Reactivity Studies of Metal–Organic Frameworks under Vapor‐Assisted Aging: Structural Interconversions and Transformations
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We systematically studied the chemical reactivities of 13 metal–organic frameworks (MOFs) under vapor‐assisted aging (VAG) at room temperature. The MOFs aged in solvent vapor at room temperature showed unexpectedly high reactivities for transformations into structures with other coordination networks. In addition, three MOFs reacted with 4,4′‐bipyridine to form three‐dimensional microporous MOFs under VAG conditions at room temperature.Keywords:
Reactivity
A series of ultra-microporous MOF-5-like metal-squarate frameworks exhibit moderate C 2 H 2 uptake capacity, in addition to excellent C 2 H 2 /CO 2 and C 2 H 2 /C 2 H 4 separation ability regulated by strong hydrogen bond interactions.
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Saturation H2 uptake in a series of microporous metal−organic frameworks (MOFs) has been measured at 77 K. Saturation pressures vary between 25 and 80 bar across the series, with MOF-177 showing the highest uptake on a gravimetric basis (7.5 wt %) and IRMOF-20 showing the highest uptake on a volumetric basis at 34 g/L. These results demonstrate that maximum H2 storage capacity in MOFs correlates well to surface area, and that feasible volumetric uptakes can be realized even in highly porous materials.
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Abstract Microporous metal-organic frameworks (MOFs) based on lanthanide metal ions or clusters represent a group of porous materials, featuring interesting coordination, electronic, and optical properties. These attractive properties in combination with the porosity make microporous lanthanide MOFs (Ln-MOFs) hold the promise for various applications. This review is to provide an overview of the current status of the research in microporous Ln-MOFs, and highlight their potential as types of multifunctional materials for applications in gas/solvent adsorption and separation, luminescence and chemical sensing and catalysis.
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Abstract Hierarchically porous metal–organic frameworks (HP‐MOFs) have attracted great attention owing to their advantages over microporous MOFs in some applications. Despite many attempts, the development of a facile approach to generate HP‐MOFs remains a challenge. Herein we develop a new strategy, namely the modulation of cation valence, to create hierarchical porosity in MOFs. Some of the Cu II metal nodes in MOFs can be transformed into Cu I via reducing vapor treatment (RVT), which partially changes the coordination mode and thus breaks coordination bonds, resulting in the formation of HP‐MOF based on the original microporous MOF. Both the experimental results and the first‐principles calculation show that it is easy to tailor the amount of Cu I and subsequent hierarchical porosity by tuning the RVT duration. It is found that the resultant HP‐MOFs perform much better in the capture of aromatic sulfides than the original microporous MOF.
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A Triply Interpenetrated Microporous Metal−Organic Framework for Selective Sorption of Gas Molecules
A microporous metal-organic framework Zn(ADC)(4,4'-Bpe)(0.5).xG [1; ADC = 4,4'-azobenzenedicarboxylate, 4,4'-Bpe = trans-bis(4-pyridyl)ethylene, G = guest molecules] with a triply interpenetrative primitive cubic net was synthesized and characterized. With pores of about 3.4 x 3.4 A, the activated 1a exhibits highly selective sorption behavior toward H(2)/N(2), H(2)/CO, and CO(2)/CH(4).
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Abstract Hierarchically porous metal–organic frameworks (HP‐MOFs) have attracted great attention owing to their advantages over microporous MOFs in some applications. Despite many attempts, the development of a facile approach to generate HP‐MOFs remains a challenge. Herein we develop a new strategy, namely the modulation of cation valence, to create hierarchical porosity in MOFs. Some of the Cu II metal nodes in MOFs can be transformed into Cu I via reducing vapor treatment (RVT), which partially changes the coordination mode and thus breaks coordination bonds, resulting in the formation of HP‐MOF based on the original microporous MOF. Both the experimental results and the first‐principles calculation show that it is easy to tailor the amount of Cu I and subsequent hierarchical porosity by tuning the RVT duration. It is found that the resultant HP‐MOFs perform much better in the capture of aromatic sulfides than the original microporous MOF.
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Two isostructural 2D → 2D parallel → 3D inclined interpenetrating polycatenane-like metal–organic frameworks were successfully constructed based on length-adjusted tricarboxylate ligands. With the merit of being microporous, IFMC-10 can serve as host for encapsulating lanthanide cations and I2 to exhibit luminescent sensing and rapid adsorption of iodine.
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