Structural changes and cation site ordering in Na and K forms of aluminogermanates with the zeolite gismondine topology

A. Tripathi, J. B. Parise, S. J. Kim, Yongjae Lee, G. M. Johnson, Y. S. Uh

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Two new aluminogermanates, K - AlGe-GIS (K8Al8Ge8O32 ·8H2O) and Na - AlGe-GIS (Na24Al24Ge24O96 ·40H2O), with the zeolite gismondine (GIS) type framework topology have been synthesized hydrothermally and characterized using single-crystal X-ray diffraction. K - AlGe-GIS crystallizes in the monoclinic space group I2/a with a = 10.311(2) Å, b = 9.749-(1) Å, c = 10.225(6) Å, β = 90.000(2)°, and Z = 8. Na - AlGe-GIS crystallizes in the monoclinic space group C2/c with a = 14.490(3) Å, b = 9.940(2) Å, c = 23.530(5) Å, β = 105.90(3)°, and Z = 8. Strict alternation of Ge and Al atoms over the framework sites lowers the symmetry of these aluminogermanates from their topological framework symmetry of I41/amd to the real symmetry I2/a. Both structures consist of twisted double-crankshaft chains running along the a and c axes. In K - AlGe-GIS, potassium and water statistically occupy extraframework sites along the perpendicular eight-ring channels. In Na - AlGe-GIS, all three sodium sites are fully occupied and only three out of seven sites containing water are statistically occupied. A zigzag-ordered arrangement of Na sites in Na - AlGe-GIS results in unit cell symmetry hitherto unobserved for GIS. The synthesis of Na - AlGe-GIS requires the presence of organic bases, while K - AlGe-GIS can be synthesized from gels with or without organic bases. Time-resolved synchrotron X-ray powder diffraction patterns obtained as a function of temperature for Na - AlGe-GIS show a gradual disappearance of the C-centered cell between 150 and 180 °C with a simultaneous appearance of an I-centered monoclinic phase. Calculated powder diffraction patterns indicate that this phase change results from disordering of Na sites in the eight-ring channels. Results of a single-crystal diffraction study for a 50% Na-exchanged K - AlGe-GIS (K4Na4Al8Ge8O32 ·8H2O) shows that the space group I2/a is retained with a 0.3% increase in the unit cell volume. Both the AlGe frameworks retain the GIS topology until ca. 750 °C after dehydration. The average Al-O-Ge (T-O-T) bond angle of 135.75° in K - AlGe-GIS and 135.29° in Na - AlGe-GIS is smaller than the average Al - O - Si bond angle of 145° in aluminosilicates.

Original languageEnglish
Pages (from-to)3760-3769
Number of pages10
JournalChemistry of Materials
Volume12
Issue number12
DOIs
Publication statusPublished - 2000 Dec 1

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Zeolites
Diffraction patterns
Cations
Positive ions
Topology
Single crystals
Crankshafts
Water
Aluminosilicates
Synchrotrons
Dehydration
X ray powder diffraction
Potassium
Gels
Diffraction
Sodium
X ray diffraction
Atoms
Temperature
Powder Diffraction

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Tripathi, A. ; Parise, J. B. ; Kim, S. J. ; Lee, Yongjae ; Johnson, G. M. ; Uh, Y. S. / Structural changes and cation site ordering in Na and K forms of aluminogermanates with the zeolite gismondine topology. In: Chemistry of Materials. 2000 ; Vol. 12, No. 12. pp. 3760-3769.
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title = "Structural changes and cation site ordering in Na and K forms of aluminogermanates with the zeolite gismondine topology",
abstract = "Two new aluminogermanates, K - AlGe-GIS (K8Al8Ge8O32 ·8H2O) and Na - AlGe-GIS (Na24Al24Ge24O96 ·40H2O), with the zeolite gismondine (GIS) type framework topology have been synthesized hydrothermally and characterized using single-crystal X-ray diffraction. K - AlGe-GIS crystallizes in the monoclinic space group I2/a with a = 10.311(2) {\AA}, b = 9.749-(1) {\AA}, c = 10.225(6) {\AA}, β = 90.000(2)°, and Z = 8. Na - AlGe-GIS crystallizes in the monoclinic space group C2/c with a = 14.490(3) {\AA}, b = 9.940(2) {\AA}, c = 23.530(5) {\AA}, β = 105.90(3)°, and Z = 8. Strict alternation of Ge and Al atoms over the framework sites lowers the symmetry of these aluminogermanates from their topological framework symmetry of I41/amd to the real symmetry I2/a. Both structures consist of twisted double-crankshaft chains running along the a and c axes. In K - AlGe-GIS, potassium and water statistically occupy extraframework sites along the perpendicular eight-ring channels. In Na - AlGe-GIS, all three sodium sites are fully occupied and only three out of seven sites containing water are statistically occupied. A zigzag-ordered arrangement of Na sites in Na - AlGe-GIS results in unit cell symmetry hitherto unobserved for GIS. The synthesis of Na - AlGe-GIS requires the presence of organic bases, while K - AlGe-GIS can be synthesized from gels with or without organic bases. Time-resolved synchrotron X-ray powder diffraction patterns obtained as a function of temperature for Na - AlGe-GIS show a gradual disappearance of the C-centered cell between 150 and 180 °C with a simultaneous appearance of an I-centered monoclinic phase. Calculated powder diffraction patterns indicate that this phase change results from disordering of Na sites in the eight-ring channels. Results of a single-crystal diffraction study for a 50{\%} Na-exchanged K - AlGe-GIS (K4Na4Al8Ge8O32 ·8H2O) shows that the space group I2/a is retained with a 0.3{\%} increase in the unit cell volume. Both the AlGe frameworks retain the GIS topology until ca. 750 °C after dehydration. The average Al-O-Ge (T-O-T) bond angle of 135.75° in K - AlGe-GIS and 135.29° in Na - AlGe-GIS is smaller than the average Al - O - Si bond angle of 145° in aluminosilicates.",
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Structural changes and cation site ordering in Na and K forms of aluminogermanates with the zeolite gismondine topology. / Tripathi, A.; Parise, J. B.; Kim, S. J.; Lee, Yongjae; Johnson, G. M.; Uh, Y. S.

In: Chemistry of Materials, Vol. 12, No. 12, 01.12.2000, p. 3760-3769.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural changes and cation site ordering in Na and K forms of aluminogermanates with the zeolite gismondine topology

AU - Tripathi, A.

AU - Parise, J. B.

AU - Kim, S. J.

AU - Lee, Yongjae

AU - Johnson, G. M.

AU - Uh, Y. S.

PY - 2000/12/1

Y1 - 2000/12/1

N2 - Two new aluminogermanates, K - AlGe-GIS (K8Al8Ge8O32 ·8H2O) and Na - AlGe-GIS (Na24Al24Ge24O96 ·40H2O), with the zeolite gismondine (GIS) type framework topology have been synthesized hydrothermally and characterized using single-crystal X-ray diffraction. K - AlGe-GIS crystallizes in the monoclinic space group I2/a with a = 10.311(2) Å, b = 9.749-(1) Å, c = 10.225(6) Å, β = 90.000(2)°, and Z = 8. Na - AlGe-GIS crystallizes in the monoclinic space group C2/c with a = 14.490(3) Å, b = 9.940(2) Å, c = 23.530(5) Å, β = 105.90(3)°, and Z = 8. Strict alternation of Ge and Al atoms over the framework sites lowers the symmetry of these aluminogermanates from their topological framework symmetry of I41/amd to the real symmetry I2/a. Both structures consist of twisted double-crankshaft chains running along the a and c axes. In K - AlGe-GIS, potassium and water statistically occupy extraframework sites along the perpendicular eight-ring channels. In Na - AlGe-GIS, all three sodium sites are fully occupied and only three out of seven sites containing water are statistically occupied. A zigzag-ordered arrangement of Na sites in Na - AlGe-GIS results in unit cell symmetry hitherto unobserved for GIS. The synthesis of Na - AlGe-GIS requires the presence of organic bases, while K - AlGe-GIS can be synthesized from gels with or without organic bases. Time-resolved synchrotron X-ray powder diffraction patterns obtained as a function of temperature for Na - AlGe-GIS show a gradual disappearance of the C-centered cell between 150 and 180 °C with a simultaneous appearance of an I-centered monoclinic phase. Calculated powder diffraction patterns indicate that this phase change results from disordering of Na sites in the eight-ring channels. Results of a single-crystal diffraction study for a 50% Na-exchanged K - AlGe-GIS (K4Na4Al8Ge8O32 ·8H2O) shows that the space group I2/a is retained with a 0.3% increase in the unit cell volume. Both the AlGe frameworks retain the GIS topology until ca. 750 °C after dehydration. The average Al-O-Ge (T-O-T) bond angle of 135.75° in K - AlGe-GIS and 135.29° in Na - AlGe-GIS is smaller than the average Al - O - Si bond angle of 145° in aluminosilicates.

AB - Two new aluminogermanates, K - AlGe-GIS (K8Al8Ge8O32 ·8H2O) and Na - AlGe-GIS (Na24Al24Ge24O96 ·40H2O), with the zeolite gismondine (GIS) type framework topology have been synthesized hydrothermally and characterized using single-crystal X-ray diffraction. K - AlGe-GIS crystallizes in the monoclinic space group I2/a with a = 10.311(2) Å, b = 9.749-(1) Å, c = 10.225(6) Å, β = 90.000(2)°, and Z = 8. Na - AlGe-GIS crystallizes in the monoclinic space group C2/c with a = 14.490(3) Å, b = 9.940(2) Å, c = 23.530(5) Å, β = 105.90(3)°, and Z = 8. Strict alternation of Ge and Al atoms over the framework sites lowers the symmetry of these aluminogermanates from their topological framework symmetry of I41/amd to the real symmetry I2/a. Both structures consist of twisted double-crankshaft chains running along the a and c axes. In K - AlGe-GIS, potassium and water statistically occupy extraframework sites along the perpendicular eight-ring channels. In Na - AlGe-GIS, all three sodium sites are fully occupied and only three out of seven sites containing water are statistically occupied. A zigzag-ordered arrangement of Na sites in Na - AlGe-GIS results in unit cell symmetry hitherto unobserved for GIS. The synthesis of Na - AlGe-GIS requires the presence of organic bases, while K - AlGe-GIS can be synthesized from gels with or without organic bases. Time-resolved synchrotron X-ray powder diffraction patterns obtained as a function of temperature for Na - AlGe-GIS show a gradual disappearance of the C-centered cell between 150 and 180 °C with a simultaneous appearance of an I-centered monoclinic phase. Calculated powder diffraction patterns indicate that this phase change results from disordering of Na sites in the eight-ring channels. Results of a single-crystal diffraction study for a 50% Na-exchanged K - AlGe-GIS (K4Na4Al8Ge8O32 ·8H2O) shows that the space group I2/a is retained with a 0.3% increase in the unit cell volume. Both the AlGe frameworks retain the GIS topology until ca. 750 °C after dehydration. The average Al-O-Ge (T-O-T) bond angle of 135.75° in K - AlGe-GIS and 135.29° in Na - AlGe-GIS is smaller than the average Al - O - Si bond angle of 145° in aluminosilicates.

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