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Coordination of aluminum in saponite-like material as a function of synthesis pH

Published online by Cambridge University Press:  28 February 2025

Liva Dzene Open the ORCID record for Liva Dzene [Opens in a new window] ,
Patrick Dutournié ,
Séverinne Rigolet ,
Loïc Vidal ,
Benedikt Lassalle-Kaiser Open the ORCID record for Benedikt Lassalle-Kaiser [Opens in a new window] ,
Delphine Vantelon  and
Erwan Paineau
Liva Dzene*
Affiliation:
Institut de Science des Matériaux de Mulhouse, CNRS UMR 7361, Université de Haute-Alsace, Université de Strasbourg, 68093 Mulhouse, France
Patrick Dutournié
Affiliation:
Institut de Science des Matériaux de Mulhouse, CNRS UMR 7361, Université de Haute-Alsace, Université de Strasbourg, 68093 Mulhouse, France
Séverinne Rigolet
Affiliation:
Institut de Science des Matériaux de Mulhouse, CNRS UMR 7361, Université de Haute-Alsace, Université de Strasbourg, 68093 Mulhouse, France
Loïc Vidal
Affiliation:
Institut de Science des Matériaux de Mulhouse, CNRS UMR 7361, Université de Haute-Alsace, Université de Strasbourg, 68093 Mulhouse, France
Benedikt Lassalle-Kaiser
Affiliation:
Synchrotron SOLEIL, l’Orme des Merisiers, Départementale 128, 91190 Saint Aubin, France
Delphine Vantelon
Affiliation:
Synchrotron SOLEIL, l’Orme des Merisiers, Départementale 128, 91190 Saint Aubin, France
Erwan Paineau
Affiliation:
Université Paris-Saclay, CNRS, Laboratoire de Physique des Solides, Orsay 91405, France
*
Corresponding author: Liva Dzene; Email: [email protected]
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Abstract

Saponite-like materials have a wide range of potential applications, especially in heterogeneous catalysis. Despite the simplicity of the synthesis, the mechanisms of the formation of saponite are not well understood yet. The aim of the present study was to investigate a possible correlation between the coordination of Al in the solid phase and in the solution. For this, samples were prepared by varying the initial OH:Si molar ratio from 0.18 to 2.14, leading to a pH in the supernatant after the hydrothermal treatment of 6.7 to 12.7, respectively. The characterization of the material was performed by combining nuclear magnetic resonance (NMR) and X-ray absorption near edge structure (XANES) spectroscopies, and good agreement was obtained between the two techniques. Between pH7 and pH10, 60–65% of aluminum was found to be in tetrahedral coordination, while this percentage increased above pH10 (up to 81%). These results correlated with the speciation of the aluminum in aqueous solution. Indeed, above pH10, all available aluminum was in the soluble form Al(OH)4–.

Keywords

aluminum coordinationclay mineral synthesisOH:Si molar ratiosaponite
Type
Original Paper
Information
Clays and Clay Minerals , Volume 73 , 2025 , e8
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Copyright
© The Author(s), 2025. Published by Cambridge University Press on behalf of The Clay Minerals Society

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References

Andrini, L., Moreira Toja, R., Gauna, M.R., Conconi, M.S., Requejo, F.G., & Rendtorff, N.M. (2017). Extended and local structural characterization of a natural and 800°C fired Na-montmorillonite–Patagonian bentonite by XRD and Al/Si XANES. Applied Clay Science, 137, 233–240.CrossRefGoogle Scholar
Baldermann, A., Dohrmann, R., Kaufhold, S., Nickel, C., Letofsky-Papst, I., & Dietzel, M. (2014). The Fe-Mg-saponite solid solution series – a hydrothermal synthesis study. Clay Minerals, 49, 391–415.CrossRefGoogle Scholar
Ball, J.W., & Nordstrom, D.K. (2001). User’s Manual for Wateq4F, with revised thermodynamic data base and test cases for calculating speciation of major, trace, and redox elements in natural waters, pp. 91–183Google Scholar
Besselink, R., Stawski, T.M., Freeman, H.M., Hövelmann, J., Tobler, D.J., & Benning, L.G. (2020). Mechanism of saponite crystallization from a rapidly formed amorphous intermediate. Crystal Growth and Design, 20, 3365–3373.CrossRefGoogle Scholar
Bisio, C., Gatti, G., Boccaleri, E., Marchese, L., Bertinetti, L., & Coluccia, S. (2008). On the acidity of saponite materials: a combined HRTEM, FTIR, and solid-state NMR study. Langmuir, 24, 2808–2819.CrossRefGoogle ScholarPubMed
Blukis, R., Schindler, M., Couasnon, T., & Benning, L.G. (2022). Mechanism and control of saponite synthesis from a self-assembling nanocrystalline precursor. Langmuir, 38, 7678–7688.CrossRefGoogle ScholarPubMed
Brindley, G.W., & Brown, G. (1982). Crystal Structures of Clay Minerals and their X-ray Identification, 495 pp. Brookfield Publishing.Google Scholar
Busca, G., & Gervasini, A. (2020). Solid acids, surface acidity and heterogeneous acid catalysis. In Advances in Catalysis, 67, 1–90.CrossRefGoogle Scholar
Carniato, F., Gatti, G., & Bisio, C. (2020). An overview of the recent synthesis and functionalization methods of saponite clay. New Journal of Chemistry, 44, 9969–9980.CrossRefGoogle Scholar
Cornélis, A., & Laszlo, P. (2004). Montmorillonite K10. Major Reference Works. Encyclopedia of Reagents for Organic Synthesis. Wiley, New York.CrossRefGoogle Scholar
Criouet, I., Viennet, J.C., Baron, F., Balan, E., Buch, A., Delbes, L., Guillaumet, M., Remusat, L., & Bernard, S. (2023). Influence of pH on the hydrothermal synthesis of Al-substituted smectites (saponite, beidellite, and nontronite). Clays and Clay Minerals, 71, 539–558.CrossRefGoogle Scholar
de Kimpe, C., Gastuche, M.C., & Brindley, G.. (1961). Ionic coordination in alumino-silicic gels in relation to clay mineral formation. American Mineralogist, 46, 1370–1381.Google Scholar
Dien, L., Mingsheng, P., & Murata, T. (1999). Coordination and local structure of magnesium in silicate minerals and glasses; Mg K-edge XANES study. The Canadian Mineralogist, 37, 199–206.Google Scholar
Dzene, L., Doggaz, A., Dutournié, P., Inoué, S., Abdelmoula, M., Jourdain, A., Le Meins, J.-M., Brendlé, J., Martin, C., & Michau, N. (2024). Formation of iron-rich phyllosilicates in the FeO–SiO2–H2O system during hydrothermal synthesis as a function of pH. Clay Minerals, 59, 73–84.CrossRefGoogle Scholar
Editorial (2020). Zeolite catalysts come into focus. Nature Materials, 19, 1037–1037.CrossRefGoogle Scholar
Földvári, M. (2011). Handbook of Thermogravimetric System of Minerals and its Use in Geological Practice, 180 pp. Geological Institute of Hungary, Budapest.Google Scholar
Frank-Kamenetzkij, V.A., Kotov, N.V., & Tomashenko, A.N. (1973). The role of AlIV and AlVI in transformation and synthesis of layer silicates. Kristall und Technik, 8, 425–435.CrossRefGoogle Scholar
Gebretsadik, F.B., Mance, D., Baldus, M., Salagre, P., & Cesteros, Y. (2015). Microwave synthesis of delaminated acid saponites using quaternary ammonium salt or polymer as template. Study of pH influence. Applied Clay Science, 114, 20–30.CrossRefGoogle Scholar
Gilson, J.-P., Edwards, G.C., Peters, A.W., Rajagopalan, K., Wormsbecher, R.F., Roberie, T.G., & Shatlock, M.P. (1987). Penta-co-ordinated aluminium in zeolites and aluminosilicates. Journal of the Chemical Society, Chemical Communications, 91–92.CrossRefGoogle Scholar
Gómez-Sanz, F., Morales-Vargas, M.V., González-Rodríguez, B., Rojas-Cervantes, M.L., & Pérez-Mayoral, E. (2017). Acid clay minerals as eco-friendly and cheap catalysts for the synthesis of β-amino ketones by Mannich reaction. Applied Clay Science, 143, 250–257.CrossRefGoogle Scholar
Ildefonse, P., Calas, G., Flank, A.M., & Lagarde, P. (1995). Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 97, 172–175.CrossRefGoogle Scholar
Ildefonse, P., Cabaret, D., Sainctavit, P., Calas, G., Flank, A.-M., & Lagarde, P. (1998). Aluminium X-ray absorption near edge structure in model compounds and Earth’s surface minerals. Physics and Chemistry of Minerals, 25, 112–121.CrossRefGoogle Scholar
Inoue, K., Nishiki, Y., Fukushi, K., Suma, R., Sato, T., Sakuma, H., Tamura, K., Yokoyama, S., Shimbashi, M., Mizukami, T., Unami, K., Noji, Y., Kitajima, T., Fukaya, S., Takeichi, Y., Yamashita, S., Suga, H., & Takahashi, Y. (2023). Systematic comparison of Mg K-edge XANES spectra of magnesium-bearing clay minerals and magnesium silicate hydrates: a promising tool for identifying magnesium silicate hydrate in natural samples. Applied Clay Science, 245, 107152.CrossRefGoogle Scholar
Jaber, M., Komarneni, S., & Zhou, C.-H. (2013). Synthesis of clay minerals. In Handbook of Clay Science Fundamentals (ed. Bergaya, F. and Lagaly, G.), pp. 223–241.CrossRefGoogle Scholar
Kloprogge, J.T. (1999). Synthesis of smectite clay minerals: a critical review. Clays and Clay Minerals, 47, 529–554.CrossRefGoogle Scholar
Li, D., Bancroft, G.M., Fleet, M.E., & Feng, X.H. (1995). Silicon K-edge XANES spectra of silicate minerals. Physics and Chemistry of Minerals, 22, 115–122.CrossRefGoogle Scholar
Massiot, D., Fayon, F., Capron, M., King, I., Le Calvé, S., Alonso, B., Durand, J.-O., Bujoli, B., Gan, Z., & Hoatson, G. (2002). Modelling one- and two-dimensional solid-state NMR spectra. Magnetic Resonance in Chemistry, 40, 70–76.CrossRefGoogle Scholar
N’Guessan, N.E., Joussein, E., Courtin-Nomade, A., Paineau, E., Soubrand, M., Grauby, O., Robin, V., Cristina, C.D., Vantelon, D., Launois, P., Fondanèche, P., Rossignol, S., Texier-Mandoki, N., & Bourbon, X. (2021). Role of cations on the dissolution mechanism of kaolinite in high alkaline media. Applied Clay Science, 205, 106037.CrossRefGoogle Scholar
Okada, K., Arimitsu, N., Kameshima, Y., Nakajima, A., & MacKenzie, K.J.D. (2006). Solid acidity of 2:1 type clay minerals activated by selective leaching. Applied Clay Science, 31, 185–193.CrossRefGoogle Scholar
Ponce, C.P., & Kloprogge, J.T. (2020). Urea-assisted synthesis and characterization of saponite with different octahedral (Mg, Zn, Ni, Co) and tetrahedral metals (Al, Ga, B), a review. Life, 10, 1–32.CrossRefGoogle Scholar
Ravel, B., & Newville, M. (2005). ATHENA and ARTEMIS Interactive Graphical Data Analysis using IFEFFIT. Physica Scripta, T115, 1007.CrossRefGoogle Scholar
Theng, B.K.G. (2018). Clay Mineral Catalysis of Organic Reactions, 426 pp. CRC Press.CrossRefGoogle Scholar
Tkachenko, O.P., Kustov, L.M., Kapustin, G.I., Mishin, I.V., & Kuperman, A. (2017). Synthesis and acid-base properties of Mg-saponite. Mendeleev Communications, 27, 407–409.CrossRefGoogle Scholar
Vantelon, D., Trcera, N., Roy, D., Moreno, T., Mailly, D., Guilet, S., Metchalkov, E., Delmotte, F., Lassalle, B., Lagarde, P., & Flank, A.M. (2016). The LUCIA beamline at SOLEIL. Journal of Synchrotron Radiation, 23, 635–640.CrossRefGoogle ScholarPubMed
Wang, Z., Jiang, Y., Lafon, O., Trébosc, J., Duk Kim, K., Stampfl, C., Baiker, A., Amoureux, J.-P., & Huang, J. (2016). Brønsted acid sites based on penta-coordinated aluminum species. Nature Communications, 7, 13820.CrossRefGoogle ScholarPubMed
Zhang, C., Petit, S., He, H., Villiéras, F., Razafitianamaharavo, A., Baron, F., Tao, Q., & Zhu, J. (2020). Crystal growth of smectite: a study based on the change in crystal chemistry and morphology of saponites with synthesis time. ACS Earth and Space Chemistry, 4, 14–23.CrossRefGoogle Scholar
Zhang, D., Zhou, C.-H., Lin, C.-X., Tong, D.-S., & Yu, W.-H. (2010). Synthesis of clay minerals. Applied Clay Science, 50, 1–11.CrossRefGoogle Scholar
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