Hybrid MOFs-graphene composites: Correlation between thermal transport and kinetics of hydrogen adsorption

Walshe

Devaux

et al. 2022

Chemistry A European J

A series of Zr-based UiO-n MOF materials (n = 66, 67, 68) have been studied for iodine capture. Gaseous iodine adsorption was collected kinetically from a home-made setup allowing the continuous measurement of iodine content trapped within UiO-n compounds, with organic functionalities (À H, À CH 3 , À Cl, À Br, À (OH) 2 , À NO 2 , À NH 2 , (À NH 2 ) 2 , À CH 2 NH 2 ) by in-situ UV-Vis spectroscopy. This study emphasizes the role of the amino groups attached to the aromatic rings of the ligands connecting the {Zr 6 O 4 (OH) 4 } brick. In particular, the preferential interaction of iodine with lone-pair groups, such as amino functions, has been experimentally observed and is also based on DFT calculations. Indeed, higher iodine contents were systematically measured for amino-functional-ized UiO-66 or UiO-67, compared to the pristine material (up to 1211 mg/g for UiO-67-(NH 2 ) 2 ). However, DFT calculations revealed the highest computed interaction energies for alkylamine groups (À CH 2 NH 2 ) in UiO-67 (À 128.5 kJ/mol for the octahedral cavity), and pointed out the influence of this specific functionality compared with that of an aromatic amine. The encapsulation of iodine within the pore system of UiO-n materials and their amino-derivatives has been analyzed by UV-Vis and Raman spectroscopy. We showed that a systematic conversion of molecular iodine (I 2 ) species into anionic I À ones, stabilized as I À •••I 2 or I 3 À complexes within the MOF cavities, occurs when I 2 @UiO-n samples are left in ambient light.

true F (t) = 1 - \exp [- k_{LDF} t]

…”

Section: Resultsmentioning

confidence: 99%

“…[31] It has been successfully applied to the study of adsorption kinetics of gaseous species in MOF materials. [32][33][34] The LDF equation is given by:…”

Section: Kinetic Study Of Gaseous Iodine Sorption In Uio-66 Series: I...mentioning

confidence: 99%

Capture of Gaseous Iodine in Isoreticular Zirconium‐Based UiO‐n Metal‐Organic Frameworks: Influence of Amino Functionalization, DFT Calculations, Raman and EPR Spectroscopic Investigation

Walshe

Devaux

et al. 2022

Chemistry A European J

“…49 This approach has been successfully applied to the study of adsorption kinetics of gaseous species in MOF materials. 50,51 The fitted and experimental curves can be observed in Figure S14. Of note, as the UiO-66 powder presents a second small but consistent uptake of iodine (measurement done twice), the resulting fitting is mediocre.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…For practical comparisons between the materials, a simple analytic equation derived from the Linear Driving Force (LDF) model has been used for the kinetic curves . This approach has been successfully applied to the study of adsorption kinetics of gaseous species in MOF materials. , The fitted and experimental curves can be observed in Figure S14. Of note, as the UiO-66 powder presents a second small but consistent uptake of iodine (measurement done twice), the resulting fitting is mediocre.…”

Section: Resultsmentioning

confidence: 99%

Extrusion-Spheronization of UiO-66 and UiO-66_NH₂ into Robust-Shaped Solids and Their Use for Gaseous Molecular Iodine, Xenon, and Krypton Adsorption

Абрамова

Couzon²,

ACS Appl. Mater. Interfaces

et al. 2022

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“…[44] It has been successfully applied to the study of adsorption kinetics of gaseous species in MOF materials. [45][46][47] The LDF equation is given by:…”

Section: Kinetic Study Of Gaseous Iodine Sorption In Uio-66 Series: I...mentioning

confidence: 99%

Cover Feature: Capture of Gaseous Iodine in Isoreticular Zirconium‐Based UiO‐n Metal‐Organic Frameworks: Influence of Amino Functionalization, DFT Calculations, Raman and EPR Spectroscopic Investigation (Chem. Eur. J. 14/2022)

Walshe

Devaux

et al. 2022

Chemistry A European J

Gaseous iodine has been captured by using a series of zirconium‐based UiO‐n metal–organic framework (MOF) sorbents. This study highlights the significant role of amino groups attached to the organic linker, which enhance the iodine uptake capacity, as well as its conversion into anionic iodide I3− species, trapped within UiO‐n cavities. More information can be found in the Research Article by T. Loiseau et al. (DOI: 10.1002/chem.202104437). Margot Friscourt and Orfeas Plastiras are thanked for the cover artwork.