Hostname: page-component-848d4c4894-tn8tq Total loading time: 0 Render date: 2024-06-23T19:29:05.325Z Has data issue: false hasContentIssue false

Influence of Octahedral Cation Distribution in Montmorillonite on Interlayer Hydrogen Counter-Ion Retention Strength via First-Principles Calculations

Published online by Cambridge University Press:  01 January 2024

Yayu W. Li*
Affiliation:
Department of Plant Science and Landscape Architecture, University of Connecticut, Storrs, CT 06269-4067, USA
Cristian P. Schulthess
Affiliation:
Department of Plant Science and Landscape Architecture, University of Connecticut, Storrs, CT 06269-4067, USA
Kevin Co
Affiliation:
Department of Material Science and Engineering, University of Connecticut, Storrs, CT 06269, USA
Sanjubala Sahoo
Affiliation:
Department of Material Science and Engineering, University of Connecticut, Storrs, CT 06269, USA
S. Pamir Alpay
Affiliation:
Department of Material Science and Engineering, University of Connecticut, Storrs, CT 06269, USA Department of Physics, University of Connecticut, Storrs, CT 06269, USA
*
*E-mail address of corresponding author: yayu.li@uconn.edu

Abstract

Although multiple types of adsorption sites have long been observed in montmorillonite, a consistent explanation about the chemical structure of these adsorption sites has not yet been established. Identifying the cation interlayer adsorption sites based on the octahedral cation distribution on montmorillonite was investigated in this study by using a Density Functional Theory (DFT) simulation. A clay structural model (H[Al6MgFe]Si16O40(OH)8) with a similar composition to Wyoming SWy-1 montmorillonite was built, where two octahedral Al were respectively substituted by Fe and Mg, and H+ was the charge compensating cation. This model had twenty-one different possible configurations as a function of the distribution of octahedral Al, Fe, and Mg cations. The DFT simulations of 15 of these different configurations showed no preference for the formation of any configuration with a specific octahedral Fe-Mg distance. However, the H+ adsorption energy was separated into three distinct groups based on the number of octahedral jumps from Fe to Mg atoms. The H+ adsorption energy significantly decreased with increasing number of octahedral jumps from Fe to Mg. Assuming an even probability of occurrence of 21 octahedral structures in montmorillonite, the percentages of these three groups are 43, 43, and 14%, respectively, which are very close to the three major sites on montmorillonite from published cation adsorption data. These DFT simulations offer an entirely new explanation for the location and chemical structure of the three major adsorption sites on montmorillonite, namely, all three sites are in the interlayer, and their adsorption strengths are a function of the number of octahedral jumps from Fe to Mg atoms.

Type
Article
Copyright
Copyright © Clay Minerals Society 2020

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Agmon, N. (1999). Proton solvation and proton mobility. Israel Journal of Chemistry, 39, 493502.Google Scholar
Benson, L. V. (1982). A tabulation and evaluation of ion exchange data on smectites. Environmental Geology, 4, 2329.CrossRefGoogle Scholar
Blöchl, P. E. (1994). Projector augmented-wave method. Physical review B, 50, 1795317979.CrossRefGoogle ScholarPubMed
Bradbury, M. H., & Baeyens, B. (1997). A mechanistic description of Ni and Zn sorption on Na-montmorillonite. Part II: Modelling. Journal of Contaminant Hydrology, 27, 223248.Google Scholar
Carey, F.A., & Sundberg, R.J. (2007). Advanced organic chemistry. Part A: Structure and mechanisms. Springer Science & Business Media.Google Scholar
Chatterjee, A., Iwasaki, T., Ebina, T., & Miyamoto, A. (1999). A DFT study on clay-cation-water interaction in montmorillonite and beidellite. Computational Materials Science, 14, 119124.CrossRefGoogle Scholar
Cornell, R. (1993). Adsorption of cesium on minerals: A review. Journal of Radioanalytical and Nuclear Chemistry, 171, 483500.CrossRefGoogle Scholar
Cuadros, J., Sainz-Diaz, C. I., Ramirez, R., & Hernandez-Laguna, A. (1999). Analysis of Fe segregation in the octahedral sheet of bentonitic illite-smectite by means of FTIR, 27Al MAS NMR and reverse Monte Carlo simulations. American Journal of Science, 299, 289308.CrossRefGoogle Scholar
Drits, V. A., McCarty, D. K., & Zviagina, B. B. (2006). Crystalchemical factors responsible for the distribution of octahedral cations over trans- and cis-sites in dioctahedral 2: 1 layer silicates. Clays and Clay Minerals, 54, 131152.CrossRefGoogle Scholar
Dzene, L., Tertre, E., Hubert, F., & Ferrage, E. (2015). Nature of the sites involved in the process of cesium desorption from vermiculite. Journal of Colloid and Interface Science, 455, 254260.CrossRefGoogle ScholarPubMed
Emmerich, K., & Kahr, G. (2001). The cis-and trans-vacant variety of a montmorillonite: an attempt to create a model smectite. Applied Clay Science, 20, 119127.CrossRefGoogle Scholar
Escamilla-Roa, E., Nieto, F., & Sainz-Díaz, C. I. (2016). Stability of the hydronium cation in the structure of illite. Clays and Clay Minerals, 64, 413424.CrossRefGoogle Scholar
Ferreira, D. R., Schulthess, C. P., & Giotto, M. V. (2011). An investigation of strong sodium retention mechanisms in nanopore environments using nuclear magnetic resonance spectroscopy. Environmental Science and Technology, 46, 300306.CrossRefGoogle ScholarPubMed
Finck, N., Schlegel, M. L., & Bauer, A. (2015). Structural iron in dioctahedral and trioctahedral smectites: A polarized XAS study. Physics and Chemistry of Minerals, 42, 847859.CrossRefGoogle Scholar
Gajdoš, M., Hummer, K., Kresse, G., Furthmüller, J., & Bechstedt, F. (2006). Linear optical properties in the projector-augmented wave methodology. Physical Review B, 73, (045112), 19.CrossRefGoogle Scholar
Hernández-Laguna, A., Escamilla-Roa, E., Timón, V., Dove, M. T., & Sainz-Díaz, C. I. (2006). DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2: 1 phyllosilicates. Physics and Chemistry of Minerals, 33, 655666.CrossRefGoogle Scholar
Hernández-Haro, N., Ortega-Castro, J., Pruneda, M., Sainz-Díaz, C. I., & Hernández-Laguna, A. (2014). Theoretical study on the influence of the Mg2+ and Al3+ octahedral cations on the vibrational spectra of the hydroxy groups of dioctahedral 2: 1 phyllosilicate models. Journal of Molecular Modeling, 20, (2402), 110.CrossRefGoogle ScholarPubMed
Jacquier, P., Ly, J., & Beaucaire, C. (2004). The ion-exchange properties of the Tournemire argillite: I. Study of the H, Na, K, Cs, Ca and Mg behaviour. Applied Clay Science, 26, 163170.CrossRefGoogle Scholar
Kaufhold, S., Kremleva, A., Krüger, S., Rösch, N., Emmerich, K., & Dohrmann, R. (2017). Crystal-chemical composition of dicoctahedral smectites: An energy-based assessment of empirical relations. ACS Earth and Space Chemistry, 1, 629636.CrossRefGoogle Scholar
Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B, 54, 1116911186.CrossRefGoogle ScholarPubMed
Kresse, G., & Joubert, D. (1999). From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 59, 17581775.CrossRefGoogle Scholar
Lantenois, S., Muller, F., Bény, J. M., Mahiaoui, J., & Champallier, R. (2008). Hydrothermal synthesis of beidellites: Characterization and study of the cis-and trans-vacant character. Clays and Clay Minerals, 56, 3948.CrossRefGoogle Scholar
Lavikainen, L. P., Tanskanen, J. T., Schatz, T., Kasa, S., & Pakkanen, T. A. (2015). Montmorillonite interlayer surface chemistry: Effect of magnesium ion substitution on cation adsorption. Theoretical Chemistry Accounts, 134, (51), 17.CrossRefGoogle Scholar
Macht, F., Eusterhues, K., Pronk, G. J., & Totsche, K. U. (2011). Specific surface area of clay minerals: Comparison between atomic force microscopy measurements and bulk-gas (N2) and-liquid (EGME) adsorption methods. Applied Clay Science, 53, 2026.CrossRefGoogle Scholar
Martin, L. A., Wissocq, A., Benedetti, M. F., & Latrille, C. (2018). Thallium (Tl) sorption onto illite and smectite: Implications for Tl mobility in the environment. Geochimica et Cosmochimica Acta, 230, 116.CrossRefGoogle Scholar
McKinley, J. P., Zachara, J. M., Smith, S. C., & Turner, G. D. (1995). The influence of uranyl hydrolysis and multiple site-binding reactions on adsorption of U(VI) to montmorillonite. Clays and Clay Minerals, 43, 586598.CrossRefGoogle Scholar
Missana, T., Benedicto, A., García-Gutiérrez, M., & Alonso, U. (2014). Modeling cesium retention onto Na-, K- and Ca-smectite: Effects of ionic strength, exchange and competing cations on the determination of selectivity coefficients. Geochimica et Cosmochimica Acta, 128, 266277.CrossRefGoogle Scholar
Monkhorst, H. J., & Pack, J. D. (1976). Special points for Brillouinzone integrations. Physical Review B, 13, 51885192.CrossRefGoogle Scholar
Motellier, S., Ly, J., Gorgeon, L., Charles, Y., Hainos, D., Meier, P., & Page, J. (2003). Modelling of the ion-exchange properties and indirect determination of the interstitial water composition of an argillaceous rock. Application to the Callovo-Oxfordian low-watercontent formation. Applied Geochemistry, 18, 15171530.CrossRefGoogle Scholar
Muller, F., Besson, G., Manceau, A., & Drits, V. A. (1997). Distribution of isomorphous cations within octahedral sheets in montmorillonite from Camp-Bertaux. Physics and Chemistry of Minerals, 24, 159166.CrossRefGoogle Scholar
Muller, F., Drits, V., Plançon, A., & Robert, J. L. (2000). Structural transformation of 2: 1 dioctahedral layer silicates during dehydroxylation-rehydroxylation reactions. Clays and Clay Minerals, 48, 572585.CrossRefGoogle Scholar
Neumann, A., Petit, S., & Hofstetter, T. B. (2011). Evaluation of redoxactive iron sites in smectites using middle and near infrared spectroscopy. Geochimica et Cosmochimica Acta, 75, 23362355.CrossRefGoogle Scholar
Nolin, D. (1997). Rétention de radioéléments à vie longue par des matériaux argileux. Influence d'anions contenus dans les eaux naturelles. Ph.D. Thesis, Universite Pierre Et Marie Curie, Paris 6.Google Scholar
Norrish, K. (1954). The swelling of montmorillonite. Discussions of the Faraday Society, 18, 1 120134.CrossRefGoogle Scholar
Ohkubo, T., Okamoto, T., Kawamura, K., Guégan, R., Deguchi, K., Ohki, S., Shimizu, T., Tachi, Y., & Iwadate, Y. (2018). New insights into the Cs adsorption on montmorillonite clay from 133Cs solidstate NMR and density functional theory calculations. The Journal of Physical Chemistry A, 122, 93269337.CrossRefGoogle Scholar
Ortega-Castro, J., Hernández-Haro, N., Dove, M. T., HernándezLaguna, A., & Sainz-Díaz, C. I. (2010). Density functional theory and Monte Carlo study of octahedral cation ordering of Al/Fe/Mg cations in dioctahedral 2: 1 phyllosilicates. American Mineralogist, 95, 209220.CrossRefGoogle Scholar
Pauling, L. (1960). The Nature of the chemical bond. Ithaca, NY: Cornell University Press.Google Scholar
Perdew, J. P., Burke, K., & Ernzerhof, M. (1996). Generalized gradient approximation made simple. Physical Review Letters, 77, 38653868.CrossRefGoogle ScholarPubMed
Poinssot, C., Baeyens, B., & Bradbury, M. H. (1999). Experimental and modelling studies of caesium sorption on illite. Geochimica et Cosmochimica Acta, 63, 32173227.CrossRefGoogle Scholar
Robin, V., Tertre, E., Beaufort, D., Regnault, O., Sardini, P., & Descostes, M. (2015). Ion exchange reactions of major inorganic cations (H+, Na+, Ca2+, Mg2+ and K+) on beidellite: Experimental results and new thermodynamic database. Toward a better prediction of contaminant mobility in natural environments. Applied Geochemistry, 59, 7484.CrossRefGoogle Scholar
Robin, V., Tertre, E., Beaucaire, C., Regnault, O., & Descostes, M. (2017). Experimental data and assessment of predictive modeling for radium ion-exchange on beidellite, a swelling clay mineral with a tetrahedral charge. Applied Geochemistry, 85, 19.CrossRefGoogle Scholar
Rotenberg, B., Morel, J. P., Marry, V., Turq, P., & Morel-Desrosiers, N. (2009). On the driving force of cation exchange in clays: Insights from combined microcalorimetry experiments and molecular simulation. Geochimica et Cosmochimica Acta, 73, 40344044.CrossRefGoogle Scholar
Sainz-Diaz, C. I., Hernández-Laguna, A., & Dove, M. T. (2001). Theoretical modelling of cis-vacant and trans-vacant configurations in the octahedral sheet of illites and smectites. Physics and Chemistry of Minerals, 28, 322331.CrossRefGoogle Scholar
Sawhney, B. (1972). Selective sorption and fixation of cations by clay minerals: A review. Clays and Clay Minerals, 20, 93100.CrossRefGoogle Scholar
Schulthess, C. P., & Huang, C. P. (1990). Adsorption of heavy metals by silicon and aluminum oxide surfaces on clay minerals. Soil Science Society of America Journal, 54, 679688.CrossRefGoogle Scholar
Schulthess, C. P., Taylor, R. W., & Ferreira, D. R. (2011). The nanopore inner sphere enhancement effect on cation adsorption: Sodium and nickel. Soil Science Society of America Journal, 75, 378388.CrossRefGoogle Scholar
Siroux, B., Beaucaire, C., Tabarant, M., Benedetti, M. F., & Reiller, P. E. (2017). Adsorption of strontium and caesium onto an Na-MX80 bentonite: Experiments and building of a coherent thermodynamic modelling. Applied Geochemistry, 87, 167175.CrossRefGoogle Scholar
Shi, J., Liu, H., Lou, Z., Zhang, Y., Meng, Y., Zeng, Q., & Yang, M. (2013). Effect of interlayer counterions on the structures of dry montmorillonites with Si4+/Al3+ substitution. Computational Materials Science, 69, 9599.CrossRefGoogle Scholar
Sposito, G. (2008). The chemistry of soils. Oxford University Press.Google Scholar
Teppen, B. J., & Miller, D. M. (2006). Hydration energy determines isovalent cation exchange selectivity by clay minerals. Soil Science Society of America Journal, 70, 3140.CrossRefGoogle Scholar
Tertre, E., Beaucaire, C., Coreau, N., & Juery, A. (2009). Modelling Zn (II) sorption onto clayey sediments using a multi-site ion-exchange model. Applied Geochemistry, 24, 18521861.CrossRefGoogle Scholar
The Clay Minerals Society (2019). Physical and chemical data of source clays, http://www.clays.org/sourceclays_data.html, viewed 7 June 2019.Google Scholar
Tournassat, C., Neaman, A., Villiéras, F., Bosbach, D., & Charlet, L. (2003). Nanomorphology of montmorillonite particles: Estimation of the clay edge sorption site density by low-pressure gas adsorption and AFM observations. American Mineralogist, 88, 19891995.CrossRefGoogle Scholar
Tsipursky, S. I., & Drits, V. A. (1984). The distribution of octahedral cations in the 2: 1 layers of dioctahedral smectites studied by oblique-texture electron diffraction. Clay Minerals, 19, 177193.CrossRefGoogle Scholar
Tunega, D., Goodman, B. A., Haberhauer, G., Reichenauer, T. G., Gerzabek, M. H., & Lischka, H. (2007). Ab initio calculations of relative stabilities of different structural arrangements in dioctahedral phyllosilicates. Clays and Clay minerals, 55, 220232.CrossRefGoogle Scholar
Vantelon, D., Montarges-Pelletier, E., Michot, L. J., Pelletier, M., Thomas, F., & Briois, V. (2003). Iron distribution in the octahedral sheet of dioctahedral smectites. An Fe K-edge X-ray absorption spectroscopy study. Physics and Chemistry of Minerals, 30, 4453.CrossRefGoogle Scholar
Viani, A., Gualtieri, A. F., & Artioli, G. (2002). The nature of disorder in montmorillonite by simulation of X-ray powder patterns. American Mineralogist, 87, 966975.CrossRefGoogle Scholar
Wolters, F., Lagaly, G., Kahr, G., Nueeshch, R., & Emmerich, K. (2009). A comprehensive characterization of dioctahedral smectites. Clays and Clay Minerals, 57, 115133.CrossRefGoogle Scholar
Yariv, S. (1992). The effect of tetrahedral substitution of Si by Al on the surface acidity of the oxygen plane of clay minerals. International Reviews in Physical Chemistry, 11, 345375.CrossRefGoogle Scholar
Supplementary material: File

Li et al. supplementary material
Download undefined(File)
File 161.7 KB