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Interpretation of Solid state 13C and 29Si Nuclear Magnetic Resonance Spectra of Kaolinite Intercalates

Published online by Cambridge University Press:  02 April 2024

John G. Thompson
John G. Thompson*
Affiliation:
Geology Department, James Cook University of North Queensland, Townsville, Queensland 4811, Australia
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Abstract

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13C and 29Si nuclear magnetic resonance spectroscopy with magic-angle spinning bas been used to study the short-range ordering and bonding in the structures of intercalates of kaolinite with formamide, hydrazine, dimethyl sulfoxide (DMSO), and pyridine-N-oxide (PNO). The 29Si chemical shift indicated decreasing levels of bonding interaction between the silicate layer and the intercalate in the order: kaolinite: formamide (δ) = -91.9, ppm relative to tetramethylsilane), kaolinite: hydrazine (-92.0), kaolinite: DMSO (-93.1). The 29Si signal of the kaolinite:PNO intercalate (-92.1) was unexpectedly deshielded, possibly due to the aromatic nature of PNO. The degree of three-dimensional ordering of the structures was inferred from the 29Si signal width, with the kaolinite: DMSO intercalate displaying the greatest ordering and kaolinite: hydrazine the least. 13C resonances of intercalating organic molecules were shifted downfield by as much as 3 ppm in response to increased hydrogen bonding after intercalation, and in the kaolinite: DMSO intercalate the two methyl-carbon chemical environments were non-equivalent (δ = 43.7 and 42.5).

Резюме

Резюме

Спектроскопия ядерного магнетического резонанса 13C и 29Si использовалась для исследования короткодействующего упорядочения и связи в структуре прослоек каолинита с формамидом, гидразином, диметиловой сероокисью (ДМСО) и пиридино-N-окисью (ПNO). Химический сдвиг 29Si указывал на уменьшающиеся уровни взаимодействия связи между силикатными слоями и включаемым веществом в порядке: каолинит: формамид (δ = -91,9, частей на миллион по отношению к тетраметилсилану), каолинит: гидразин (-92,0), каолинит: ДМСО (-93,1). Сигнал 29Si прослойки каолинит: ПNO (-92,1) оказался неожиданно не защищенным, вероятно, в результате ароматической природы ПNO. Степень пространственного упорядочения структур была обнаружена при помощи ширины сигнала 29Si. Прослойка каолинит: ДМСО имела наибольшее упорядочение, а каолинит: гидразин—наименьшее. Резонансы 13C включаемых органических молекул перемещались вниз на величину порядка 3 частей на миллион в результате увеличивающейся водородной связи после прослаивания. В случае прослойки каолинит: ДМСО, две химические группы метил-углерод были неравновесны (δ = 43,7 и 42,5). [E.G.]

Resümee

Resümee

13C. und 29Si nuklearmagnetische Resonanzspektroskopie mit “Magic-angle Spinning” wurde verwendet, um die Nahordnung und die Bindung in den Strukturen von Wechsellagerungen von Kaolinit mit Formamid, Hydrazin, Dimethylsulfoxid (DMSO), und Pyridin-N-Oxid (PNO) zu undersuchen. Die chemische Verschiebung von 29 Si deutete auf abnehmende Niveaus der Bindungswechselwirkung zwischen der Silikatschicht und der Einlagerung hin, in der Reihenfolge: Kaolinit: Formamid (δ = -91,9, ppm in Vergleich zu Tetramethylsilan), Kaolinit: Hydrazin (-92,0), Kaolinit:DMSO (-93,1). Das 29Si-Signal der Kaolinit: PNO-Wechsellagerung (-92,1) war unerwartet wenig abgeschirmt, wahrscheinlich aufgrund der aromatischen Natur von PNO. Der Grad der dreidimensionalen Ordnung der Strukturen wurde aus der Breite des 29Si-Signals abgeleitet, wobei die Kaolinit: DMSO-Wechsellagerung den höchsten Ordnungsgrad und die Kaolinit: Hydrazin-Wechsellagerung den niedrigsten zeigte. Die 13C-Resonanzen der eingelagerten organischen Moleküle wurden bis zu 3 ppm nach geringerer magnetischer Feldstärke verschoben als Auswirkung einer zunehmenden Wasserstoffbindung nach der Einlagerung, und in der Kaolinit: DMSO-Wechsellagerung waren die zwei chemischen Methyl-Kohlenstoff-Milieus nicht gleich (S) = 43,7 und 42,5). [U.W.]

Résumé

Résumé

La spectroscopic de résonance magnétique nucléaire de 13C et de 29Si avec spin d'angle magique a été utilisée pour étudier l'ordre à court terme et les liaisons dans les structures d'intercalates de kaolinite avec la formamide, l'hydrazine, la sulphoxide diméthyle (DMSO), et l'oxide-N-pyridine (PNO). Le déplacement chimique de 29Si a indiqué des niveaux décroissants d'interaction de liaisons entre la couche silicate et l'intercalate dans l'ordre: kaolinite: formamide (δ) = -91,9, ppm relatives à la tétraméthylsilane), kaolinite: hydrazine (-92,0), kaolinite: DMSO (-93,1). Le signal 29Si de kaolinite: hydrazine (-92,1) était découvert de manière inattendue, possiblement à cause de la nature aromatique de PNO. Le degré d'ordre à trois dimensions des structures a été inféré à partir de la largeur du signal 29Si, avec l'intercalate kaolinite: DMSO montrant le plus grand ordre et la kaolinite: hydrazine, le plus petit. Les résonances 13C de molécules organiques intercalantes étaient deplacées vers le bas du champ par autant que 3 ppm en reponse à une liaison d'hydrogene augmentée après l'intercalation, et dans l'intercalate kaolinite:DMSO, les deux environements chimiques méthyl-carbone étaient non-équivalents (δ = 43,7 et 42,5). [D.J.]

Keywords

DimethylsulfoxideFormamideHydrazineIntercalateNuclear magnetic resonanceOrderingPyridine-N-oxide
Type
Research Article
Information
Clays and Clay Minerals , Volume 33 , Issue 3 , June 1985 , pp. 173 - 180
Copyright
Copyright © 1985, The Clay Minerals Society

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