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Influence of Synthesis Conditions on the Formation of a Kaolinitemethanol Complex and Simulation of its Vibrational Spectra

Published online by Cambridge University Press:  01 January 2024

Jakub Matusik ,
Eva Scholtzová ,
Daniel Tunega  and
Elsa H. Rueda
Jakub Matusik*
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, Faculty of Geology, Geophysics and Environmental Protection, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow, Poland
Eva Scholtzová
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská Cesta 9, SK-845 36 Bratislava, Slovak Republic
Daniel Tunega
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská Cesta 9, SK-845 36 Bratislava, Slovak Republic Institut für Bodenforschung, Universität für Bodenkultur, Peter-Jordan-Strasse 82b, A-1190 Vienna, Austria
Elsa H. Rueda
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, Faculty of Geology, Geophysics and Environmental Protection, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow, Poland
*
*E-mail address of corresponding author: [email protected]
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Abstract

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Kaolinite is often used as a base for the synthesis of new organo-mineral nanomaterials designed for applications in industry and in environmental protection. To make the mineral structure more likely to interact with organic molecules, a kaolinite-methanol complex (KM) can be used. In the present study, different experimental procedures were tested to investigate the formation of the KM. The kaolinitedimethyl sulfoxide intercalation compound (KDS), either wet or dried, was used as a pre-intercalate. The samples obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, CHNS elemental analysis, 13C CP-magic angle spinning nuclear magnetic resonance (MAS NMR), and 27Al and 29Si MAS NMR techniques. The method of density functional theory with dispersion corrections (DFT-D2) was used to explain the structure and to simulate the vibrational spectra of KM. Theoretical results were compared with experimental data. The most effective formation of the KM (d001 = 11.1 Å — wet; d001 = 8.7 Å — dried) was observed when the dried KDS precursor was used. In such conditions the degree of intercalation reached ~98% after 24 h of reaction time. As indicated by the CHNS elemental analysis, ~1/6 of the inner-surface OH groups were grafted by OCH3 groups. The esterification reaction was less efficient at higher temperatures or when wet KDS was used. In the latter case, the excess of very polar dimethyl sulfoxide molecules prevented intercalation of methanol and further grafting. Detailed analysis of the results of theoretical simulations revealed that the reaction of the KDS with methanol led to the formation of kaolinite with both grafted methoxy groups and intercalated methanol, and water molecules in the interlayer space. The spectra calculated revealed the contribution of individual vibrational modes into the complex bands, i.e. the energy of C-H vibrations was in the order: νasCHmet > νasCHmtx > νsCHmet > νsCHmtx.

Keywords

DFT-D2GraftingIntercalationKaoliniteMethanolVibrational Spectra
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 3 , June 2012 , pp. 227 - 239
Copyright
Copyright © Clay Minerals Society 2012

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