Interlayer Surface Modification of the Protonated Triple-Layered Perovskite HCa2Nb3O10·xH2O with n-Alcohols

Seiichi Tahara, Yoshiyuki Sugahara

    Research output: Contribution to journalArticle

    38 Citations (Scopus)

    Abstract

    Organic derivatives of the protonated triple-layered perovskite HCa 2Nb3O10·xH2O with n-alkoxyl groups on the interlayer surface have been prepared by grafting n-alcohols. Interlayer surface modification of HCa2Nb3O 10·xH2O is achieved by a direct reaction of HCa2Nb3O10·xH2O with methanol or ethanol, and single-phase n-alkoxyl derivatives of HCa 2Nb3O10·xH2O (n ≥ 3 in n-CnH2n+1O- groups) can be formed by reacting n-alkoxyl derivatives (methoxyl and n-propoxyl derivatives) with n- alcohols in an autoclave at 150 °C. X-ray diffraction analysis shows the changes in interlayer distances upon treatment of HCa2- Nb3O 10·xH2O or intermediate n- alkoxyl derivatives with n-alcohols. Solid-state 13C CP/MAS (cross polarization and magic-angle spinning) NMR spectroscopy demonstrates the presence of signals due to n-alkoxyl groups originating from the reactant n-alcohol molecules. Differential thermal analysis curves of the products exhibit exothermic peaks at temperatures higher than 200 °C. These results indicate successful preparation of HCa2Nb3O10 derivatives possessing various n-alkoxyl groups (n-CnH2n+1O-, n = 1-4, 6, 8, 10, 12, 14, 16, and 18) on the interlayer surface. Although a reaction between an n-propoxyl derivative and n-decanol does not proceed at 80 °C, a single-phase n- decoxyl derivative can be obtained at 80 °C by adding a small amount of water (1 mass %), which strongly suggests a hydrolysis-esterification mechanism, IR and solid-state 13C CP/MAS NMR spectroscopies indicate that the n-alkyl chains in n-alkoxyl derivatives (n ≥ 10 in n-CnH2+1O- groups) possess an all-trans conformation. A linear relationship with a slope of 0.166 nm/carbon atom is observed between the interlayer distance and the number of carbon atoms in the n-alkyl chains, suggesting that the n-alkyl chains of n-alkoxyl groups are present as bilayers with a tilt angle of 41° in the interlayer space.

    Original languageEnglish
    Pages (from-to)9473-9478
    Number of pages6
    JournalLangmuir
    Volume19
    Issue number22
    DOIs
    Publication statusPublished - 2003 Oct 28

    Fingerprint

    Perovskite
    Surface treatment
    interlayers
    alcohols
    Alcohols
    Derivatives
    cross polarization
    metal spinning
    Magic angle spinning
    solid state
    nuclear magnetic resonance
    Nuclear magnetic resonance spectroscopy
    autoclaves
    carbon
    Carbon
    Polarization
    spectroscopy
    atoms
    hydrolysis
    perovskite

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Colloid and Surface Chemistry

    Cite this

    Interlayer Surface Modification of the Protonated Triple-Layered Perovskite HCa2Nb3O10·xH2O with n-Alcohols. / Tahara, Seiichi; Sugahara, Yoshiyuki.

    In: Langmuir, Vol. 19, No. 22, 28.10.2003, p. 9473-9478.

    Research output: Contribution to journalArticle

    @article{2082c203d5194b9ebf9aa957eac9f82f,
    title = "Interlayer Surface Modification of the Protonated Triple-Layered Perovskite HCa2Nb3O10·xH2O with n-Alcohols",
    abstract = "Organic derivatives of the protonated triple-layered perovskite HCa 2Nb3O10·xH2O with n-alkoxyl groups on the interlayer surface have been prepared by grafting n-alcohols. Interlayer surface modification of HCa2Nb3O 10·xH2O is achieved by a direct reaction of HCa2Nb3O10·xH2O with methanol or ethanol, and single-phase n-alkoxyl derivatives of HCa 2Nb3O10·xH2O (n ≥ 3 in n-CnH2n+1O- groups) can be formed by reacting n-alkoxyl derivatives (methoxyl and n-propoxyl derivatives) with n- alcohols in an autoclave at 150 °C. X-ray diffraction analysis shows the changes in interlayer distances upon treatment of HCa2- Nb3O 10·xH2O or intermediate n- alkoxyl derivatives with n-alcohols. Solid-state 13C CP/MAS (cross polarization and magic-angle spinning) NMR spectroscopy demonstrates the presence of signals due to n-alkoxyl groups originating from the reactant n-alcohol molecules. Differential thermal analysis curves of the products exhibit exothermic peaks at temperatures higher than 200 °C. These results indicate successful preparation of HCa2Nb3O10 derivatives possessing various n-alkoxyl groups (n-CnH2n+1O-, n = 1-4, 6, 8, 10, 12, 14, 16, and 18) on the interlayer surface. Although a reaction between an n-propoxyl derivative and n-decanol does not proceed at 80 °C, a single-phase n- decoxyl derivative can be obtained at 80 °C by adding a small amount of water (1 mass {\%}), which strongly suggests a hydrolysis-esterification mechanism, IR and solid-state 13C CP/MAS NMR spectroscopies indicate that the n-alkyl chains in n-alkoxyl derivatives (n ≥ 10 in n-CnH2+1O- groups) possess an all-trans conformation. A linear relationship with a slope of 0.166 nm/carbon atom is observed between the interlayer distance and the number of carbon atoms in the n-alkyl chains, suggesting that the n-alkyl chains of n-alkoxyl groups are present as bilayers with a tilt angle of 41° in the interlayer space.",
    author = "Seiichi Tahara and Yoshiyuki Sugahara",
    year = "2003",
    month = "10",
    day = "28",
    doi = "10.1021/la0343876",
    language = "English",
    volume = "19",
    pages = "9473--9478",
    journal = "Langmuir",
    issn = "0743-7463",
    publisher = "American Chemical Society",
    number = "22",

    }

    TY - JOUR

    T1 - Interlayer Surface Modification of the Protonated Triple-Layered Perovskite HCa2Nb3O10·xH2O with n-Alcohols

    AU - Tahara, Seiichi

    AU - Sugahara, Yoshiyuki

    PY - 2003/10/28

    Y1 - 2003/10/28

    N2 - Organic derivatives of the protonated triple-layered perovskite HCa 2Nb3O10·xH2O with n-alkoxyl groups on the interlayer surface have been prepared by grafting n-alcohols. Interlayer surface modification of HCa2Nb3O 10·xH2O is achieved by a direct reaction of HCa2Nb3O10·xH2O with methanol or ethanol, and single-phase n-alkoxyl derivatives of HCa 2Nb3O10·xH2O (n ≥ 3 in n-CnH2n+1O- groups) can be formed by reacting n-alkoxyl derivatives (methoxyl and n-propoxyl derivatives) with n- alcohols in an autoclave at 150 °C. X-ray diffraction analysis shows the changes in interlayer distances upon treatment of HCa2- Nb3O 10·xH2O or intermediate n- alkoxyl derivatives with n-alcohols. Solid-state 13C CP/MAS (cross polarization and magic-angle spinning) NMR spectroscopy demonstrates the presence of signals due to n-alkoxyl groups originating from the reactant n-alcohol molecules. Differential thermal analysis curves of the products exhibit exothermic peaks at temperatures higher than 200 °C. These results indicate successful preparation of HCa2Nb3O10 derivatives possessing various n-alkoxyl groups (n-CnH2n+1O-, n = 1-4, 6, 8, 10, 12, 14, 16, and 18) on the interlayer surface. Although a reaction between an n-propoxyl derivative and n-decanol does not proceed at 80 °C, a single-phase n- decoxyl derivative can be obtained at 80 °C by adding a small amount of water (1 mass %), which strongly suggests a hydrolysis-esterification mechanism, IR and solid-state 13C CP/MAS NMR spectroscopies indicate that the n-alkyl chains in n-alkoxyl derivatives (n ≥ 10 in n-CnH2+1O- groups) possess an all-trans conformation. A linear relationship with a slope of 0.166 nm/carbon atom is observed between the interlayer distance and the number of carbon atoms in the n-alkyl chains, suggesting that the n-alkyl chains of n-alkoxyl groups are present as bilayers with a tilt angle of 41° in the interlayer space.

    AB - Organic derivatives of the protonated triple-layered perovskite HCa 2Nb3O10·xH2O with n-alkoxyl groups on the interlayer surface have been prepared by grafting n-alcohols. Interlayer surface modification of HCa2Nb3O 10·xH2O is achieved by a direct reaction of HCa2Nb3O10·xH2O with methanol or ethanol, and single-phase n-alkoxyl derivatives of HCa 2Nb3O10·xH2O (n ≥ 3 in n-CnH2n+1O- groups) can be formed by reacting n-alkoxyl derivatives (methoxyl and n-propoxyl derivatives) with n- alcohols in an autoclave at 150 °C. X-ray diffraction analysis shows the changes in interlayer distances upon treatment of HCa2- Nb3O 10·xH2O or intermediate n- alkoxyl derivatives with n-alcohols. Solid-state 13C CP/MAS (cross polarization and magic-angle spinning) NMR spectroscopy demonstrates the presence of signals due to n-alkoxyl groups originating from the reactant n-alcohol molecules. Differential thermal analysis curves of the products exhibit exothermic peaks at temperatures higher than 200 °C. These results indicate successful preparation of HCa2Nb3O10 derivatives possessing various n-alkoxyl groups (n-CnH2n+1O-, n = 1-4, 6, 8, 10, 12, 14, 16, and 18) on the interlayer surface. Although a reaction between an n-propoxyl derivative and n-decanol does not proceed at 80 °C, a single-phase n- decoxyl derivative can be obtained at 80 °C by adding a small amount of water (1 mass %), which strongly suggests a hydrolysis-esterification mechanism, IR and solid-state 13C CP/MAS NMR spectroscopies indicate that the n-alkyl chains in n-alkoxyl derivatives (n ≥ 10 in n-CnH2+1O- groups) possess an all-trans conformation. A linear relationship with a slope of 0.166 nm/carbon atom is observed between the interlayer distance and the number of carbon atoms in the n-alkyl chains, suggesting that the n-alkyl chains of n-alkoxyl groups are present as bilayers with a tilt angle of 41° in the interlayer space.

    UR - http://www.scopus.com/inward/record.url?scp=0242576053&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=0242576053&partnerID=8YFLogxK

    U2 - 10.1021/la0343876

    DO - 10.1021/la0343876

    M3 - Article

    VL - 19

    SP - 9473

    EP - 9478

    JO - Langmuir

    JF - Langmuir

    SN - 0743-7463

    IS - 22

    ER -