High-pressure synthesis of a polyethylene/zeolite nano-composite material

Santoro, Mario; Gorelli, Federico A.; Bini, Roberto; Haines, J.; Lee, Arie van der

doi:10.1038/ncomms2564

Cited by 68 publications

(75 citation statements)

References 40 publications

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“…One reason for this interest is that high pressures, combined with the confining environments of nanometric pores, may reveal unexpected chemical phenomena (e.g., pressure-induced hydration [67][68][69][70][71][72][73][74][75][76][77][78][79][80][81][82], ionic conductivity [83], guest exchange [84][85][86][87][88], or realization of new materials otherwise unattainable [89][90][91][92][93][94][95][96][97]). With this paper we would like to answer the question: how do confined supramolecular assemblies of water and chromophores respond to compression?…”

Section: Introductionmentioning

confidence: 99%

Unravelling the High-Pressure Behaviour of Dye-Zeolite L Hybrid Materials

et al. 2018

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Self-assembly of chromophores nanoconfined in porous materials such as zeolite L has led to technologically relevant host-guest systems exploited in solar energy harvesting, photonics, nanodiagnostics and information technology. The response of these hybrid materials to compression, which would be crucial to enhance their application range, has never been explored to date. By a joint high-pressure in situ synchrotron X-ray powder diffraction and ab initio molecular dynamics approach, herein we unravel the high-pressure behaviour of hybrid composites of zeolite L with fluorenone dye. High-pressure experiments were performed up to 6 GPa using non-penetrating pressure transmitting media to study the effect of dye loading on the structural properties of the materials under compression. Computational modelling provided molecular-level insight on the response to compression of the confined dye assemblies, evidencing a pressure-induced strengthening of the interaction between the fluorenone carbonyl group and zeolite L potassium cations. Our results reveal an impressive stability of the fluorenone-zeolite L composites at GPa pressures. The remarkable resilience of the supramolecular organization of dye molecules hyperconfined in zeolite L channels may open the way to the realization of optical devices able to maintain their functionality under extreme conditions.

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Section: Introductionmentioning

confidence: 99%

Unravelling the High-Pressure Behaviour of Dye-Zeolite L Hybrid Materials

et al. 2018

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“…Among these, the possibility of HP-induced polymerization has recently been demonstrated for acetylene and ethylene inserted into the MFI framework. 24,25 Pressure is the most efficient means to reduce intermolecular distances, thereby allowing chemical reactions to occur. 25 The studies performed with 'non-penetrating' media highlighted the crucial influence of the framework type and composition, and the extra-framework content, on zeolite's response to pressure in terms of deformation mechanism and compressibility.…”

Section: Introductionmentioning

confidence: 99%

“…24,25 Pressure is the most efficient means to reduce intermolecular distances, thereby allowing chemical reactions to occur. 25 The studies performed with 'non-penetrating' media highlighted the crucial influence of the framework type and composition, and the extra-framework content, on zeolite's response to pressure in terms of deformation mechanism and compressibility. 2,5,[10][11][12] Zeolite compressibility does not appear to be directly related to the material porosity, but is more closely related to the characteristics of the extra-framework cations and the number of H 2 O molecules.…”

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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“…This finding is surprising since, as already observed, confined PE is highly strained and should pull towards more compact volumes. 3 The binding energy also slightly drives towards more contracted geometry.…”

Section: Figurementioning

confidence: 99%