Temperature-Induced Structural Transitions in the Gallium-Based MIL-53 Metal–Organic Framework

Boutin, Anne; Bousquet, David; Ortiz, Aurélie U.; Coudert, François‐Xavier; Fuchs, Alain H.; Ballandras, Anthony; Weber, Guy; Bezverkhyy, Igor; Bellat, Jean-Pierre; Ortiz, Guillaume; Chaplais, Gérald; Paillaud, Jean-Louis; Marichal, Claire; Nouali, Habiba; Patarin, Joël

doi:10.1021/jp312179e

Cited by 63 publications

(100 citation statements)

References 37 publications

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“…This sharp increase in the adsorbed amount results from the flexibility of the framework, so-called "breathing effect", well-known in this type of MOF. During the adsorption of formaldehyde the structure of Ga-MIL-53 activated at high temperature, probably undergoes, as we observed for water vapor adsorption [28], a phase transition from a narrow pore form to a large pore form. In this case, it is worth noting that the adsorption-desorption process is perfectly reversible, contrary to what was observed with the other adsorbents.…”

Section: Mesoporous Silica Activated Carbon and Mofsupporting

confidence: 59%

Capture of formaldehyde by adsorption on nanoporous materials

Bellat

Bezverkhyy

Weber

et al. 2015

Journal of Hazardous Materials

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148

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Section: Mesoporous Silica Activated Carbon and Mofsupporting

confidence: 59%

Capture of formaldehyde by adsorption on nanoporous materials

Bellat

Bezverkhyy

Weber

et al. 2015

Journal of Hazardous Materials

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148

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“…Supporting Information: Lattice parameters, relative energies, calculated band gaps of reported MOFs, additional computational details, complete author list for Refs 34,36,44,65, 84 and 86, and a CP2K input example. This material is available free of charge via the Internet at http://pubs.acs.org.…”

Section: Acknowledgementsmentioning

confidence: 99%

Unusually Large Band Gap Changes in Breathing Metal–Organic Framework Materials

Ling

Slater

2015

J. Phys. Chem. C

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Many of the potential applications for metal organic frameworks (MOFs) focus on exploiting their porosity for molecular storage, release and separation where the functional behaviour is controlled by a subtle balance of host-guest interactions. Typically the host structure is relatively unperturbed by the presence of guests, however, a subset of metal organic frameworks exhibit dramatic phase change behaviour triggered by the adsorption of guests or other stimuli, for which the MIL-53 material is an archetype. In this work, we use density functional approaches to examine the electronic structure changes associated with changes of phase and density and find the associated change in band gaps can be larger than 1 eV for known MIL-53 type materials and hypothecated structures. Moreover, we show that internal pressure (via guest molecules) and external pressure can exert a major influence on the band gap size and gap states. The large response in electronic properties to breathing transitions in MOFs could be exploitable in future applications in resistive switching, phase change memory, piezoresistor, gas sensor, and thermochromic materials.structure of non-conducting MOFs, although the more widespread parlance of band gap terminology is still de facto and we will refer to both band gaps and HOMO-LUMO nomenclature in this work.The MOF literature is dominated by synthesis and characterisation reports of new materials and input from theory typically focuses on rationalising observation through classical simulations of host-guest interactions. Nevertheless, there are an increasing number of electronic studies of MOFs which date back more than decade: early work of Dovesi reported a high-level ab initio study of the electronic properties of MOF-5, 10 through tight-binding calculations, Kuc et al. found the band gaps of a series of Zn-based isoreticular MOFs (IRMOFs) are determined by the carbon sp 2 states of the organic linkers and longer linkers yield smaller band gaps. 9 In a recent density functional theory (DFT) study by Pham et al., halogen functionalization of the organic linkers of IRMOFs was found to modify the band gaps and also affect the absolute positions of the valence band maxima. 11 The nature of the metal centres also affects electronic properties; using DFT, Fuentes-Cabrera et al. studied IRMOF1 with different metal centres, including Be, Mg, Ca, Zn and Cd, and found all these materials possess similar band gaps but distinct conduction band splitting, and that the metallicity can be influenced by selective metal doping. 12 Tunable electronic properties of IRMOFs have been verified in different experiments. For example, in a recent UV/Vis spectroscopy experiment by Gascon et al., it was reported the band gaps of IRMOFs are conditioned by the organic linkers of IRMOFs, and that 1,4-or 2,6-naphthalenedicarboxylic acid organic linkers yielded the smallest band gaps (~ 3.3 eV) . 13 In another experiment by Lin et al., it was shown that the band gaps of Zn-based MOFs can be tuned by changing the cluster size...

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“…. 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%

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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Temperature-Induced Structural Transitions in the Gallium-Based MIL-53 Metal–Organic Framework

Cited by 63 publications

References 37 publications

Capture of formaldehyde by adsorption on nanoporous materials

Capture of formaldehyde by adsorption on nanoporous materials

Unusually Large Band Gap Changes in Breathing Metal–Organic Framework Materials

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

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