High Pressure Polymerization in a Confined Space: Conjugated Chain/Zeolite Nanocomposites

Scelta, Demetrio; Ceppatelli, Matteo; Santoro, Mario; Bini, Roberto; Gorelli, Federico A.; Perucchi, A.; Mézouar, M.; Lee, Arie van der; Haines, J.

doi:10.1021/cm500061f

Cited by 51 publications

(51 citation statements)

References 51 publications

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“…IR/Raman spectroscopy and X‐ray diffraction showed that the host‐guest compound, after ambient pressure recovery, contained polyethylene chains and had a greater bulk modulus than silicalite due to the filling of the pores (Figure a). Using the same zeolite as confining matrix, the same group performed the pressure‐driven‐only polymerization of acetylene: compression up to ∼4 GPa (without light irradiation) induced the penetration of the molecules in silicalite and their polymerization to polyacetylene chains running along the zeolite channels (Figure b) …”

Section: Organized Materials By High‐pressure Confinementmentioning

confidence: 99%

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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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Section: Organized Materials By High‐pressure Confinementmentioning

confidence: 99%

“…In this case, the self‐assembly process is controlled by both the confining matrix and the imposed pressure. Recently observed phenomena such as pressure‐induced polymerization or formation of complex supramolecular patterns candidate hyperconfinement as an intriguing route to new materials.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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“…It was shown that the application of external pressure produces the shortening of the intermolecular distances of confined organic molecules (e.g. ethylene, acetylene) hosted in zeolite channels, inducing polymerization reactions without catalysts or radical initiators [15,16] and contributing to stiffen the structure [17e19].…”

Section: Introductionmentioning

confidence: 99%

Compressibility and crystal–fluid interactions in all-silica ferrierite at high pressure

Lotti

Arletti

Gatta

et al. 2015

Microporous and Mesoporous Materials

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a b s t r a c tThe high-pressure behavior of a synthetic siliceous ferrierite has been studied by in situ single-crystal and powder synchrotron X-ray diffraction with a diamond anvil cell, using four different P-transmitting fluids: the non-penetrating silicone oil and the potentially pore-penetrating methanol:ethanol:H 2 O ¼ 16:3:1 mixture, ethylene glycol and 2methyl-2propen-1ol. The high-pressure experiment in silicone oil shows a remarkable flexibility of the FER framework. Two displacive phase transitions, following the path Pmnn-to-P12 1 /n1-to-P2 1 /n11 with pressure, were observed. The three polymorphs were found to share a virtually identical bulk compressibility, though showing a different anisotropic pattern. The experiments with potentially penetrating media enhanced the occurrence of a complex scenario, from which the P-induced intrusion of fluid molecules into the FER structural voids can be assumed by the different phase-transition paths and compressibility patterns, by the calculated residual electron density and by the different deformation mechanisms at the atomic scale, observed as a function of the used medium. The starting orthorhombic polymorph was always restored upon decompression in all the experiments. The roles of the different surface area in single crystal and polycrystalline samples, and of the process kinetics on the compressibility and crystalefluid interactions, are discussed.

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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%

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 Polymerization in a Confined Space: Conjugated Chain/Zeolite Nanocomposites

Abstract: International audienc

Cited by 51 publications

References 51 publications

Supramolecular Organization in Confined Nanospaces

Supramolecular Organization in Confined Nanospaces

Compressibility and crystal–fluid interactions in all-silica ferrierite at high pressure

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

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