Flux melting of metal–organic frameworks

Longley, Louis; Collins, Sean M.; Li, Shichun; Smales, Glen J.; Eruçar, İlknur; Qiao, Ang; Hou, Jingwei; Doherty, Cara M.; Thornton, Aaron W.; Hill, Anita J.; Yu, Xia; Terrill, Nicholas J.; Smith, Andrew J.; Cohen, Seth M.; Midgley, Paul A.; Keen, David A.; Telfer, Shane G.; Bennett, Thomas D.

doi:10.1039/c8sc04044c

Cited by 78 publications

(76 citation statements)

References 55 publications

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“…S19), in agreement with the reported measurement of 0.18 mmol/g and representing a decrease from the reported value of 1.21 mmol/g in the crystalline ZIF-62. 30 Hysteresis is observed in the a g ZIF-62 isotherms as a result of the diffusion limitations through the amorphous structure, increasing in magnitude with the kinetic diameter of the adsorbent, also consistent with prior work. 31,32 This is especially evident in the propene isotherm with the uptake amount appearing to diminish in the region 70-100 kPa.…”

Section: Resultssupporting

confidence: 88%

Guest size limitation in metal–organic framework crystal–glass composites

et al. 2021

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Section: Resultssupporting

confidence: 88%

Guest size limitation in metal–organic framework crystal–glass composites

et al. 2021

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“…For an all-silica zeolite, the dense phase is easily envisaged as nonporous amorphous silica, which can be accessed via simple heating. For a MOF, the dense phase can be more difficult to conceptualize due to the directionality of the ligands, but denser, amorphous phases of some MOFs, achieved thermally, are known, [22][23][24][25] and other structures transition to denser amorphous phases with the application of pressure. [26][27][28] Figure 1: Metastability of Porous Materials.…”

Section: The Energetic Penalty For Porositymentioning

confidence: 99%

Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture

2019

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Metal-organic frameworks (MOFs) have demonstrated their utility for a variety of applications involving the storage, separation, and sensing of weakly interacting gases of high purity. Exposure to more realistic, impure gas streams and interactions with corrosive and coordinating gases raises the question of chemical robustness, which remains a paramount concern for practical applications of MOFs. However, factors that determine the stability of MOFs remain incompletely understood. Although past researchers attempted to categorize framework materials as either thermodynamically stable or kinetically stable, recent work has elucidated an energetic penalty for porosity for all materials in this class with respect to a dense material. The metastability of porous phases has important implications for the design of materials for gas storage, heterogeneous catalysts, and electronic materials. Here, we focus on two main strategies for stabilization of the porous phase, either by using inert metal ions, or by increasing the heterolytic metal-ligand bond strength, both of which increase the activation barrier for framework collapse. These two strategies have led to exceptionally robust materials for the capture of coordinating and corrosive gases such as water vapor, ammonia, H2S, SO2, NOx, and even elemental halogens, and we review the progress in designing stable materials for these gases. Looking forward, we envision that the continued pursuit of strategies for kinetic stabilization in the synthesis of new MOFs will provide increasing numbers of robust frameworks suited to harsh conditions, and that short-term stability towards these challenging gases will be predictive of long-term stability for applications in less demanding environments.

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“…The two key requirements for the crystalline component in such a composite, are that the temperature of decomposition ( T d ) should exceed the glass-forming matrix T m , and that the chemical (in)compatibility is such that no flux melting occurs 24 . The two frameworks we chose, MIL-53(Al) [Al(OH)(O 2 C-C 6 H 4 -CO 2 )] and UiO-66 [Zr 6 O 4 (OH) 4 (O 2 C-C 6 H 4 -CO 2 ) 6 ] both fulfil these criteria 25,26 .…”

Section: Introductionmentioning

confidence: 99%

Metal-organic framework crystal-glass composites

et al. 2019

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The majority of research into metal-organic frameworks (MOFs) focuses on their crystalline nature. Recent research has revealed solid-liquid transitions within the family, which we use here to create a class of functional, stable and porous composite materials. Described herein is the design, synthesis, and characterisation of MOF crystal-glass composites, formed by dispersing crystalline MOFs within a MOF-glass matrix. The coordinative bonding and chemical structure of a MIL-53 crystalline phase are preserved within the ZIF-62 glass matrix. Whilst separated phases, the interfacial interactions between the closely contacted microdomains improve the mechanical properties of the composite glass. More significantly, the high temperature open pore phase of MIL-53, which spontaneously transforms to a narrow pore upon cooling in the presence of water, is stabilised at room temperature in the crystal-glass composite. This leads to a significant improvement of CO 2 adsorption capacity.

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Flux melting of metal–organic frameworks

Abstract: We show flux melting by using a liquid MOF as a solvent for a secondary, non-melting MOF component.

Cited by 78 publications

References 55 publications

Guest size limitation in metal–organic framework crystal–glass composites

Guest size limitation in metal–organic framework crystal–glass composites

Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture

Metal-organic framework crystal-glass composites

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