High-pressure behavior of synthetic mordenite-Na: an in situ single-crystal synchrotron X-ray diffraction study

Lotti, Paolo; Gatta, G. Diego; Merlini, Marco; Liermann, Hanns‐Peter

doi:10.1515/zkri-2014-1796

Cited by 19 publications

(13 citation statements)

References 30 publications

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“…This behavior suggests that the strain of the borate chain along the a ‐axis (i.e., the less compressible direction among the three crystallographic axes) is accommodated by the tilting of the three‐membered rings around the shared O2 hinges. This is a common mechanism of strain accommodation adopted by different classes of materials, as, for example, the open‐framework silicates …”

Section: Resultsmentioning

confidence: 99%

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High‐pressure behavior and P‐induced phase transition of CaB₃O₄(OH)₃·H₂O (colemanite)

et al. 2017

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Colemanite (ideally CaB3O4(OH)3·H2O, space group P21/a, unit‐cell parameters: a ~ 8.74, b ~ 11.26, c ~ 6.10 Å, β ~ 110.1°) is one of the principal mineralogical components of borate deposits and the most important mineral commodity of boron. Its high‐pressure behavior is here described, for the first time, by means of in situ single‐crystal synchrotron X‐ray diffraction with a diamond anvil cell up to 24 GPa (and 293 K). Colemanite is stable, in its ambient‐conditions polymorph, up to 13.95 GPa. Between 13.95 and 14.91 GPa, an iso‐symmetric first‐order single‐crystal to single‐crystal phase transition (reconstructive in character) toward a denser polymorph (colemanite‐II) occurs, with: aCOL‐II=3·aCOL, bCOL‐II=bCOL, and cCOL‐II=2·cCOL. Up to 13.95 GPa, the bulk compression of colemanite is accommodated by the Ca‐polyhedron compression and the tilting of the rigid three‐membered rings of boron polyhedra. The phase transition leads to an increase in the average coordination number of both the B and Ca sites. A detailed description of the crystal structure of the high‐P polymorph, compared to the ambient‐conditions colemanite, is given. The elastic behaviors of colemanite and of its high‐P polymorph are described by means of III‐ and II‐order Birch‐Murnaghan equations of state, respectively, yielding the following refined parameters: KV0=67(4) GPa and KV′=5.5(7) [βV0=0.0149(9) GPa−1] for colemanite; KV0=50(8) GPa [βV0=0.020(3) GPa−1] for its high‐P polymorph.

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Section: Resultsmentioning

confidence: 99%

“…This is a common mechanism of strain accommodation adopted by different classes of materials, as, for example, the open-framework silicates. [46][47][48]…”

Section: High-pressure Behavior Of Colemanitementioning

confidence: 99%

High‐pressure behavior and P‐induced phase transition of CaB₃O₄(OH)₃·H₂O (colemanite)

et al. 2017

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“…The framework composition profoundly affects the uptake of the pressure medium in the zeolite channels, as demonstrated by several experiments ,,,. Whereas it was not possible to incorporate ethanol and methanol inside Na‐mordenite – which already contained six Na + and 19 H 2 O in the unit cell,, Arletti et al . reported the intrusion of these molecules into the empty pores of all silica mordenite ,…”

Section: Organized Materials By High‐pressure Confinementmentioning

confidence: 99%

Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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Empty spaces are abhorred by nature, which immediately rushes in to fill the void. Humans have learnt pretty well how to make ordered empty nanocontainers, and to get useful products out of them. When such an order is imparted to molecules, new properties may appear, often yielding advanced applications. This review illustrates how the organized void space inherently present in various materials: zeolites, clathrates, mesoporous silica/organosilica, and metal organic frameworks (MOF), for example, can be exploited to create confined, organized, and self-assembled supramolecular structures of low dimensionality. Features of the confining matrices relevant to organization are presented with special focus on molecular-level aspects. Selected examples of confined supramolecular assemblies - from small molecules to quantum dots or luminescent species - are aimed to show the complexity and potential of this approach. Natural confinement (minerals) and hyperconfinement (high pressure) provide further opportunities to understand and master the atomistic-level interactions governing supramolecular organization under nanospace restrictions.

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“…A similar result has recently been reported by Lotti and coworkers for a Na-mordenite, compressed in 4 : 1 methanol : ethanol between 1.68(7) and 2.70(8) GPa. 55 The authors suggest a lowering from Cmcm to Pbnm or Pbnn s.g. (or from Cmc2 1 to Pbn2 1 when starting from the acentric Cmc2 1 s.g.). In the present case, the best fit was obtained assuming the Pbnm and Pbn2 1 s.g.…”

Section: Pccp Papermentioning

confidence: 99%

“…54 A further HP study performed on the same Na-mordenite sample by in situ single-crystal synchrotron XRD, using a 4 : 1 methanol : ethanol mixture as PTM, showed a phase transition from a C-centered to a primitive space group: possibly Pbnm, Pbnn or Pbn2 1 -probably displacive in character -between 1.68(7) and 2.70(8) GPa. 55 The structural refinements enabled the description of the deformation mechanisms in the low-P regime: bulk compression is greatly accommodated by increasing the ellipticity of the large 12-membered ring channels running along [001]. The authors suggest that the higher compressibility observed for the sample in methanol and ethanol, compared to that observed in m.e.w., might be because of the latter sample undergoing a P-induced over-hydration effect.…”

Section: Introductionmentioning

confidence: 99%

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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High-pressure behavior of synthetic mordenite-Na: an in situ single-crystal synchrotron X-ray diffraction study

Cited by 19 publications

References 30 publications

High‐pressure behavior and P‐induced phase transition of CaB₃O₄(OH)₃·H₂O (colemanite)

High‐pressure behavior and P‐induced phase transition of CaB₃O₄(OH)₃·H₂O (colemanite)

Supramolecular Organization in Confined Nanospaces

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

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High-pressure behavior of synthetic mordenite-Na: an in situ single-crystal synchrotron X-ray diffraction study

Cited by 19 publications

References 30 publications

High‐pressure behavior and P‐induced phase transition of CaB3O4(OH)3·H2O (colemanite)

High‐pressure behavior and P‐induced phase transition of CaB3O4(OH)3·H2O (colemanite)

Supramolecular Organization in Confined Nanospaces

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

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High‐pressure behavior and P‐induced phase transition of CaB₃O₄(OH)₃·H₂O (colemanite)

High‐pressure behavior and P‐induced phase transition of CaB₃O₄(OH)₃·H₂O (colemanite)