Recent advances in the chemistry and applications of fluorinated metal–organic frameworks (F-MOFs)

Morelli Venturi, Diletta; Costantino, Ferdinando

doi:10.1039/d3ra04940j

Cited by 6 publications

(1 citation statement)

References 82 publications

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“…Based on the linker used, MIP‐203 (‐F, ‐S, and ‐M) show altered selectivities in CO 2 adsorption over N 2 caused by different flexibility of the linkers [16] . In recent years fluorinated linkers or fluorinated inorganic building units have been extensively used in order to enhance some properties of the MOFs such as the water stability, the compatibility with hydrophobic polymers and selectivity towards important gases such as CO 2 and small unsaturated hydrocarbons [17] . Indeed, the presence of the dipole in the C−F bond, due to the high electronegativity and low electric polarizability of fluorine, can produce a variety of characteristics, including specific adsorption sites for polar molecules.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure and (Photo)Catalytic Behavior of Ce‐MOFs Containing Perfluoroalkylcarboxylate Linkers: Experimental and Theoretical Insights

Morelli Venturi,

Sole Notari,

Trovarelli

et al. 2024

Chemistry A European J

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Cerium‐based Metal‐Organic frameworks (Ce‐MOFs) are attracting increasing interest due to their similar structural features to zirconium MOFs. The redox behavior of Ce(III/IV) adds a range of properties to the compounds. Recently, perfluorinated linkers have been used in the synthesis of MOFs to introduce new characteristic into the structure. We report the synthesis and structural characterization of Ce(IV)‐based MOFs constructed using two perfluorinated alkyl linkers. Their structure, based on hexanuclear Ce6O4(OH)412+ clusters linked to each other by the dicarboxylate ions, has been solved ab‐initio from X‐ray powder diffraction data and refined by the Rietveld method. The crystallization kinetics and the MOF formation mechanism was also invesitigated by Synchrotron radiation with XAS spectroscopies (EXAFS and XANES). The MOFs present the same fcu cubic topology as observed in MOF‐801 and UiO‐66, and they showed good stability in water at different pH conditions. The electronic structure of these MOFs has been studied by DFT calculations in order to obtain insights into the density of states structure of the reported compounds, resulting in band gaps in the range of 2.8‐3.1 eV. Their catalytic properties were tested both thermally and under visible light irradiation for the degradation of methyl orange (MO) dye.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Structure and (Photo)Catalytic Behavior of Ce‐MOFs Containing Perfluoroalkylcarboxylate Linkers: Experimental and Theoretical Insights

Morelli Venturi,

Sole Notari,

Trovarelli

et al. 2024

Chemistry A European J

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Fluorinated Nanosized Zeolitic-Imidazolate Frameworks as Potential Devices for Mechanical Energy Storage

Amayuelas,

Farrando-Perez,

Missyul

et al. 2024

ACS Appl. Mater. Interfaces

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Fluorination is one of the most efficient and universal strategies to increase the hydrophobicity of materials and consequently their water stability. Zeolitic-imidazolate frameworks (ZIFs), which have limited stability in aqueous media and even lower stability when synthesized on a nanometric scale, can greatly benefit from the incorporation of fluorine atoms, not only to improve their stability but also to provide additional properties. Herein, we report the preparation of two different fluorinated ZIFs through a simple and scalable approach by using mixed ligands [2-methylimidazole, as a common ligand, and 4-(4-fluorophenyl)-1H-imidazole (monof luorinated linker) or 2-methyl-5-(trifluoromethyl)-1H-imidazole (trifluorinated linker) as a dopant], demonstrating the high versatility of the synthetic method developed to incorporate different fluorine-containing imidazole-based ligands. Second, we demonstrate for the first time that these nanoscale fluorinated ZIFs outperform the pristine ZIF-8 for water intrusion/extrusion, i.e., for storing mechanical energy via forced intrusion of nonwetting water due to the improved hydrophobicity and modified framework dynamics. Moreover, we also show that by varying the nature of the F-imidazole ligand, the performance of the resulting ZIFs, including the pressure thresholds and stored/dissipated energy, can be finely tuned, thus opening the path for the design of a library of fluorine-modified ZIFs with unique behavior.

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Relaxometric properties and biocompatibility of a novel nanostructured fluorinated gadolinium metal–organic framework

Trovarelli,

Mirarchi,

Arcuri

et al. 2024

Dalton Trans.

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Recent advances in the chemistry and applications of fluorinated metal–organic frameworks (F-MOFs)

Abstract: Fluorinated building blocks as a source of new properties for metal–organic frameworks.

Cited by 6 publications

References 82 publications

Synthesis, Structure and (Photo)Catalytic Behavior of Ce‐MOFs Containing Perfluoroalkylcarboxylate Linkers: Experimental and Theoretical Insights

Synthesis, Structure and (Photo)Catalytic Behavior of Ce‐MOFs Containing Perfluoroalkylcarboxylate Linkers: Experimental and Theoretical Insights

Fluorinated Nanosized Zeolitic-Imidazolate Frameworks as Potential Devices for Mechanical Energy Storage

Relaxometric properties and biocompatibility of a novel nanostructured fluorinated gadolinium metal–organic framework

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