Chemical and hydrostatic pressure in natrolites: Pressure-induced hydration of an aluminogermanate natrolite

Yongjae Lee, Dong Hoon Seoung, Jianming Bai, Chi Chang Kao, John B. Parise, Thomas Vogt

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The ambient structure and pressure-induced structural changes of a synthetic sodium aluminogermanate with a natrolite (NAT) framework topology (Na-AlGe-NAT) were characterized by using Rietveld refinements of high-resolution synchrotron X-ray powder diffraction data at ambient and high pressures. Unlike a previously established model for Na8Al 8Ge12O40A•8H2O based on a single-crystal study, the ambient structure of the Na-AlGe-NAT is found to adopt a monoclinic space group Cc (or Fd) with a ca. 6% expanded unit cell. The refined ambient structure of Na8Al8Ge12O 40A•12H2O indicates an increased water content of 50%, compared to the single-crystal structure. The unit-cell volume and water-content relationships observed between the two Na-AlGe-NAT structures at ambient conditions with 8 and 12 H2O respectively seem to mirror the ones found under hydrostatic pressure between the Na8Al 8Si12O40A•8H2O and the parantrolite phase Na8Al8Si12O 40A•12H2O. Under hydrostatic pressures mediated by a pore-penetrating alcohol and water mixture, the monoclinic Na-AlGe-NAT exhibits a gradual decrease of the unit-cell volume up to ca. 2.0 GPa, where the unit-cell volume then contracts abruptly by ca. 4.6%. This is in marked contrast to what is observed in the Na-AlSi-NAT and Na-GaSi-NAT systems, where one observes a pressure-induced hydration and volume expansion due to the auxetic nature of the frameworks. Above 2 GPa, the monoclinic phase of Na-AlGe-NAT transforms into a tetragonal structure with the unit-cell composition of Na 8Al8Ge12O40A•16H2O, revealing pressure-induced hydration and a unit cell volume contraction. Unlike in the Na-Al,Si-paranatrolite phase, however, the sodium cations in the Na-AlGe-NAT maintain a 6-fold coordination in the monoclinic structure and only become 7-fold coordinated at higher pressures in the tetragonal structure. When comparing the pressure-induced hydration in the observed natrolite-type zeolites, Na-AlGe-NAT appears to have a nonauxetic framework and reveals the highest onset pressure for complete superhydration.

Original languageEnglish
Pages (from-to)18805-18811
Number of pages7
JournalJournal of Physical Chemistry C
Volume114
Issue number44
DOIs
Publication statusPublished - 2010 Nov 11

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Hydrostatic pressure
hydrostatic pressure
Hydration
hydration
cells
moisture content
Water content
sodium
Sodium
Single crystals
single crystals
Rietveld refinement
zeolites
contraction
natrolite
Zeolites
Synchrotrons
synchrotrons
X ray powder diffraction
alcohols

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Lee, Yongjae ; Seoung, Dong Hoon ; Bai, Jianming ; Kao, Chi Chang ; Parise, John B. ; Vogt, Thomas. / Chemical and hydrostatic pressure in natrolites : Pressure-induced hydration of an aluminogermanate natrolite. In: Journal of Physical Chemistry C. 2010 ; Vol. 114, No. 44. pp. 18805-18811.
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abstract = "The ambient structure and pressure-induced structural changes of a synthetic sodium aluminogermanate with a natrolite (NAT) framework topology (Na-AlGe-NAT) were characterized by using Rietveld refinements of high-resolution synchrotron X-ray powder diffraction data at ambient and high pressures. Unlike a previously established model for Na8Al 8Ge12O40A•8H2O based on a single-crystal study, the ambient structure of the Na-AlGe-NAT is found to adopt a monoclinic space group Cc (or Fd) with a ca. 6{\%} expanded unit cell. The refined ambient structure of Na8Al8Ge12O 40A•12H2O indicates an increased water content of 50{\%}, compared to the single-crystal structure. The unit-cell volume and water-content relationships observed between the two Na-AlGe-NAT structures at ambient conditions with 8 and 12 H2O respectively seem to mirror the ones found under hydrostatic pressure between the Na8Al 8Si12O40A•8H2O and the parantrolite phase Na8Al8Si12O 40A•12H2O. Under hydrostatic pressures mediated by a pore-penetrating alcohol and water mixture, the monoclinic Na-AlGe-NAT exhibits a gradual decrease of the unit-cell volume up to ca. 2.0 GPa, where the unit-cell volume then contracts abruptly by ca. 4.6{\%}. This is in marked contrast to what is observed in the Na-AlSi-NAT and Na-GaSi-NAT systems, where one observes a pressure-induced hydration and volume expansion due to the auxetic nature of the frameworks. Above 2 GPa, the monoclinic phase of Na-AlGe-NAT transforms into a tetragonal structure with the unit-cell composition of Na 8Al8Ge12O40A•16H2O, revealing pressure-induced hydration and a unit cell volume contraction. Unlike in the Na-Al,Si-paranatrolite phase, however, the sodium cations in the Na-AlGe-NAT maintain a 6-fold coordination in the monoclinic structure and only become 7-fold coordinated at higher pressures in the tetragonal structure. When comparing the pressure-induced hydration in the observed natrolite-type zeolites, Na-AlGe-NAT appears to have a nonauxetic framework and reveals the highest onset pressure for complete superhydration.",
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Chemical and hydrostatic pressure in natrolites : Pressure-induced hydration of an aluminogermanate natrolite. / Lee, Yongjae; Seoung, Dong Hoon; Bai, Jianming; Kao, Chi Chang; Parise, John B.; Vogt, Thomas.

In: Journal of Physical Chemistry C, Vol. 114, No. 44, 11.11.2010, p. 18805-18811.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chemical and hydrostatic pressure in natrolites

T2 - Pressure-induced hydration of an aluminogermanate natrolite

AU - Lee, Yongjae

AU - Seoung, Dong Hoon

AU - Bai, Jianming

AU - Kao, Chi Chang

AU - Parise, John B.

AU - Vogt, Thomas

PY - 2010/11/11

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N2 - The ambient structure and pressure-induced structural changes of a synthetic sodium aluminogermanate with a natrolite (NAT) framework topology (Na-AlGe-NAT) were characterized by using Rietveld refinements of high-resolution synchrotron X-ray powder diffraction data at ambient and high pressures. Unlike a previously established model for Na8Al 8Ge12O40A•8H2O based on a single-crystal study, the ambient structure of the Na-AlGe-NAT is found to adopt a monoclinic space group Cc (or Fd) with a ca. 6% expanded unit cell. The refined ambient structure of Na8Al8Ge12O 40A•12H2O indicates an increased water content of 50%, compared to the single-crystal structure. The unit-cell volume and water-content relationships observed between the two Na-AlGe-NAT structures at ambient conditions with 8 and 12 H2O respectively seem to mirror the ones found under hydrostatic pressure between the Na8Al 8Si12O40A•8H2O and the parantrolite phase Na8Al8Si12O 40A•12H2O. Under hydrostatic pressures mediated by a pore-penetrating alcohol and water mixture, the monoclinic Na-AlGe-NAT exhibits a gradual decrease of the unit-cell volume up to ca. 2.0 GPa, where the unit-cell volume then contracts abruptly by ca. 4.6%. This is in marked contrast to what is observed in the Na-AlSi-NAT and Na-GaSi-NAT systems, where one observes a pressure-induced hydration and volume expansion due to the auxetic nature of the frameworks. Above 2 GPa, the monoclinic phase of Na-AlGe-NAT transforms into a tetragonal structure with the unit-cell composition of Na 8Al8Ge12O40A•16H2O, revealing pressure-induced hydration and a unit cell volume contraction. Unlike in the Na-Al,Si-paranatrolite phase, however, the sodium cations in the Na-AlGe-NAT maintain a 6-fold coordination in the monoclinic structure and only become 7-fold coordinated at higher pressures in the tetragonal structure. When comparing the pressure-induced hydration in the observed natrolite-type zeolites, Na-AlGe-NAT appears to have a nonauxetic framework and reveals the highest onset pressure for complete superhydration.

AB - The ambient structure and pressure-induced structural changes of a synthetic sodium aluminogermanate with a natrolite (NAT) framework topology (Na-AlGe-NAT) were characterized by using Rietveld refinements of high-resolution synchrotron X-ray powder diffraction data at ambient and high pressures. Unlike a previously established model for Na8Al 8Ge12O40A•8H2O based on a single-crystal study, the ambient structure of the Na-AlGe-NAT is found to adopt a monoclinic space group Cc (or Fd) with a ca. 6% expanded unit cell. The refined ambient structure of Na8Al8Ge12O 40A•12H2O indicates an increased water content of 50%, compared to the single-crystal structure. The unit-cell volume and water-content relationships observed between the two Na-AlGe-NAT structures at ambient conditions with 8 and 12 H2O respectively seem to mirror the ones found under hydrostatic pressure between the Na8Al 8Si12O40A•8H2O and the parantrolite phase Na8Al8Si12O 40A•12H2O. Under hydrostatic pressures mediated by a pore-penetrating alcohol and water mixture, the monoclinic Na-AlGe-NAT exhibits a gradual decrease of the unit-cell volume up to ca. 2.0 GPa, where the unit-cell volume then contracts abruptly by ca. 4.6%. This is in marked contrast to what is observed in the Na-AlSi-NAT and Na-GaSi-NAT systems, where one observes a pressure-induced hydration and volume expansion due to the auxetic nature of the frameworks. Above 2 GPa, the monoclinic phase of Na-AlGe-NAT transforms into a tetragonal structure with the unit-cell composition of Na 8Al8Ge12O40A•16H2O, revealing pressure-induced hydration and a unit cell volume contraction. Unlike in the Na-Al,Si-paranatrolite phase, however, the sodium cations in the Na-AlGe-NAT maintain a 6-fold coordination in the monoclinic structure and only become 7-fold coordinated at higher pressures in the tetragonal structure. When comparing the pressure-induced hydration in the observed natrolite-type zeolites, Na-AlGe-NAT appears to have a nonauxetic framework and reveals the highest onset pressure for complete superhydration.

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