The Effect of High Pressure on MOF‐5: Guest‐Induced Modification of Pore Size and Content at High Pressure

Graham, Alexander; Allan, David R.; Muszkiewicz, Anna; Morrison, Carole A.; Moggach, Stephen A.

doi:10.1002/anie.201104285

Cited by 139 publications

(144 citation statements)

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“…9,10,[11][12][13] Structural changes of these types have been observed over a wide range of conditions in cases where significant guest uptakes occur, ranging from low temperatures and pressures 14 to room temperature and very high pressures. 15,16 At very high pressures, the PV energy term associated with the ingress of molecules from fluids into pores becomes comparable with typical energies of adsorption.…”

Section: Introductionmentioning

confidence: 99%

“…Sc2BDC3(ip) does not therefore experience the stabilizing effect of channel 'super-filling' which occurs with methanol, which also occurs in other MOFs with one, two and three-dimensional channel connectivity. 15,23,30 Larger di-branched hydrocarbons can also penetrate into the pores of Sc2BDC3 at high pressures. Using 2,3-dimethylbutane and 2-methylheptane as hydrostatic media, a similar transformation is observed (see Figure 5a and b), though in each case the rotation is not as significant as in Sc2BDC3(ip): 21.2° for 2,3-dimethylbutane and 28.2° for 2-methylheptane.…”

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Pore Shape Modification of a Microporous Metal–Organic Framework Using High Pressure: Accessing a New Phase with Oversized Guest Molecules

et al. 2016

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Pressures up to 0.8 GPa have been used to squeeze a range of sterically 'oversized' C5-C8 alkane guest molecules into the cavities of a small-pore Sc-based metal-organic framework. Guest inclusion causes a pronounced reorientation of the aromatic rings of one third of the terephthalate linkers, which act as 'torsion springs', resulting in a fully reversible change in the local pore structure. The study demonstrates how pressure-induced guest uptake can be used to investigate framework flexibility relevant to 'breathing' behavior and to understand the uptake of guest molecules in MOFs relevant to hydrocarbon separation.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Pore Shape Modification of a Microporous Metal–Organic Framework Using High Pressure: Accessing a New Phase with Oversized Guest Molecules

et al. 2016

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“…A small increase in the unit cell volume of <1% was observed at 3 kbar, which is a frequent observation in other high-pressure inclusion studies on other MOFs including Sc2BDC3. [11,15] As seen with the inclusion of methanol, the expansion seemed to rely mostly on an increase along the a-axis, which corresponds to the channel directions (SI-IV). The continued increase of the a-axis with increasing pressure is in line with further CH4 being forced inside the framework, but overall the unit cell volume started to decrease above 6 kbar.…”

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confidence: 92%

Locating Gases in Porous Materials: Cryogenic Loading of Fuel‐Related Gases Into a Sc‐based Metal–Organic Framework under Extreme Pressures

et al. 2015

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An alternative approach to loading metal organic frameworks with gas molecules at high (kbar) pressures is reported. The technique, which uses liquefied gases as pressure transmitting media within a diamond anvil cell along with a single-crystal of a porous metal organic framework, is demonstrated to have considerable advantages over other gas-loading methods when investigating host-guest interactions. Specifically, loading the metal organic framework Sc2BDC3 with liquefied CO2 at 2 kbar reveals the presence of three adsorption sites, one previously unreported, and resolves previous inconsistencies between structural data and adsorption isotherms. A further study with supercritical CH4 at 3 -25 kbar demonstrates hyperfilling of the Sc2BDC3 and two high pressure displacive and reversible phase transitions are induced as the filled MOF adapts to reduce the volume of the system.Understanding how guest molecules in metal-organic framework (MOFs) interact with each other and the framework they occupy upon adsorption is vital for the development and commercial application of MOFs, for example in carbon capture and gas sequestration technologies. [1] Spectroscopic techniques, such as IR [2] and solid state NMR [3] are often used for probing these interactions. Crystallographic studies, both X-ray and neutron, utilizing various environmental cells have proven invaluable in determining the nature of host-guest interactions within MOFs and their guest-driven structural flexibility. [4] This is particularly important in the many cases where the uptake behavior, which can include conformational changes in the framework itself, can be perturbed by the type and amount of guest adsorbed. [5] One of the main reasons why so little data is available is that the experimental location of gas molecules in MOFs is challenging. The gas molecules are often disordered and exhibit thermal motion which is difficult to model crystallographically even when cooled close to the freezing temperature of the gas adsorbed. In-situ cells have been developed for collecting crystallographic data whilst exposing a MOF to a gaseous environment at tens, or even hundreds of bars of pressure in an effort to saturate the pores with gas molecules, though even here, the gas molecules are often difficult to observe experimentally. For these reasons, despite the intensive research in carbon capture technologies, relatively few crystallographic studies have been reported where CO2 molecules have been unambiguously located within MOFs. [6] The use of condensed gases as pressure transmitting media (PTM) in diamond anvil cells is commonplace in the fields of condensed matter physics and high-pressure mineralogy due to their excellent hydrostatic properties at very high-pressures (> 10 GPa) relative to common liquid PTMs. [7] He, Ar and Ne are typically used because they are chemically inert, whilst other gases have been studied for their diverse structural behavior. High temperature and pressure phases of CO2 and CH4 are of interest for understandin...

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“…They have already been shown to be highly selective CO 2 adsorbers, 13 and they are also efficient for separating mixed solvents. 14 In g-CD-MOFs, the cations, preferentially of the 1st and 2nd group metals, are coordinated by the g-cyclodextrin molecules in the presence of hydroxide counter-ions. In particular, potassium easily yields high-quality crystals with g-cyclodextrin.…”

Section: Introductionmentioning

confidence: 99%

Pressure inverse solubility and polymorphism of an edible γ-cyclodextrin-based metal–organic framework

Patyk‐Kaźmierczak

Warren

Allan

et al. 2017

Phys. Chem. Chem. Phys.

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A very exceptional effect of pressure-induced dissolution has been revealed for an edible metal-organic framework, g-CD-MOF-1, formed using g-cyclodextrin and KOH base. In addition, a new polymorph of g-CD-MOF-1 has been obtained. The trigonal structure is a symmetry sub-group modification of the cubic form. The pressure-induced dissolution of g-CD-MOF-1 and its polymorphism are shown to be closely related and regulated by adsorption in the pores, as well as the guest framework interactions.

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The Effect of High Pressure on MOF‐5: Guest‐Induced Modification of Pore Size and Content at High Pressure

Cited by 139 publications

References 24 publications

Pore Shape Modification of a Microporous Metal–Organic Framework Using High Pressure: Accessing a New Phase with Oversized Guest Molecules

Pore Shape Modification of a Microporous Metal–Organic Framework Using High Pressure: Accessing a New Phase with Oversized Guest Molecules

Locating Gases in Porous Materials: Cryogenic Loading of Fuel‐Related Gases Into a Sc‐based Metal–Organic Framework under Extreme Pressures

Pressure inverse solubility and polymorphism of an edible γ-cyclodextrin-based metal–organic framework

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