Structural evolution of natrolite during over-hydration: a high-pressure neutron diffraction study

Seryotkin, Yurii V.; Bakakin, V. V.; Fursenko, B. A.; Belitsky, Igor A.; Joswig, W.; Radaelli, P. G.

doi:10.1127/0935-1221/2005/0017-0305

Cited by 45 publications

(26 citation statements)

References 14 publications

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“…It is worth noting that the increase of the extra-framework content of both H-ZSM-5 and Na-ZSM-5, although extremely high, occurs without any cell volume expansion, similarly to that found for gismondine [12], boggsite [15] and NaA [34], and contrary to that reported for other zeolites of the fibrous family [35][36][37][38]. The abrupt volume expansion observed in these last cases was ascribed to the penetration of additional water molecules in new extraframework sites, while in gismondine, boggsite and Na-ZSM-5 the extra molecules contribute to increase the occupancy of already existing extraframework sites.…”

Section: P (Gpa)supporting

confidence: 55%

Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

Quartieri¹,

Montagna²,

Arletti³

et al. 2011

Journal of Solid State Chemistry

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High pressure structure Elastic behavior Synchrotron X-ray powder diffraction a b s t r a c tThe elastic behavior of H-ZSM-5 was investigated by in-situ synchrotron X-ray powder diffraction, using both silicone oil (s.o.) and (16:3:1) methanol:ethanol:water (m.e.w.) as ''non-penetrating'' and ''penetrating'' pressure transmitting media, respectively. From P amb to 6.2 GPa the volume reduction observed in s.o. is 16.6%. This testifies that H-ZSM-5 is one of the most flexible microporous materials up to now compressed in s.o. Volume reduction observed in m.e.w. up to 7.6 GPa is 14.6%. A strong increase in the total electron number of the extraframework system, due to the penetration of water/ alcohol molecules in the pores, is observed in m.e.w. This effect is the largest up to now observed in zeolites undergoing this phenomenon without cell volume expansion. The higher compressibility in s.o. than in m.e.w. can be ascribed to the penetration of the extra-water/alcohol molecules, which stiffen the structure and contrast the channel deformations.

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Section: P (Gpa)supporting

confidence: 55%

Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

Quartieri¹,

Montagna²,

Arletti³

et al. 2011

Journal of Solid State Chemistry

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“…Besson et al, 1992;Colligan et al, 2005;Seryotkin et al, 2005). Experiments on the elastic parameters of some zeolites at room conditions have been done by Brillouin-scattering spectroscopy (e.g.…”

Section: In Situ High-pressure Experiments On Zeolites: Technical Aspmentioning

confidence: 99%

“…Later, experiments addressed the Pinduced penetration of 'external' molecules in natural or synthetic zeolites with different frameworks, opening a new area in the crystal chemistry of this class of materials (e.g. Lee et al, 2002aLee et al, ,b, 2004aLee et al, ,b,c, 2010Lee et al, , 2011Likhacheva et al, 2006Likhacheva et al, , 2007Colligan et al, 2005;Seryotkin et al, 2005;Ori et al, 2008a). The experiments on over-hydration effects and (more in general) P-induced penetration of external molecules, showed that this unusual phenomenon can give rise to (1) new extra-framework sites, changing the configuration of the extra-framework species significantly (as in fibrous zeolites or in laumontite, Lee et al, 2002aLee et al, , 2004b or (2) increasing the occupancy factors of sites partly occupied at room P without new sites (e.g.…”

Section: In Situ High-pressure Experiments On Zeolites: Technical Aspmentioning

confidence: 99%

Zeolites at high pressure: A review

2014

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This is a review of the elastic behaviour and pressure (P)-induced structural evolution of zeolites and presents a comparative analysis of the deformation mechanisms of the Si/Al-framework and the rearrangement of the extra-framework species in response to applied pressure. The interaction between P-transmitting fluids and zeolites, which can lead to phenomena such as 'P-induced over-hydration', is described. The comparative elastic analysis and the high-P structural data of zeolites reported so far allow us to make some generalizations: (1) The range of compressibility among this class of openframework silicates is large, with bulk moduli ranging between 15 and 70 GPa; (2) Microporosity does not necessarily imply high compressibility, as several zeolites are less compressible than other nonzeolitic rock-forming minerals; (3) Compressibilities of zeolites do not seem to be directly related to microporosity, at least if we model microporosity with the 'framework density'; (4) The flexibility observed in zeolites under hydrostatic compression is mainly governed by tilting of rigid tetrahedra around O atoms that behave as hinges within the framework. Pressure-induced tilting commonly leads to continuous rearrangement of the framework without any phase transition. More rarely, tilting induces displacive phase transitions and isothermal P-induced reconstructive phase transitions (i.e. with change in framework topology), have not been reported in this class of materials; (5) Deformation mechanisms in response to applied pressure are generally dictated by the topological configuration of the framework rather than the Si/Al-distribution or the extra-framework content. The channel content governs the compressibility of the cavities, leading to different unit-cell-volume compressibilities in isotypic structures.

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“…The high-pressure (P) behaviour of zeolites, including zeolitewater interaction, phase transitions, ion mobility, has been a topic of extensive investigations in the last decade [2][3][4][5][6][7][8], which revealed a number of unusual properties. An excellent example is P-induced additional hydration (over-hydration) of small pores of natrolite and related fibrous zeolites [9][10][11][12], leading to the doubling of water content and associated volume expansion by about 4-5% at 1-2 GPa. Such an excess hydration was shown to result in an appreciable increase of the diffusion mobility of H 2 O molecules [3], and thereby it provides large opportunities for various applications of this phenomenon.…”

Section: Introductionmentioning

confidence: 99%

Non-hydrostatic compression of zeolite NaA in water medium: connection to anomalous conductivity

Likhacheva¹,

Малышев²,

Manakov³

et al. 2009

Zeitschrift Für Kristallographie

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Zeolite NaA / High pressure / Compressibility / Over-hydration / Powder diffraction structure analysis / X-ray diffraction Abstract. High-pressure synchrotron X-ray powder diffraction measurements of a synthetic zeolite NaA were carried out up to 2.5 GPa using pure water as pressure-transmitting (P) medium to provide non-hydrostatic (wet) conditions in a diamond anvil cell. The compressibility of wet zeolite NaA is similar to that measured at hydrostatic compression in water within the P-range 0-0.8 GPa, whereas between 1-2 GPa the zeolite becomes slightly more compressible and progressively amorphizes due to the non-hydrostatic conditions. Rietveld refinement at 0.37 GPa reveals a selective additional filling of the H 2 O sites in a-and b-cage, leading to about 30% increase of the total water content. The over-hydrated state of the zeolite is partially preserved after the pressure release. The over-hydration of zeolite pores, combined with a partial disordering at the onset of amorphization, apparently provides necessary conditions for the P-induced enhancement of water-cationic diffusion and the corresponding increase of ionic conductivity observed in zeolite NaA in non-hydrostatic water medium.

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Structural evolution of natrolite during over-hydration: a high-pressure neutron diffraction study

Cited by 45 publications

References 14 publications

Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

Zeolites at high pressure: A review

Non-hydrostatic compression of zeolite NaA in water medium: connection to anomalous conductivity

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