Elastic behavior of MFI-type zeolites: 3 – Compressibility of silicalite and mutinaite

Quartieri, Simona; Arletti, Rossella; Vezzalini, Giovanna; Renzo, Francesco Di; Dmitriev, Vladimir

doi:10.1016/j.jssc.2012.03.039

Cited by 21 publications

(49 citation statements)

References 30 publications

(44 reference statements)

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“…In fact, in the same P range, the volume variation is about 5% for silicalite-1 F and silicalite-1 OH, 9 2.6% for siliceous Y, 69 and 3.96% for Si-ferrierite. 68 Since MOR has a 'framework density' (FD 47 ) much higher than zeolite Y (17.2 and 12.7, respectively), these results confirm once again that zeolite compressibility is not simply related to the material porosity.…”

Section: Discussionmentioning

confidence: 89%

“…As a consequence, some zeolites characterized by large pores can be unexpectedly less compressible than other pure-Si phases with empty cavities. Various authors [7][8][9][10][11][12][13] came to the same conclusions working on materials sharing the same framework type, but with different extra-frameworks and framework compositions. The compression of zeolites using non-penetrating media has also been exploited to induce the so-called ''pressureinduced amorphization'' (PIA).…”

Section: Introductionmentioning

confidence: 90%

“…ref. [4][5][6][7][8][9][10][11][12][13]. High-pressure studies performed using pore penetrating media have attracted great attention because of the so-called pressure-induced hydration effect (PIH), 14 in which the water content inside the cavity increases in response to the applied pressure through selective sorption of H 2 O molecules from the PTM.…”

Section: Introductionmentioning

confidence: 99%

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Pressure-induced penetration of guest molecules in high-silica zeolites: the case of mordenite

Arletti

Leardini

Vezzalini

et al. 2015

Phys. Chem. Chem. Phys.

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A synthetic high-silica mordenite (HS-MOR) has been compressed in both non-penetrating (silicone oil, s.o.) and penetrating [methanol : ethanol : water (16 : 3 : 1) (m.e.w.), water : ethanol (3 : 1) (w.e.), and ethylene glycol (e.gl.)] pressure transmitting media (PTM). In situ high-pressure (HP) synchrotron X-ray powder diffraction (XRPD) experiments allowed the unit cell parameters to be followed up to 1.6, 1.8, 8.4, and 6.7 GPa in s.o., w.e., m.e.w., and e.gl., respectively. Moreover, e.gl. was also used as a PTM in in situ HP Raman and ex situ IR experiments. The structural refinement of HS-MOR compressed in e.gl.at 0.1 GPa -the lowest investigated pressure -revealed the presence of 3.5 ethylene glycol molecules per unit cell. The infrared spectrum of the recovered sample, after compression to 1 GPa, is consistent with the insertion of ethylene glycol molecules in the pores. XRPD and Raman spectroscopy experiments performed under pressure indicated the insertion of a small number of guest molecules. Ethylene glycol is partially retained inside mordenite upon pressure release. A symmetry lowering was observed in s.o. above 0.8 GPa, while above 1.6 GPa the patterns indicated a rapid loss of long range order. From ambient pressure (P amb ) to 1.6 GPa, a high cell volume contraction (DV = À9.5%) was determined. The patterns collected with penetrating PTM suggested the penetration of guest molecules into the porous host matrix, starting from a very low P regime. The entrapment of PTM molecules inside micropores contributes to the stiffening of the structure and, as a consequence, to the decrease of the compressibility with respect to that measured in s.o. From the structural point of view, HS-MOR reacts to compression and to the penetration of different guest species with appropriate framework deformations. Interestingly, ethylene glycol is partially retained inside mordenite upon pressure release, which is of importance for potential application of this composite material.

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Section: Discussionmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Pressure-induced penetration of guest molecules in high-silica zeolites: the case of mordenite

Arletti

Leardini

Vezzalini

et al. 2015

Phys. Chem. Chem. Phys.

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“…The former are usually aqueous/alcohol mixtures, with molecular sizes small enough to penetrate the zeolite porosities (see for example [15] and [16] for a review); the latter are usually silicone oil or glycerol, with molecules too large to penetrate the zeolite (see e.g. [14,[17][18][19][20][21][22][23][24]). While non-penetrating PTM are mainly used to study zeolite compressibility, Pinduced phase transitions, and amorphization, the penetrating ones can be usefully exploited for investigating the so-called pressure induced hydration (PIH) effect [25], which consists in the penetration of additional H 2 O molecules into the zeolite channels.…”

Section: Introductionmentioning

confidence: 99%

“…The interest in the confinement of water in nanoscopic spaces, like zeolitic cavities, stems from the fact that the properties of confined water are believed to be very different from those of the bulk fluid. Finally, it has been shown that the intrusion of extra-guest species into zeolite cavities also has important consequences on the overall elastic behavior of the material, since the new guest molecules generally contribute to stiffening the structure and countering P-induced deformations [18,23,24,[27][28][29].…”

Section: Introductionmentioning

confidence: 99%

Pressure-induced water intrusion in FER-type zeolites and the influence of extraframework species on structural deformations

Arletti

Vezzalini

Quartieri

et al. 2014

Microporous and Mesoporous Materials

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The response to pressure of a natural ferrierite from Monastir (Sardinia, Italy) (Mon-FER) and of the synthetic all-silica phase (Si-FER) was investigated by means of in-situ synchrotron X-ray powder diffraction in the presence of penetrating (methanol:ethanol:water 16:3:1, m.e.w.) and non-penetrating (silicone oil, s.o.) pressure transmitting media (PTM). The following aspects are discussed: i) the penetration of extra-water molecules into the all-silica phase and the related structural aspects involving both framework and extraframework systems; ii) the influence of the zeolite composition and of the different PTM used in the compression experiments on the overall elastic parameters of the two investigated samples; iii) the elastic parameters and the unit cell P-induced deformations of the mineral phase; iv) the reversibility extents of the observed phenomena. Evidence of water penetration during compression of Si-FER in m.e.w. was found. The refinement performed at 0.2 GPa enabled location of 15 water molecules forming bulk-like and monodimensional water clusters. No methanol or ethanol penetration was observed. The results demonstrate that the free volume of the porous material is not the only parameter influencing water condensation since applied pressure is an additional fundamental factor. The bulk modulus value calculated from Pamb to 4.9 GPa for Mon-FER (K0 =44 GPa, Kp=0.2) is intermediate between the lowest (about 14 GPa) and the highest (about 72 GPa) values determined to date for zeolites compressed in non-penetrating PTM. The highest P-induced deformations are observed for Si-FER compressed in s.o. In general, higher rigidity for the natural sample was found in both media. All the reviewers requests were fulfilled: the references were corrected and the keywords were added after the abstract. UNIVERSITA' DEGLI STUDI DI TORINO Dipartimento di Scienze della TerraWe hope that now our paper will be suitable for publication. Best regard Rossella Arletti List of Revisions Highlights Penetration of 15 water molecules in synthetic Si-FER compressed in m.e.w was found. Eleven water molecules in the 10MR channels, forming bulk-like clusters. Four molecules were located in the FER cage as monodimensional clusters. Natural FER shows higher rigidity in m.e.w. and s.o. respect to the synthetic one. The presence of extraframework species in natural FER stiffens the structure. *Highlights (for review) *Graphical Abstract (for review) Pressure-induced water intrusion in FER-type zeolites and the influence of extraframework species on structural deformations AbstractThe response to pressure of a natural ferrierite from Monastir (Sardinia, Italy) (Mon-FER)and of the synthetic all-silica phase (Si-FER) was investigated by means of in-situ synchrotron Xray powder diffraction in the presence of penetrating (methanol:ethanol:water 16:3:1, m.e.w.) and non-penetrating (silicone oil, s.o.) pressure transmitting media (PTM). The following aspects are discussed: i) the penetration of extra-H 2 O molecules into t...

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Crystal structure and chemical composition of compounds with MFI type zeolite frameworks

Baur¹,

Fischer

2017

Microporous and Other Framework Materials With Zeolite-Type Structures

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Elastic behavior of MFI-type zeolites: 3 – Compressibility of silicalite and mutinaite

Cited by 21 publications

References 30 publications

Pressure-induced penetration of guest molecules in high-silica zeolites: the case of mordenite

Pressure-induced penetration of guest molecules in high-silica zeolites: the case of mordenite

Pressure-induced water intrusion in FER-type zeolites and the influence of extraframework species on structural deformations

Crystal structure and chemical composition of compounds with MFI type zeolite frameworks

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