Structural changes in nanoporous solids due to fluid adsorption: thermodynamic analysis and Monte Carlo simulations

Jeffroy, Marie; Fuchs, Alain H.; Boutin, Anne

doi:10.1039/b805117h

Cited by 39 publications

(70 citation statements)

References 31 publications

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“…More recent experimental work on the deformation of carbons during the adsorption of different gases has been reported by Fomkin and co-workers [6][7][8] and a dilatometric investigation of the deformation of carbon xerogels has been made by Balzer and co-workers [9] who concluded that micropores in the adsorbents made the most significant contribution to the expansion and contraction of these materials. Recognizing the significance of the effect of adsorption-induced deformation, more attention is paid on this phenomenon for various systems beside carbonaceous materials, such as porous glass [10], zeolites [11], silica gels [12], porous silicon [13,14] and metal-organic frameworks (MOFs) [15,16]. A review of the general area of adsorption deformation has been published by Tvardovski [17].…”

Section: Introductionmentioning

confidence: 99%

Solid deformation induced by the adsorption of methane and methanol under sub- and supercritical conditions

Nguyen

Nicholson

2012

Journal of Colloid and Interface Science

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Section: Introductionmentioning

confidence: 99%

Solid deformation induced by the adsorption of methane and methanol under sub- and supercritical conditions

Nguyen

Nicholson

2012

Journal of Colloid and Interface Science

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“…78,79 The osmotic free energy can be also obtained by another pathway, i.e., the integration of the adsorption isotherm with respect to the chemical potential, and this method has been applied to investigate the adsorption-induced structural transition of zeolites. [90][91][92] In contrast to the direct simulation method, free-energy analysis can represent the equilibrium behavior of the adsorption-induced structural transition successfully, but there are some limitations. One is the impossibility of reproducing the dynamics of the deformation, and the other is the difficulty of quantitatively determining the hysteretic behavior.…”

Section: Introductionmentioning

confidence: 99%

Simulation study for adsorption-induced structural transition in stacked-layer porous coordination polymers: Equilibrium and hysteretic adsorption behaviors

Numaguchi

Tanaka

Watanabe

et al. 2013

The Journal of Chemical Physics

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We conduct grand canonical Monte Carlo simulations and a free-energy analysis for a simplified model of a stacked-layer porous coordination polymer to understand the gate phenomenon, which is a structural transition of a host framework induced by the adsorption of guest particles. Our calculations demonstrate that stabilization of the system due to the guest adsorption causes host deformation under thermodynamic equilibrium. We also investigate spontaneous transition behaviors (gate opening and closing under metastable conditions). The structural transition should occur when the required activation energy, which is determined using the free-energy analysis, becomes equal to the system energy fluctuation. To estimate the system energy fluctuation, we construct a kinetic transition model based on the transition state theory. In this model, the system energy fluctuation can be calculated by setting the adsorption time and transition domain size of the host framework. The model demonstrates that a smaller domain size results in a gate-opening transition at lower pressure. Furthermore, we reveal that the slope of the logarithm of the equilibrium structural transition pressure versus reciprocal temperature shows transition enthalpy, and that slopes of the gate-opening and -closing transition pressures versus reciprocal temperature show activation enthalpies.

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“…One of the few examples of zeolites where flexibility has a known influence on adsorption is silicalite-1. This material was shown to possess three different crystalline structures, [25] with almost the same unit cell volumes (~0.6 % difference), between which adsorption-induced transitions were observed. [25,26] Other known flexible zeolites display this flexibility in other ways, including reversible shrinking of the framework upon solvent removal (e.g.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Methods and Models to Study Flexible Metal–Organic Frameworks

et al. 2011

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Much attention has recently been focused on a fascinating subclass of metal-organic frameworks that behave in a remarkable stimuli-responsive fashion. These soft porous crystals feature dynamic crystalline frameworks displaying reversible, large-amplitude structural deformations under external physical constraints such as temperature, electric field or gas exposure. The number of reported syntheses of such materials is rapidly growing and they are promising for practical applications, such as gas capture, purification and fluid separation. Herein, we summarize the recently developed thermodynamic tools that can help understand the process of fluid adsorption and fluid mixture coadsorption in these flexible nanoporous materials. These tools, which include both molecular simulation methods and analytical models, can help rationalize experimental results and predict adsorption properties over a wide range of thermodynamic conditions. A particular focus is given on how these methods can guide the experimental exploration of a large number of materials and working conditions (temperature, pressure, composition) to help design efficient processes relying on fluid adsorption in soft porous crystals.

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Structural changes in nanoporous solids due to fluid adsorption: thermodynamic analysis and Monte Carlo simulations

Abstract: A thermodynamic analysis based on the osmotic ensemble scheme enables the prediction of structural changes occurring in silicalite-1 zeolite upon halocarbon molecule adsorption.

Cited by 39 publications

References 31 publications

Solid deformation induced by the adsorption of methane and methanol under sub- and supercritical conditions

Solid deformation induced by the adsorption of methane and methanol under sub- and supercritical conditions

Simulation study for adsorption-induced structural transition in stacked-layer porous coordination polymers: Equilibrium and hysteretic adsorption behaviors

Thermodynamic Methods and Models to Study Flexible Metal–Organic Frameworks

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