sites and diffusion barriers of a Ga adatom on the GaAs(001)-c(464) surface from firstprinciples computations Physical Review B 82 165335–165340.CrossRefGoogle Scholar
Roland, S. Martin, H.G. Hans, L. and Daniel, T., 2011 Wettability of kaolinite (001) surfaces - molecular dynamic study Geoderma 169 47–54.Google Scholar
Sato, H. Ono, K. Johnston, C.T. and Yamagishi, A., 2005 First-principles studies on the elastic constants of a 1:1 layered kaolinite mineral American Mineralogist 90 1824–1826.CrossRefGoogle Scholar
Teppen, B.J. Rasmussen, K. Bertsch, P.M. Miller, D.M. and Schäferll, L., 1997 Molecular dynamic modeling of clay minerals. 1. Gibbsite, kaolinite, pyrophyllite, and beidellite The Journal of Physical Chemistry B 101 1579–1587.CrossRefGoogle Scholar
Yang, J.Y. Meng, S. Xu, L.F. and Wang, E.G., 2004 Ice tessellation on a hydroxylated silica surface Physical Review Letters 92 146,102–146,105.CrossRefGoogle ScholarPubMed
Yin, X. and Miller, J.D., 2012 Wettability of kaolinite basal planes based on surface force measurements using atomic force microscopy Minerals & Metallurgical Processing (Special Industrial Minerals Issue) 29 13–19.Google Scholar
Yoshihiko, K. Yoshiyuki, S. and Kazuyuki, K., 1999 Intercalation of alkylamines and water into kaolinite with methanol kaolinite as an intermediate Applied Clay Science 15 241–252.Google Scholar
Wei, S.H. and Zhang, S.B., 2002 Chemical trends of defect formation and doping limit in II-VI semiconductors: The case of CdTe Physical Review B 66 155211–155221.CrossRefGoogle Scholar