Characterization of Bi5Nb3O15 by refinement of neutron diffraction pattern, acid treatment and reaction of the acid-treated product with n-alkylamines

Seiichi Tahara, Akira Shimada, Nobuhiro Kumada, Yoshiyuki Sugahara

    Research output: Contribution to journalArticle

    30 Citations (Scopus)

    Abstract

    The structure of Bi5Nb3O15 was investigated by refinement of the powder neutron diffraction pattern as well as by structural change through acid treatment and subsequent treatments of an acid-treated product with n-alkylamines. Rietveld refinement suggests that Bi5Nb3O15 adopts a mixed-layer Aurivillius-related phase structure, [Bi2O2]+[NbO4]+[Bi2O2]+[BiNb2O7] [Pnc2 (space group No. 30)] with a = 2.1011 (4), b = 0.5473 (1) and c = 0.5463 (1) nm. After the acid treatment of Bi5Nb3O15 with 3 mol/L HCl, a new reflection (at 2.25 nm after drying at room temperature or at 1.89 nm after drying at 120 °C) appeared in the X-ray diffraction (XRD) pattern in addition to the reflections due to Bi5Nb3O15. Upon acid treatment, a part of the Bi ions were lost and essentially no Nb ions were dissolved during acid treatment to give a Bi/Nb molar ratio of 1.4. The TG curves of the acid-treated product showed mass loss (ca. 4 mass%) in the range of 300-600 °C. It was also demonstrated that the particle shapes did not change upon acid treatment. The reaction of the acid-treated product (after drying at room temperature) with n-alkylamines led to a shift of the newly appearing reflection to a lower angle, and the d-value of the low-angle reflection increased linearly in accordance with the increment of the number of carbon atoms in n-alkylamines. These results indicate that the [Bi2O2] sheet in Bi5Nb3O15 was partially leached by acid treatment to form a layered compound H4BiNb3O11·xH2O, capable of accommodating n-alkylamines in the interlayer space, and its anhydrous form, H4BiNb3O11, upon drying. Based on the variation in the interlayer distance upon intercalation of n-alkylamines into the acid-treated product, the structure of the acid-treated product can be suggested to comprise alternately stacked protonated [BiNb2O7] and [NbO4] sheets, a result consistent with the Rietveld refinement of Bi5Nb3O15.

    Original languageEnglish
    Pages (from-to)2517-2524
    Number of pages8
    JournalJournal of Solid State Chemistry
    Volume180
    Issue number9
    DOIs
    Publication statusPublished - 2007 Sep

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    Neutron diffraction
    Diffraction patterns
    neutron diffraction
    diffraction patterns
    acids
    Acids
    products
    drying
    Drying
    Rietveld refinement
    interlayers
    Ions
    room temperature
    Phase structure
    Intercalation
    intercalation
    Neutrons
    ions
    Carbon
    Powders

    Keywords

    • Acid treatment
    • Aurivillius phase
    • Crystal structure
    • Intercalation
    • Intergrowth
    • Ion exchange
    • Layered perovskite
    • Neutron diffraction

    ASJC Scopus subject areas

    • Inorganic Chemistry
    • Physical and Theoretical Chemistry
    • Materials Chemistry

    Cite this

    Characterization of Bi5Nb3O15 by refinement of neutron diffraction pattern, acid treatment and reaction of the acid-treated product with n-alkylamines. / Tahara, Seiichi; Shimada, Akira; Kumada, Nobuhiro; Sugahara, Yoshiyuki.

    In: Journal of Solid State Chemistry, Vol. 180, No. 9, 09.2007, p. 2517-2524.

    Research output: Contribution to journalArticle

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    title = "Characterization of Bi5Nb3O15 by refinement of neutron diffraction pattern, acid treatment and reaction of the acid-treated product with n-alkylamines",
    abstract = "The structure of Bi5Nb3O15 was investigated by refinement of the powder neutron diffraction pattern as well as by structural change through acid treatment and subsequent treatments of an acid-treated product with n-alkylamines. Rietveld refinement suggests that Bi5Nb3O15 adopts a mixed-layer Aurivillius-related phase structure, [Bi2O2]+[NbO4]+[Bi2O2]+[BiNb2O7] [Pnc2 (space group No. 30)] with a = 2.1011 (4), b = 0.5473 (1) and c = 0.5463 (1) nm. After the acid treatment of Bi5Nb3O15 with 3 mol/L HCl, a new reflection (at 2.25 nm after drying at room temperature or at 1.89 nm after drying at 120 °C) appeared in the X-ray diffraction (XRD) pattern in addition to the reflections due to Bi5Nb3O15. Upon acid treatment, a part of the Bi ions were lost and essentially no Nb ions were dissolved during acid treatment to give a Bi/Nb molar ratio of 1.4. The TG curves of the acid-treated product showed mass loss (ca. 4 mass{\%}) in the range of 300-600 °C. It was also demonstrated that the particle shapes did not change upon acid treatment. The reaction of the acid-treated product (after drying at room temperature) with n-alkylamines led to a shift of the newly appearing reflection to a lower angle, and the d-value of the low-angle reflection increased linearly in accordance with the increment of the number of carbon atoms in n-alkylamines. These results indicate that the [Bi2O2] sheet in Bi5Nb3O15 was partially leached by acid treatment to form a layered compound H4BiNb3O11·xH2O, capable of accommodating n-alkylamines in the interlayer space, and its anhydrous form, H4BiNb3O11, upon drying. Based on the variation in the interlayer distance upon intercalation of n-alkylamines into the acid-treated product, the structure of the acid-treated product can be suggested to comprise alternately stacked protonated [BiNb2O7] and [NbO4] sheets, a result consistent with the Rietveld refinement of Bi5Nb3O15.",
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    T1 - Characterization of Bi5Nb3O15 by refinement of neutron diffraction pattern, acid treatment and reaction of the acid-treated product with n-alkylamines

    AU - Tahara, Seiichi

    AU - Shimada, Akira

    AU - Kumada, Nobuhiro

    AU - Sugahara, Yoshiyuki

    PY - 2007/9

    Y1 - 2007/9

    N2 - The structure of Bi5Nb3O15 was investigated by refinement of the powder neutron diffraction pattern as well as by structural change through acid treatment and subsequent treatments of an acid-treated product with n-alkylamines. Rietveld refinement suggests that Bi5Nb3O15 adopts a mixed-layer Aurivillius-related phase structure, [Bi2O2]+[NbO4]+[Bi2O2]+[BiNb2O7] [Pnc2 (space group No. 30)] with a = 2.1011 (4), b = 0.5473 (1) and c = 0.5463 (1) nm. After the acid treatment of Bi5Nb3O15 with 3 mol/L HCl, a new reflection (at 2.25 nm after drying at room temperature or at 1.89 nm after drying at 120 °C) appeared in the X-ray diffraction (XRD) pattern in addition to the reflections due to Bi5Nb3O15. Upon acid treatment, a part of the Bi ions were lost and essentially no Nb ions were dissolved during acid treatment to give a Bi/Nb molar ratio of 1.4. The TG curves of the acid-treated product showed mass loss (ca. 4 mass%) in the range of 300-600 °C. It was also demonstrated that the particle shapes did not change upon acid treatment. The reaction of the acid-treated product (after drying at room temperature) with n-alkylamines led to a shift of the newly appearing reflection to a lower angle, and the d-value of the low-angle reflection increased linearly in accordance with the increment of the number of carbon atoms in n-alkylamines. These results indicate that the [Bi2O2] sheet in Bi5Nb3O15 was partially leached by acid treatment to form a layered compound H4BiNb3O11·xH2O, capable of accommodating n-alkylamines in the interlayer space, and its anhydrous form, H4BiNb3O11, upon drying. Based on the variation in the interlayer distance upon intercalation of n-alkylamines into the acid-treated product, the structure of the acid-treated product can be suggested to comprise alternately stacked protonated [BiNb2O7] and [NbO4] sheets, a result consistent with the Rietveld refinement of Bi5Nb3O15.

    AB - The structure of Bi5Nb3O15 was investigated by refinement of the powder neutron diffraction pattern as well as by structural change through acid treatment and subsequent treatments of an acid-treated product with n-alkylamines. Rietveld refinement suggests that Bi5Nb3O15 adopts a mixed-layer Aurivillius-related phase structure, [Bi2O2]+[NbO4]+[Bi2O2]+[BiNb2O7] [Pnc2 (space group No. 30)] with a = 2.1011 (4), b = 0.5473 (1) and c = 0.5463 (1) nm. After the acid treatment of Bi5Nb3O15 with 3 mol/L HCl, a new reflection (at 2.25 nm after drying at room temperature or at 1.89 nm after drying at 120 °C) appeared in the X-ray diffraction (XRD) pattern in addition to the reflections due to Bi5Nb3O15. Upon acid treatment, a part of the Bi ions were lost and essentially no Nb ions were dissolved during acid treatment to give a Bi/Nb molar ratio of 1.4. The TG curves of the acid-treated product showed mass loss (ca. 4 mass%) in the range of 300-600 °C. It was also demonstrated that the particle shapes did not change upon acid treatment. The reaction of the acid-treated product (after drying at room temperature) with n-alkylamines led to a shift of the newly appearing reflection to a lower angle, and the d-value of the low-angle reflection increased linearly in accordance with the increment of the number of carbon atoms in n-alkylamines. These results indicate that the [Bi2O2] sheet in Bi5Nb3O15 was partially leached by acid treatment to form a layered compound H4BiNb3O11·xH2O, capable of accommodating n-alkylamines in the interlayer space, and its anhydrous form, H4BiNb3O11, upon drying. Based on the variation in the interlayer distance upon intercalation of n-alkylamines into the acid-treated product, the structure of the acid-treated product can be suggested to comprise alternately stacked protonated [BiNb2O7] and [NbO4] sheets, a result consistent with the Rietveld refinement of Bi5Nb3O15.

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    KW - Aurivillius phase

    KW - Crystal structure

    KW - Intercalation

    KW - Intergrowth

    KW - Ion exchange

    KW - Layered perovskite

    KW - Neutron diffraction

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