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Efficient Solvent‐Free Carbon Dioxide Fixation Reactions with Epoxides Under Mild Conditions by Mixed‐Ligand Zinc(II) Metal–Organic Frameworks
Author(s) -
Patel Parth,
Parmar Bhavesh,
Kureshy Rukhsana I.,
Khan Noorul,
Suresh Eringathodi
Publication year - 2018
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201800137
Subject(s) - cycloaddition , catalysis , epoxide , chemistry , isophthalic acid , metal organic framework , carbon fixation , ligand (biochemistry) , organic chemistry , inorganic chemistry , polymer chemistry , terephthalic acid , carbon dioxide , adsorption , biochemistry , receptor , polyester
Mixed‐ligand 3 D/2 D Zn metal–organic frameworks (MOFs) {[Zn(bdc)( L1 )]⋅ x G} n ( ZnMOF‐1 ) and {[Zn(ipa)( L2 )]} n ( ZnMOF‐2 ; in which H 2 BDC=benzene‐1,4‐dicarboxylic acid, L1 =4‐pyridyl carboxaldehyde isonicotinoylhydrazone, H 2 IPA=isophthalic acid, L2 =3‐pyridyl carboxaldehyde nicotinoyl hydrazone, and G=lattice guests) were synthesized using versatile synthetic routes that include a green mechanochemical (grinding) reaction. Chemical and thermal stability, phase purity, and characterization of the ZnMOFs synthesized by different approaches were established by using various analytical methods. Both ZnMOFs can be used as a highly active, solvent‐free, binary catalyst for CO 2 cycloaddition with epoxides under ambient reaction conditions of 1 atm pressure and room temperature/40 °C, in the presence of the cocatalyst n Bu 4 NBr. The yield, recyclability, and stability of ZnMOF‐1 as a potential catalyst towards epoxide to cyclic carbonate conversion are excellent under ambient conditions. From literature and experimental inferences, a rationalized mechanism mediated by the Zn center of ZnMOFs for the CO 2 ‐epoxide cycloaddition reaction has been proposed. To the best of our knowledge, very few MOF‐based catalysts have been reported to realize the conversion of CO 2 to useful products under similar mild conditions. In the present investigation, that is, catalyst preparation by green mechanochemical synthesis and catalysis under ambient, solvent‐free conditions were performed with minimum energy utilization.