Comparative Guest, Thermal, and Mechanical Breathing of the Porous Metal Organic Framework MIL-53(Cr): A Computational Exploration Supported by Experiments

Ghoufi, Aziz; Subercaze, Alexandre; Ma, Quanyu; Yot, Pascal G.; Ke, Yanxiong; Puente‐Orench, Inés; Devic, Thomas; Guillerm, Vincent; Zhong, Chongli; Serre, Christian; Férey, Gérard; Maurin, Guillaume

doi:10.1021/jp303686m

Cited by 96 publications

(135 citation statements)

References 39 publications

Supporting

Mentioning

127

Contrasting

Order By: Relevance

“…Several other force fields also exist that present two distinct minima for the chromium variant of MIL-53. [7,14] These theoretical calculations gave seminal insight into the nanoscale interactions enforcing breathing. 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.…”

Section: Mil-53(al)mentioning

confidence: 99%

“…. Depending on the specific nature of the material, various stimuli were found to induce the breathing such as temperature [6][7][8], pressure [7,9], guest molecules [5,7,10], . .…”

Section: Introductionmentioning

confidence: 99%

“…MIL-53(Cr) is found in its large-pore shape at low pressure and ambient temperature. Mechanical pressure can induce a transition to its narrow-pore (np) shape [7]. Gas adsorption can also cause an lp to np transition and, surprisingly, subsequently an np to lp transition at higher gas pressures.…”

Section: Introductionmentioning

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

View full text Add to dashboard Cite

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.

show abstract

Section: Mil-53(al)mentioning

confidence: 99%

“…. Depending on the specific nature of the material, various stimuli were found to induce the breathing such as temperature [6][7][8], pressure [7,9], guest molecules [5,7,10], . .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Vanduyfhuys

Ghysels

Rogge

et al. 2015

Molecular Simulation

View full text Add to dashboard Cite

show abstract

“…58 Moreover, exible MOFs are also promising for the absorption of shocks or for the storage of other forms of mechanical energy because of their structural transitions at moderate pressures of several tens of MPa. 59 64 Hence, to aid their further development, a complete understanding of the mechanical behaviour of MOFs over a broad range of pressures is essential.…”

Section: Introductionmentioning

confidence: 99%

A Comparison of Barostats for the Mechanical Characterization of Metal–Organic Frameworks

Rogge

Vanduyfhuys

Ghysels

et al. 2015

J. Chem. Theory Comput.

Self Cite

167

View full text Add to dashboard Cite

In this paper, three barostat coupling schemes for pressure control, which are commonly used in molecular dynamics simulations, are critically compared to characterise the rigid MOF-5 and the exible MIL-53(Al) metal-organic frameworks. We investigate the performance of the three barostats, the Berendsen, the Martyna-Tuckerman-TobiasKlein (MTTK) and the Langevin coupling methods, in reproducing the cell parameters and the pressure versus volume behaviour in isothermal-isobaric simulations. A thermodynamic integration method is used to construct the free energy pro les as a function of volume at nite temperature. It is observed that the aforementioned static properties are well reproduced with the three barostats. However, for static properties depending nonlinearly on the pressure, the Berendsen barostat might give deviating results as it suppresses pressure uctuations more drastically. Finally, dynamic properties, which *

show abstract

“…1 MOFs offer a wide range of physico-chemical properties, especially noted for their high surface area combined with chemical tunability 2 and framework flexibility. 3 Fabrication of MOF-based membranes and thin-film coatings has provided novel platforms for emergent technologies encompassing gas separation, water purification, sensors, and low-k dielectrics. [4][5][6][7] Polyimides are ideal for membrane applications by virtue of their high gas permeability and intrinsic permselectivity (e.g., CO 2 /N 2 , H 2 /CO 2 , and H 2 /CH 4 ) compared to polycarbonate, polysulfone, and other polymeric materials.…”

mentioning

confidence: 99%

Fine-scale tribological performance of zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes

et al. 2014

View full text Add to dashboard Cite

We combined zeolitic imidazolate framework nanoparticles (ZIF-8: ˜150 nm diameter) with Matrimid® 5218 polymer to form permeable mixed matrix membranes, featuring different weight fractions of nanoparticles (up to 30 wt. % loading). We used ball-on-disc micro-tribological method to measure the frictional coefficient of the nanocomposite membranes, as a function of nanoparticle loading and annealing heat treatment. The tribological results reveal that the friction and wear of the unannealed samples rise steadily with greater nanoparticle loading because ZIF-8 is relatively harder than the matrix, thus promoting abrasive wear mechanism. After annealing, however, we discover that the nanocomposites display an appreciably lower friction and wear damage compared with the unannealed counterparts. Evidence shows that the major improvement in tribological performance is associated with the greater amounts of wear debris derived from the annealed nanocomposite membranes. We propose that detached Matrimid-encapsulated ZIF-8 nanoparticles could function as “spacers,” which are capable of not only reducing direct contact between two rubbing surfaces but also enhancing free-rolling under the action of lateral forces.

show abstract

Comparative Guest, Thermal, and Mechanical Breathing of the Porous Metal Organic Framework MIL-53(Cr): A Computational Exploration Supported by Experiments

Cited by 96 publications

References 39 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

A Comparison of Barostats for the Mechanical Characterization of Metal–Organic Frameworks

Fine-scale tribological performance of zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes

Contact Info

Product

Resources

About