Breathing Transitions in MIL‐53(Al) Metal–Organic Framework Upon Xenon Adsorption

Boutin, Anne; Springuel‐Huet, Marie‐Anne; Nossov, Andreï; Gédéon, A.; Loiseau, Thierry; Volkringer, Christophe; Férey, Gérard; Coudert, François‐Xavier; Fuchs, Alain H.

doi:10.1002/anie.200903153

Cited by 185 publications

(226 citation statements)

References 27 publications

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“…10), with a volume within a wide range (V int = 1170 − 1300Å 3 ) and which also includes adsorbed particles. We will compare our results with the experimental and theoretical study of Boutin et al [15], in which this phase is denoted as np. However we will denote this phase as int, to make the distinction with the empty np phase and to be consistent with the work of Bousquet et al [16][15].…”

Section: Xenon Adsorption In Mil-53(al)mentioning

confidence: 80%

“…However we will denote this phase as int, to make the distinction with the empty np phase and to be consistent with the work of Bousquet et al [16][15]. Boutin et al [15] used the thermodynamic model of Coudert et al [17] to determine the relative stability of two phases with a well defined volume: a large pore with a volume V lp = 1419Å 3 and a intermediate pore with a volume that is 23.5 % smaller than the lp volume (V int = 1085Å 3 ).…”

Section: Xenon Adsorption In Mil-53(al)mentioning

confidence: 90%

“…One must however be careful when rationalizing breathing solely on basis of potential energy curves at 0 K. The occurrence of certain macroscopically observed phases is a result of a thermodynamic process and thus one should describe the phenomenon in the correct thermodynamic ensemble. Boutin et al studied the breathing behavior of MIL-53(Al) upon Xenon adsorption and found breathing transitions in the measured adsorption isotherms in the temperature range 195 − 323 K [15]. They also developed a thermodynamic model to explain the observed behavior of the material.…”

Section: Mil-53(al)mentioning

confidence: 99%

“…The minimizations towards volume and number of adsorbed particles are not performed simultaneously but in two subsequent steps, allowing to compute intermediate volume-dependent contributions to the osmotic potential and unravel the physical processes that lie at the basis of breathing. The semi-analytical model is tested on two well known case studies : the MIL-53(Cr) for which a phase transition was observed upon adsorption of CO 2 at room temperature while this was not the case for CH 4 and MIL-53(Al) for which recently new data appeared on the breathing behavior upon Xenon adsorption [15].…”

Section: Mil-53(al)mentioning

confidence: 99%

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Semi-analytical mean-field model for predicting breathing in metal–organic frameworks

Vanduyfhuys

Ghysels

Rogge

et al. 2015

Molecular Simulation

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A new semi-analytical mean-field model is proposed to rationalize breathing of MIL-53 type materials. The model is applied on two case studies, the guest-induced breathing of MIL-53(Cr) with CO 2 and CH 4 , and the phase transformations for MIL-53(Al) upon xenon adsorption. Experimentally, MIL-53(Cr) breathes upon CO 2 adsorption, which was not observed for CH 4 . This result could be ascribed to the stronger interaction of carbon dioxide with the host matrix. For MIL-53(Al) a phase transition from the large pore phase could be enforced to an intermediate phase with volumes of about 1160 − 1300Å 3 , which corresponds well to the phase observed experimentally upon xenon adsorption. Our thermodynamic model correlates nicely with the adsorption pressure model proposed by Coudert et al. Furthermore the model can predict breathing behavior of other flexible materials, if the user can determine the free energy of the empty host, the interaction energy between a guest molecule and the host matrix and the pore volume accessible to the guest molecules. This will allow to generate the osmotic potential from which the equilibria can be deduced and the anticipated experimentally observed phase may be predicted.

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Section: Xenon Adsorption In Mil-53(al)mentioning

confidence: 80%

Section: Xenon Adsorption In Mil-53(al)mentioning

confidence: 90%

Section: Mil-53(al)mentioning

confidence: 99%

Section: Mil-53(al)mentioning

confidence: 99%

See 2 more Smart Citations

Semi-analytical mean-field model for predicting breathing in metal–organic frameworks

Vanduyfhuys

Ghysels

Rogge

et al. 2015

Molecular Simulation

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show abstract

“…73 This large scale rearrangement of molecular building blocks and crystal lattice is challenging to computationally predict, and this has not yet been reported for PMMs. However, CSP techniques can identify additional polymorphs lying close in energy, and therefore hypothetically accessible, and solvent stabilisation effects on hypothetical polymorphs assessed in an attempt to identify solvents that can stabilise a given structure.…”

mentioning

confidence: 99%

Application of computational methods to the design and characterisation of porous molecular materials

et al. 2017

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Composed from discete units, porous molecular materials (PMMs) possess unique properties not observed for conventional, extended, solids, such as solution processibility and permanent porosity in the liquid phase. However, identifying the origin of porosity is not a trivial process, especially for amorphous or liquid phases. Furthermore, the assembly of molecular components is typically governed by a subtle balance of weak intermolecular forces that makes structure prediction challenging. Accordingly, in this review we canvass the crucial role of molecular simulations in the characterisation and design of PMMs. We will outline strategies for modelling porosity in crystalline, amorphous and liquid phases and also describe the state-of-the-art methods used for high-throughput screening of large datasets to identify materials that exhibit novel performance characteristics.

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Metal‐Organic Frameworks: Aluminium‐Based Frameworks

Stock

2014

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Metal–organic frameworks (MOFs) containing light and environmentally benign metals have attracted researchers from industry and academia since they are believed to be well suited for applications especially in the field of gas storage. Aluminum is one element of choice for the synthesis of such MOFs since it leads to stable and highly porous materials that can also be formed in water as a green solvent. The stability and the small number of Al‐based MOFs stems from the same factors: the high charge (+3) of the metal ion and the small ionic radius. Hence dissolution of these MOFs in water is often kinetically hindered and at the same time they are almost exclusively obtained as microcrystalline products. The latter fact has impeded the structure elucidation and the determination of structure property relationships and hence the intensive investigation of this class of compounds. Recent progress in the synthesis and characterization of Al‐MOFs has demonstrated that certain structural motifs are predominantly observed, depending on the substitution pattern of the polycarboxylate based linker molecules and the solvent employed. Here, the synthesis and structural trends in Al‐based MOFs are summarized.

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Breathing Transitions in MIL‐53(Al) Metal–Organic Framework Upon Xenon Adsorption

Abstract: Porous metal-organic frameworks (MOFs) are a topical class of materials that display an extremely large range of crystal structures and host-guest properties, potentially giving them a major impact in many areas of science and technology.

Cited by 185 publications

References 27 publications

Semi-analytical mean-field model for predicting breathing in metal–organic frameworks

Semi-analytical mean-field model for predicting breathing in metal–organic frameworks

Application of computational methods to the design and characterisation of porous molecular materials

Metal‐Organic Frameworks: Aluminium‐Based Frameworks

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