Sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O (x ≈ 1.6, n ≈ 3.0): Synthesis, phase transitions and dynamical disorder of the hydrogen dihydroxide anion, H3O2, in the Cubic high‐temperature form

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Autoren

  • Michael Wiebcke
  • Peter Sieger
  • Jürgen Felsche
  • Günter Engelhardt
  • Peter Behrens
  • Jürg Schefer

Externe Organisationen

  • Universität Konstanz
  • Universität Stuttgart
  • Paul Scherrer Institut (PSI)
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Details

OriginalspracheEnglisch
Seiten (von - bis)1321-1329
Seitenumfang9
FachzeitschriftZAAC ‐ Journal of Inorganic and General Chemistry
Jahrgang619
Ausgabenummer7
PublikationsstatusVeröffentlicht - Juli 1993
Extern publiziertJa

Abstract

Crystalline sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O with x ≈ 1.6 and n ≈ 3.0 has been synthesized by reacting Al2O3, GeO2 and NaOH solution under hydrothermal conditions, and characterized by means of simultaneous thermal analysis, differential scanning calorimetry, X‐ray and neutron diffraction as well as 1H and 23Na MAS NMR and IR spectroscopy. The material undergoes a reversible structural phase transition at Tc = 166 K (heating mode), which is actually a complex two‐step transformation as detected in DSC measurements. Structure refinements of the cubic high‐temperature form (cell constant a = 9.034(2) Å, room temperature) with single‐crystal X‐ray and powder neutron diffraction data have not yielded overall satisfactory results, probably due to the solid‐solution character of the hydrosodalite. The refinements nevertheless demonstrate that (i) the sodalite host framework is a strictly alternating array of corner‐linked AlO4 and GeO4 tetrahedra, and (ii) most polyhedral [4668] cavities are occupied by four sodium cations and one orientationally disordered hydrogen dihydroxide anion, H3O2, which possesses a strong central hydrogen bond. Variable‐temperature 1H MAS NMR spectra unambiguously confirm the presence of H3O2 ions and, in addition, reveal a dynamical intraionic exchange between the central and terminal protons and a rotational diffusion of those anions to occur in the high‐temperature form. The nature of the guest complexes filling the remaining cages could not be unambiguously determined. Results are compared with those obtained in recent studies on the related sodium aluminosilicate hydrosodalite system of the general formula Na6+x[Al6Si6O24] (OH)x · nH2O.

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@article{830b4b2258674f10816dfc72d2b14834,
title = "Sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O (x ≈ 1.6, n ≈ 3.0): Synthesis, phase transitions and dynamical disorder of the hydrogen dihydroxide anion, H3O2−, in the Cubic high‐temperature form",
abstract = "Crystalline sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O with x ≈ 1.6 and n ≈ 3.0 has been synthesized by reacting Al2O3, GeO2 and NaOH solution under hydrothermal conditions, and characterized by means of simultaneous thermal analysis, differential scanning calorimetry, X‐ray and neutron diffraction as well as 1H and 23Na MAS NMR and IR spectroscopy. The material undergoes a reversible structural phase transition at Tc = 166 K (heating mode), which is actually a complex two‐step transformation as detected in DSC measurements. Structure refinements of the cubic high‐temperature form (cell constant a = 9.034(2) {\AA}, room temperature) with single‐crystal X‐ray and powder neutron diffraction data have not yielded overall satisfactory results, probably due to the solid‐solution character of the hydrosodalite. The refinements nevertheless demonstrate that (i) the sodalite host framework is a strictly alternating array of corner‐linked AlO4 and GeO4 tetrahedra, and (ii) most polyhedral [4668] cavities are occupied by four sodium cations and one orientationally disordered hydrogen dihydroxide anion, H3O2−, which possesses a strong central hydrogen bond. Variable‐temperature 1H MAS NMR spectra unambiguously confirm the presence of H3O2− ions and, in addition, reveal a dynamical intraionic exchange between the central and terminal protons and a rotational diffusion of those anions to occur in the high‐temperature form. The nature of the guest complexes filling the remaining cages could not be unambiguously determined. Results are compared with those obtained in recent studies on the related sodium aluminosilicate hydrosodalite system of the general formula Na6+x[Al6Si6O24] (OH)x · nH2O.",
keywords = "crystal structure, dynamical proton exchange, hydrogen dihydroxide anion, MAS NMR, phase transition, sodalite, Sodium aluminogermanate",
author = "Michael Wiebcke and Peter Sieger and J{\"u}rgen Felsche and G{\"u}nter Engelhardt and Peter Behrens and J{\"u}rg Schefer",
year = "1993",
month = jul,
doi = "10.1002/zaac.19936190728",
language = "English",
volume = "619",
pages = "1321--1329",
journal = "ZAAC ‐ Journal of Inorganic and General Chemistry",
issn = "0044-2313",
publisher = "Wiley-VCH Verlag",
number = "7",

}

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TY - JOUR

T1 - Sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O (x ≈ 1.6, n ≈ 3.0)

T2 - Synthesis, phase transitions and dynamical disorder of the hydrogen dihydroxide anion, H3O2−, in the Cubic high‐temperature form

AU - Wiebcke, Michael

AU - Sieger, Peter

AU - Felsche, Jürgen

AU - Engelhardt, Günter

AU - Behrens, Peter

AU - Schefer, Jürg

PY - 1993/7

Y1 - 1993/7

N2 - Crystalline sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O with x ≈ 1.6 and n ≈ 3.0 has been synthesized by reacting Al2O3, GeO2 and NaOH solution under hydrothermal conditions, and characterized by means of simultaneous thermal analysis, differential scanning calorimetry, X‐ray and neutron diffraction as well as 1H and 23Na MAS NMR and IR spectroscopy. The material undergoes a reversible structural phase transition at Tc = 166 K (heating mode), which is actually a complex two‐step transformation as detected in DSC measurements. Structure refinements of the cubic high‐temperature form (cell constant a = 9.034(2) Å, room temperature) with single‐crystal X‐ray and powder neutron diffraction data have not yielded overall satisfactory results, probably due to the solid‐solution character of the hydrosodalite. The refinements nevertheless demonstrate that (i) the sodalite host framework is a strictly alternating array of corner‐linked AlO4 and GeO4 tetrahedra, and (ii) most polyhedral [4668] cavities are occupied by four sodium cations and one orientationally disordered hydrogen dihydroxide anion, H3O2−, which possesses a strong central hydrogen bond. Variable‐temperature 1H MAS NMR spectra unambiguously confirm the presence of H3O2− ions and, in addition, reveal a dynamical intraionic exchange between the central and terminal protons and a rotational diffusion of those anions to occur in the high‐temperature form. The nature of the guest complexes filling the remaining cages could not be unambiguously determined. Results are compared with those obtained in recent studies on the related sodium aluminosilicate hydrosodalite system of the general formula Na6+x[Al6Si6O24] (OH)x · nH2O.

AB - Crystalline sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O with x ≈ 1.6 and n ≈ 3.0 has been synthesized by reacting Al2O3, GeO2 and NaOH solution under hydrothermal conditions, and characterized by means of simultaneous thermal analysis, differential scanning calorimetry, X‐ray and neutron diffraction as well as 1H and 23Na MAS NMR and IR spectroscopy. The material undergoes a reversible structural phase transition at Tc = 166 K (heating mode), which is actually a complex two‐step transformation as detected in DSC measurements. Structure refinements of the cubic high‐temperature form (cell constant a = 9.034(2) Å, room temperature) with single‐crystal X‐ray and powder neutron diffraction data have not yielded overall satisfactory results, probably due to the solid‐solution character of the hydrosodalite. The refinements nevertheless demonstrate that (i) the sodalite host framework is a strictly alternating array of corner‐linked AlO4 and GeO4 tetrahedra, and (ii) most polyhedral [4668] cavities are occupied by four sodium cations and one orientationally disordered hydrogen dihydroxide anion, H3O2−, which possesses a strong central hydrogen bond. Variable‐temperature 1H MAS NMR spectra unambiguously confirm the presence of H3O2− ions and, in addition, reveal a dynamical intraionic exchange between the central and terminal protons and a rotational diffusion of those anions to occur in the high‐temperature form. The nature of the guest complexes filling the remaining cages could not be unambiguously determined. Results are compared with those obtained in recent studies on the related sodium aluminosilicate hydrosodalite system of the general formula Na6+x[Al6Si6O24] (OH)x · nH2O.

KW - crystal structure

KW - dynamical proton exchange

KW - hydrogen dihydroxide anion

KW - MAS NMR

KW - phase transition

KW - sodalite

KW - Sodium aluminogermanate

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U2 - 10.1002/zaac.19936190728

DO - 10.1002/zaac.19936190728

M3 - Article

AN - SCOPUS:0007981923

VL - 619

SP - 1321

EP - 1329

JO - ZAAC ‐ Journal of Inorganic and General Chemistry

JF - ZAAC ‐ Journal of Inorganic and General Chemistry

SN - 0044-2313

IS - 7

ER -