Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion

Rogge, Sven M. J.; Wieme, Jelle; Vanduyfhuys, Louis; Vandenbrande, Steven; Maurin, Guillaume; Verstraelen, Toon; Waroquier, Michel; Speybroeck, Véronique Van

doi:10.1021/acs.chemmater.6b01956

Cited by 101 publications

(187 citation statements)

References 114 publications

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“…Conspicuously characteristic peaks below 10° disappeared while most of the others tended to merge into broad peaks. These findings are in agreement with previous works on computational characterization of the mechanical stability of flexible MIL‐53(Al) and rigid UiO‐66 , . These works predicted the loss of crystallinity of rigid UiO‐66 at 1.83 GPa.…”

Section: Resultssupporting

confidence: 92%

Solvent‐Free Encapsulation at High Pressure with Carboxylate‐Based MOFs

Monteagudo‐Olivan

Paseta

Potier³

et al. 2018

Eur J Inorg Chem

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The solvent‐free encapsulation of caffeine and kojic acid was carried out in different carboxylate‐based MOFs [MIL‐53(Al), UiO‐66 and Mg‐MOF‐74] by high pressure (0.32 GPa) contact. This methodology enables fast and ecofriendly encapsulation and gives rise to additive@MOFs with physical and features equivalent to those of materials obtained by common liquid phase encapsulation processes. It could be applied to other host–guest systems, simplifying the procedures, reducing the use and waste of harmful chemicals, and approaching the conditions of interest in the industry. The characterization carried out by thermogravimetry, X‐ray diffraction, N2 adsorption, and 13C NMR provided information about the presence and conformation of the additives in the MOFs. The highest encapsulation values for caffeine (37 %) and kojic acid (32 %) were obtained with MIL‐53(Al).

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Section: Resultssupporting

confidence: 92%

Solvent‐Free Encapsulation at High Pressure with Carboxylate‐Based MOFs

Monteagudo‐Olivan

Paseta

Potier³

et al. 2018

Eur J Inorg Chem

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“…It must however be emphasized that such behavior will be critically dependent on the particular cavity and channel structure of this nanoporous material. The pores on UiO‐66, where the included sphere diameter ranges from 6 to 9 Å, are large enough to enable structuring of the methanol molecules, certainly when defects are present.…”

Section: Resultsmentioning

confidence: 99%

“…. The defect structure denoted as type 6 in the work of Rogge was chosen here, as this structure ensures the highest accessibility for guest species, as shown in our earlier work . We gave preference to the situation where active sites were created showing the best perspective for guest intrusion and accessibility of the metal center.…”

Section: Methodsmentioning

confidence: 99%

“…Ar ationalization of these two-linker defects has been done in Ref. [18].T he defect structure denoted as type 6 in the work of Rogge [18b] was chosen here, as this structure ensures the highest accessibility for guest species, as shown in our earlier work. [5,[9][10] We gave preference to the situation where active sites were created showing the best perspective for guest intrusion and accessibility of the metal center.I na ddition, the symmetry of this linker deficiency allows to reduce the dimension of the unit cell to two bricks.…”

Section: Static Dft Calculationsmentioning

confidence: 99%

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Influence of a Confined Methanol Solvent on the Reactivity of Active Sites in UiO‐66

et al. 2018

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UiO‐66, composed of Zr‐oxide bricks and terephthalate linkers, is currently one of the most studied metal–organic frameworks due to its exceptional stability. Defects can be introduced in the structure, creating undercoordinated Zr atoms which are Lewis acid sites. Here, additional Brønsted sites can be generated by coordinated protic species from the solvent. In this Article, a multilevel modeling approach was applied to unravel the effect of a confined methanol solvent on the active sites in UiO‐66. First, active sites were explored with static periodic density functional theory calculations to investigate adsorption of water and methanol. Solvent was then introduced in the pores with grand canonical Monte Carlo simulations, followed by a series of molecular dynamics simulations at operating conditions. A hydrogen‐bonded network of methanol molecules is formed, allowing the protons to shuttle between solvent methanol, adsorbed water, and the inorganic brick. Upon deprotonation of an active site, the methanol solvent aids the transfer of protons and stabilizes charged configurations via hydrogen bonding, which could be crucial in stabilizing reactive intermediates. The multilevel modeling approach adopted here sheds light on the important role of a confined solvent on the active sites in the UiO‐66 material, introducing dynamic acidity in the system at finite temperatures by which protons may be easily shuttled from various positions at the active sites.

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“…In particular, the group of V. Van Speybroeck provided a thermodynamic characterization of the high-pressure behaviour of UiO-66 as a function of missing linker defects and linker expansion in the absence of guests. Indeed, for the defect-containing and/or expanded linker samples, a reduced mechanical stability is observed [223].…”

Section: Characterization Of Defectsmentioning

confidence: 98%

Metal–organic frameworks in Germany: From synthesis to function

Evans

Garai

Reinsch

et al. 2019

Coordination Chemistry Reviews

104

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Metal-organic frameworks (MOFs) are constructed from a combination of inorganic and organic units to produce materials which display high porosity, among other unique and exciting properties. MOFs have shown promise in many wide ranging applications, such as catalysis and gas separations. In this review, we highlight MOF research conducted by Germany-based research groups. Specifically, we feature approaches for the synthesis of new MOFs, high-throughput MOF production, advanced characterization methods and examples of advanced functions and properties.

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Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion

Cited by 101 publications

References 114 publications

Solvent‐Free Encapsulation at High Pressure with Carboxylate‐Based MOFs

Solvent‐Free Encapsulation at High Pressure with Carboxylate‐Based MOFs

Influence of a Confined Methanol Solvent on the Reactivity of Active Sites in UiO‐66

Metal–organic frameworks in Germany: From synthesis to function

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