Design and Characterization of
            <scp>MOF</scp>
            s (Metal–Organic Frameworks) for Innovative Applications

Vitillo, Jenny G.; Atzori, Cesare; Civalleri, Bartolomeo; Barbero, Nadia; Barolo, Claudia; Bonino, Francesca

doi:10.1002/9783527807130.ch10

Cited by 8 publications

(4 citation statements)

References 137 publications

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“…Both qualitative expectations and previous cluster calculations showed that the superposition of the electrostatic potential from two opposite walls in a material pore fades quickly with increasing pore dimension. In this case, the pore size is increased by 7 Å, a significant amount for this kind of phenomenon.…”

Section: Discussionsupporting

confidence: 87%

Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg₂(dobpdc) Case Study

Vitillo

Ricchiardi

2017

J. Phys. Chem. C

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Mg2(dobpdc) (H4-dobpdc = 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylic acid) is an attractive metal organic framework (MOFs), because of its unique performances in carbon dioxide capture when combined with aliphatic amines. We have adopted this material as a paradigmatic case for the study of the effect of pore size, availability of open metal sites and structural defectivity on the sorptive properties of MOFs, with the aim of enabling the design of better sorbents and better tools for their characterization. In this study the adsorption of CO2, CO, and N2 has been investigated by means of infrared spectroscopy and high quality periodic quantum mechanical B3LYP-D* calculations. Comparison with literature data on the isomorph MOF-74-Mg, characterized by the shorter dobdc linker, allowed to verify a small, although appreciable effect of the pore size on the perturbation of the adsorbates. Although is is generally observed that the interaction energy with adsorbates decreases with increasing pore size, Mg2(dobpdc) represent an exception in the IRMOF-74 family and its interaction energy with adsorbates is greater than that of the smaller pore member of the family. The origin of this counterintuitive behavior was found in the increase of the dispersion energy component and in the lower framework deformation. The other typical aspects that can influence the interaction with guest molecules were investigated: the presence of residual solvents competing for adsorption and structural damage. For what concerns solvation, the affinity for solvents with different polarity was tested. Selective capping of the main adsorption sites (Mg 2+ ) was achieved by preadsorbing CH3OH on the open metal sites. IR spectroscopy of CO adsorption at 100 K revealed to be able to detect the presence of molecules pre-coordinated to Mg 2+ and then to check the quality of activation procedures for MOFs with open Mg 2+ sites. Because of Mg2(dobpdc) air-sensitivity, a full IR characterization was also performed after damaging by exposure to a water saturated atmosphere. Surprisingly, in spite of the drastic structural collapse verified by nitrogen volumetry (decrease of 83% in the surface area), the effect of damaging on the infrared spectrum of the MOF was negligible. Similarly, the only change observed in the spectra of the probe molecules was a slight decrease in their intensity after damaging. This means that IR spectroscopy is not a reliable technique to evidence the degradation of this MOF, unlike what reported for other systems.

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Section: Discussionsupporting

confidence: 87%

Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg₂(dobpdc) Case Study

Vitillo

Ricchiardi

2017

J. Phys. Chem. C

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“…For what concerns the energetics, the calculated ∆H c for CO 2 is lower than the experimentally determined value reported in Refs. [51][52][53], as expected because of the small dimension of the cluster used in this study [54]. The spurious effect of the H atoms is then mainly affecting the vibrational features of CO 2 , whereas it does not increase significantly the energetics of the interaction and the considerations that can be driven from these values.…”

Section: Eto-co 2 /Zif-8mentioning

confidence: 65%

ZIF-8 as a Catalyst in Ethylene Oxide and Propylene Oxide Reaction with CO2 to Cyclic Organic Carbonates

2019

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CO2 is an important by-product in epoxides synthesis, accounting for 0.02% of worldwide greenhouse emissions. The CO2 cycloaddition to ethylene and propylene oxides is an important class of reactions due to the versatile nature of the corresponding organic carbonates as chemical feedstocks. We report that these reactions can be catalyzed by ZIF-8 (Zeolitic Imidazole Framework-8) in the absence of solvent or co-catalyst and in mild conditions (40 °C and 750 mbar). In situ infrared spectroscopy places the onset time for ethylene and propylene carbonate formation to 80 and 30 min, respectively. Although there is low catalytic activity, these findings suggest the possibility to cut the CO2 emissions from epoxides production through their direct conversion to these highly valuable chemical intermediates, eliminating de facto energetically demanding steps as the CO2 capture and storage.

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“…23 The synthesis of MOFs typically involves mixing metal salts and organic ligands in a suitable solvent under controlled conditions, such as temperature, pH, and time, resulting in a three-dimensional framework with high surface areas and tunable pore sizes. 203 A number of techniques, including X-ray diffraction and gas sorption studies, can be used to better characterize MOF crystals. MOFs have shown potential as heterogeneous catalysts, gas storage materials, drug delivery vehicles, and sensing and imaging agents, among other applications.…”

Section: Reticular Membranesmentioning

confidence: 99%

Emerging trends in membrane-based wastewater treatment: electrospun nanofibers and reticular porous adsorbents as key components

Kumar,

Chowdhury,

Randhawa

2024

Environ. Sci.: Water Res. Technol.

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Design and Characterization of MOF s (Metal–Organic Frameworks) for Innovative Applications

Cited by 8 publications

References 137 publications

Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg₂(dobpdc) Case Study

Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg₂(dobpdc) Case Study

ZIF-8 as a Catalyst in Ethylene Oxide and Propylene Oxide Reaction with CO2 to Cyclic Organic Carbonates

Emerging trends in membrane-based wastewater treatment: electrospun nanofibers and reticular porous adsorbents as key components

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Design and Characterization of MOF s (Metal–Organic Frameworks) for Innovative Applications

Cited by 8 publications

References 137 publications

Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg2(dobpdc) Case Study

Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg2(dobpdc) Case Study

ZIF-8 as a Catalyst in Ethylene Oxide and Propylene Oxide Reaction with CO2 to Cyclic Organic Carbonates

Emerging trends in membrane-based wastewater treatment: electrospun nanofibers and reticular porous adsorbents as key components

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Product

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Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg₂(dobpdc) Case Study

Effect of Pore Size, Solvation, and Defectivity on the Perturbation of Adsorbates in MOFs: The Paradigmatic Mg₂(dobpdc) Case Study