Acid-functionalized UiO-66(Zr) MOFs and their evolution after intra-framework cross-linking: structural features and sorption properties

Ragon, Florence; Campo, Betiana; Yang, Qingyuan; Martineau, Charlotte; Wiersum, Andrew D.; Lago, Ana Belén; Guillerm, Vincent; Hemsley, Callum; Eubank, Jarrod F.; Vishnuvarthan, M.; Taulèlle, Francis; Horcajada, Patricia; Vimont, Alexandré; Llewellyn, Philip L.; Daturi, Marco; Devautour‐Vinot, Sabine; Maurin, Guillaume; Serre, Christian; Devic, Thomas; Clet, Guillaume

doi:10.1039/c4ta03992k

Cited by 193 publications

(168 citation statements)

References 81 publications

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“…Except for the UiO‐66_Cl 2 AzoBDC solid, these values are almost equal to those calculated from the Gualtieri model, being both E

_{a_{n}}

and E

_{a_{g}}

. Finally, if one compares these values with those reported for other MOFs,10, 11 the values for UiO‐66 and UiO‐66_NDC are, to date, the lowest reported so far, close to those typically reported for inorganic solids 16. However, the values for UiO‐66_BPDC and UiO‐66_Cl 2 AzoBDC are in the same order of magnitude to the E a reported for other MOFs,10f,j such as, for instance, E

_{a_{n}}

of 71(3) and E

_{a_{g}}

of 66(6) kJ mol −1 for Zr‐fumarate 10a…”

Section: Resultssupporting

confidence: 60%

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Impact of the Nature of the Organic Spacer on the Crystallization Kinetics of UiO‐66(Zr)‐Type MOFs

Ragon

Chevreau

Devic

et al. 2015

Chemistry A European J

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The influence of the constitutive dicarboxylate linkers (size, functional group) over the crystallization kinetics of a series of porous Zr metal-organic frameworks with the UiO-66 topology has been investigated by in situ time-resolved energy dispersive X-ray diffraction (EDXRD). Both large aromatic spacers (2,6-naphthalene-, 4,4'-biphenyl- and 3,3'-dichloro-4,4'-azobenzene-dicarboxylates) and a series of X-functionalized terephthalates (X=NH2 , NO2 , Br, CH3 ) were investigated in dimethylformamide (DMF) at different temperatures and compared with the parent UiO-66. Using different crystallization models, rate constants and further kinetic parameters (such as activation energy) have been extracted. Finally, the impact of the replacement of the toxic DMF by water on the crystallization kinetics was studied through the synthesis of the functionalized UiO-66-NO2 solid.

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“…Except for the UiO‐66_Cl 2 AzoBDC solid, these values are almost equal to those calculated from the Gualtieri model, being both E

_{a_{n}}

and E

_{a_{g}}

_{a_{n}}

of 71(3) and E

_{a_{g}}

of 66(6) kJ mol −1 for Zr‐fumarate 10a…”

Section: Resultssupporting

confidence: 60%

“…Finally, it was recently highlighted that, providing that the ligand is soluble enough, several UiO‐66‐type solids could also be prepared in water 10a. 11 The influence of the solvent (water vs. DMF) on the crystallization rate was also assessed for UiO‐66‐NO 2 .…”

Section: Introductionmentioning

confidence: 99%

Impact of the Nature of the Organic Spacer on the Crystallization Kinetics of UiO‐66(Zr)‐Type MOFs

Ragon

Chevreau

Devic

et al. 2015

Chemistry A European J

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“…This refinement gave a unit cell volume of 1411 Å 3 , which is slightly smaller than its corresponding dehydrated phase (1431 Å 3 ) despite the fact that no strong interactions are expected between the additional -Cl groups and the MeOH guest molecules that might result in a contraction of the framework. 31 In contrast to the other frameworks, the -(OH) 2 modified framework contracts during thermal treatment and this contraction is complete by 110 °C. Furthermore, all of the frameworks showed some hysteresis upon cooling to room temperature; the frameworks remained in their respective dehydrated phases to temperatures lower than those required to dehydrate them.…”

Section: Structural Flexibilitymentioning

confidence: 99%

The flexibility of modified-linker MIL-53 materials

et al. 2016

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The flexibility of eight aluminum hydroxo terephthalates [Al(OH)(BDC-X)]·n(guest) (BDC = 1,4-benzene-dicarboxylate; X = -H, -CH3, -Cl, -Br, -NH2, -NO2, -(OH)2, -CO2H) crystallising in the MIL-53-type structure was investigated upon thermal dehydration of as-made samples, superhydration and methanol adsorption/desorption using in situ powder X-ray diffraction (PXRD). Profile fitting was used to determine lattice parameters as a function of time and/or temperature to describe their structural evolution. It has thus been shown that while methanol vapour adsorption induces an opening of all the modified frameworks, except the -NH2 material, superhydration only leads to open structures for Al-MIL-53-NO2, -Br and -(OH)2. All the MIL-53 solids, except Al-MIL-53-(OH)2 are present in the open structures upon thermal dehydration. In addition to the exploration of the breathing behavior of this MIL-53 series, the issue of disorder in the distribution of the functional groups between the organic linkers was explored. As a typical illustration, density functional theory calculations were carried out on different structures of Al-MIL-53-Cl, in which the distribution of -Cl within two adjacent BDC linkers is varied. The results show that the most energetically stable configuration leads to the best agreement with the experimental PXRD pattern. This observation supports that the distribution of the selected linker substituent in the functionalised solid is governed by energetics and that there is a preference for an ordering of this arrangement.

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“…Techniques such as X-ray diffraction must be able to penetrate the reaction vessel. The existing literature on in situ diffraction studies of MOF formation remain sparse, and generally utilize energy dispersive XRD (EDXRD); [1][2][3][4][5][6][7] more recently, advances in technology have made monochromatic XRD experiments feasible, although so far only work on mechanochemical MOF synthesis has been published. [8] Monochromatic in situ XRD experiments have mostly been limited to small-volume reaction using heated capillary microreactors; a range of systems have been studied, including ternary sulfides, metal oxides and bismuth chalcogenides.…”

Section: Introductionmentioning

confidence: 99%

An in situ study of resin-assisted solvothermal metal-organic framework synthesis

Moorhouse

O’Hare

2016

Journal of Solid State Chemistry

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Acid-functionalized UiO-66(Zr) MOFs and their evolution after intra-framework cross-linking: structural features and sorption properties

Abstract: International audienc

Cited by 193 publications

References 81 publications

Impact of the Nature of the Organic Spacer on the Crystallization Kinetics of UiO‐66(Zr)‐Type MOFs

Impact of the Nature of the Organic Spacer on the Crystallization Kinetics of UiO‐66(Zr)‐Type MOFs

The flexibility of modified-linker MIL-53 materials

An in situ study of resin-assisted solvothermal metal-organic framework synthesis

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