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Impact of the Nature of the Organic Spacer on the Crystallization Kinetics of UiO‐66(Zr)‐Type MOFs
Author(s) -
Ragon Florence,
Chevreau Hubert,
Devic Thomas,
Serre Christian,
Horcajada Patricia
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406119
Subject(s) - crystallization , kinetics , naphthalene , activation energy , azobenzene , materials science , dimethylformamide , metal organic framework , crystallography , chemistry , chemical engineering , polymer chemistry , organic chemistry , molecule , adsorption , physics , quantum mechanics , solvent , engineering
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=NH 2 , NO 2 , Br, CH 3 ) 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‐NO 2 solid.