Solid-State 31P Nuclear Magnetic Resonance Study of Interlayer Hydroxide Surfaces of Kaolinite Probed with an Interlayer Triethylphosphine Oxide Monolayer

Shingo MacHida, Minoru Sohmiya, Yusuke Ide, Yoshiyuki Sugahara

    Research output: Contribution to journalArticle

    5 Citations (Scopus)

    Abstract

    The solid acidity of the interlayer aluminol surfaces of kaolinite was explored by solid-state 31P nuclear magnetic resonance with magic angle spinning (MAS) using triethylphosphine oxide (TEPO), which formed a monolayer with a uniform orientation between the layers of kaolinite as a probe molecule. Intercalation of TEPO between the layers of kaolinite was achieved using methoxy-modified kaolinite as an intermediate. The presence of TEPO in the reaction products was revealed by the two signals at 21 and 7 ppm, which were assignable to ethyl groups in TEPO, in the solid-state 13C nuclear magnetic resonance with cross polarization and magic angle spinning techniques (13C CP/MAS NMR). The presence of TEPO between the layers of kaolinite was demonstrated by the expansion of basal spacing from 0.86 nm, the interlayer distance of methoxy-modified kaolinite to 1.16 nm, as shown by the X-ray diffraction patterns, suggesting the formation of a TEPO monolayer between the layers of kaolinite. The formation of hydrogen bonds between the P=O groups of TEPO and the aluminol groups on the interlayer surfaces of kaolinite was also revealed by the appearance of an additional OH stretching band at 3598 cm-1 in the Fourier-transform infrared spectrum and narrow solid-state 31P MAS NMR signals observed at 55-53 ppm which were shifted from the position of the physisorbed TEPO (50 ppm). These results clearly indicate that the solid acidity of interlayer aluminol groups of methoxy-modified kaolinite was probed using an interacted TEPO monolayer.

    Original languageEnglish
    Pages (from-to)12694-12701
    Number of pages8
    JournalLangmuir
    Volume34
    Issue number43
    DOIs
    Publication statusPublished - 2018 Oct 30

    Fingerprint

    Kaolin
    kaolinite
    Kaolinite
    Oxides
    hydroxides
    interlayers
    Monolayers
    Nuclear magnetic resonance
    solid state
    nuclear magnetic resonance
    oxides
    Magic angle spinning
    metal spinning
    Acidity
    acidity
    hydroxide ion
    cross polarization
    Intercalation
    Reaction products
    intercalation

    ASJC Scopus subject areas

    • Materials Science(all)
    • Condensed Matter Physics
    • Surfaces and Interfaces
    • Spectroscopy
    • Electrochemistry

    Cite this

    Solid-State 31P Nuclear Magnetic Resonance Study of Interlayer Hydroxide Surfaces of Kaolinite Probed with an Interlayer Triethylphosphine Oxide Monolayer. / MacHida, Shingo; Sohmiya, Minoru; Ide, Yusuke; Sugahara, Yoshiyuki.

    In: Langmuir, Vol. 34, No. 43, 30.10.2018, p. 12694-12701.

    Research output: Contribution to journalArticle

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    abstract = "The solid acidity of the interlayer aluminol surfaces of kaolinite was explored by solid-state 31P nuclear magnetic resonance with magic angle spinning (MAS) using triethylphosphine oxide (TEPO), which formed a monolayer with a uniform orientation between the layers of kaolinite as a probe molecule. Intercalation of TEPO between the layers of kaolinite was achieved using methoxy-modified kaolinite as an intermediate. The presence of TEPO in the reaction products was revealed by the two signals at 21 and 7 ppm, which were assignable to ethyl groups in TEPO, in the solid-state 13C nuclear magnetic resonance with cross polarization and magic angle spinning techniques (13C CP/MAS NMR). The presence of TEPO between the layers of kaolinite was demonstrated by the expansion of basal spacing from 0.86 nm, the interlayer distance of methoxy-modified kaolinite to 1.16 nm, as shown by the X-ray diffraction patterns, suggesting the formation of a TEPO monolayer between the layers of kaolinite. The formation of hydrogen bonds between the P=O groups of TEPO and the aluminol groups on the interlayer surfaces of kaolinite was also revealed by the appearance of an additional OH stretching band at 3598 cm-1 in the Fourier-transform infrared spectrum and narrow solid-state 31P MAS NMR signals observed at 55-53 ppm which were shifted from the position of the physisorbed TEPO (50 ppm). These results clearly indicate that the solid acidity of interlayer aluminol groups of methoxy-modified kaolinite was probed using an interacted TEPO monolayer.",
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