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Electrically Induced Breathing of the MIL-53(Cr) Metal-Organic Framework.

ABSTRACT: The breathing behavior of the MIL-53(Cr) metal-organic framework (MOF) has been explored previously upon guest-adsorption and thermal and mechanical stimuli. Here, advanced molecular simulations based on the use of an accurate force field to describe the flexibility of this porous framework demonstrate that the application of an electrical field induces the structural switching of this MOF leading to a first-order transition and a volume change of more than 40%. This motivated us to electrically tune the pore size of MIL-53(Cr) with the idea to propose a new concept to selectively capture CO₂ over CH₄ via a molecular sieving that paves the way toward the optimization of current separation-based processes.

SUBMITTER: Ghoufi A

PROVIDER: S-EPMC5445524 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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Electrically Induced Breathing of the MIL-53(Cr) Metal-Organic Framework.

Ghoufi Aziz A Benhamed Karima K Boukli-Hacene Leila L Maurin Guillaume G

ACS central science 20170407 5

The breathing behavior of the MIL-53(Cr) metal-organic framework (MOF) has been explored previously upon guest-adsorption and thermal and mechanical stimuli. Here, advanced molecular simulations based on the use of an accurate force field to describe the flexibility of this porous framework demonstrate that the application of an electrical field induces the structural switching of this MOF leading to a first-order transition and a volume change of more than 40%. This motivated us to electrically ...[more]

PMID: 28573200

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Thermodynamics of the Flexible Metal-Organic Framework Material MIL-53(Cr) From First Principles.

Project description:We use first-principles density functional theory total energy and linear response phonon calculations to compute the Helmholtz and Gibbs free energy as a function of temperature, pressure, and cell volume in the flexible metal-organic framework material MIL-53(Cr) within the quasiharmonic approximation. GGA and metaGGA calculations were performed, each including empirical van der Waals (vdW) forces under the D2, D3, or D3(BJ) parameterizations. At all temperatures up to 500 K and pressures from -30 MPa to 30 MPa, two minima in the free energy versus volume are found, corresponding to the narrow pore (np) and large pore (lp) structures. Critical positive and negative pressures are identified, beyond which there is only one free energy minimum. While all results overestimated the stability of the np phase relative to the lp phase, the best overall agreement with experiment is found for the metaGGA PBEsol+RTPSS+U+J approach with D3 or D3(BJ) vdW forces. For these parameterizations, the calculated free energy barrier for the np-lp transition is only 3 to 6 kJ per mole of Cr4(OH)4(C8H4O4)4.

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Pressure-induced postsynthetic cluster anion substitution in a MIL-53 topology scandium metal-organic framework.

Project description:Postsynthetic modification of metal-organic frameworks (MOFs) has proven to be a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the μ2-OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for μ2-OCH3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity - in this case chemisorption of methanol - has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials.

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MIL-53 Metal-Organic Framework as a Flexible Cathode for Lithium-Oxygen Batteries.

Project description:Li-air batteries possess higher specific energies than the current Li-ion batteries. Major drawbacks of the air cathode include the sluggish kinetics of the oxygen reduction (OER), high overpotentials and pore clogging during discharge processes. Metal-Organic Frameworks (MOFs) appear as promising materials because of their high surface areas, tailorable pore sizes and catalytic centers. In this work, we propose to use, for the first time, aluminum terephthalate (well known as MIL-53) as a flexible air cathode for Li-O2 batteries. This compound was synthetized through hydrothermal and microwave-assisted routes, leading to different particle sizes with different aspect ratios. The electrochemical properties of both materials seem to be equivalent. Several behaviors are observed depending on the initial value of the first discharge capacity. When the first discharge capacity is higher, no OER occurs, leading to a fast decrease in the capacity during cycling. The nature and the morphology of the discharge products are investigated using ex situ analysis (XRD, SEM and XPS). For both MIL-53 materials, lithium peroxide Li2O2 is found as the main discharge product. A morphological evolution of the Li2O2 particles occurs upon cycling (stacked thin plates, toroids or pseudo-spheres).

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MIL-53-based homochiral metal-organic framework as a stationary phase for open-tubular capillary electrochromatography.

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Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites.

Project description:Metal-organic framework crystal-glass composites (MOF-CGCs) are materials in which a crystalline MOF is dispersed within a MOF glass. In this work, we explore the room-temperature stabilization of the open-pore form of MIL-53(Al), usually observed at high temperature, which occurs upon encapsulation within a ZIF-62(Zn) MOF glass matrix. A series of MOF-CGCs containing different loadings of MIL-53(Al) were synthesized and characterized using X-ray diffraction and nuclear magnetic resonance spectroscopy. An upper limit of MIL-53(Al) that can be stabilized in the composite was determined for the first time. The nanostructure of the composites was probed using pair distribution function analysis and scanning transmission electron microscopy. Notably, the distribution and integrity of the crystalline component in a sample series were determined, and these findings were related to the MOF-CGC gas adsorption capacity in order to identify the optimal loading necessary for maximum CO2 sorption capacity.

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Metal-Organic Framework MIL-101(Cr) as an Efficient Heterogeneous Catalyst for Clean Synthesis of Benzoazoles.

Project description:A metal-organic framework [MIL-101(Cr)] was used as an efficient heterogeneous catalyst in the synthesis of benzoazoles (benzimidazole, benzothiazole, and benzoxazole), and quantitative conversion of products were obtained under optimized reaction conditions. The catalyst could be simply extracted from the reaction mixture, providing an efficient and clean synthetic methodology for the synthesis of benzoazoles. The MIL-101(Cr) catalyst could be reused without a remarkable decrease in its catalytic efficiency.

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An electrically switchable metal-organic framework.

Project description:Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

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| S-EPMC6832246 | biostudies-literature

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