Ionic‐Liquid‐Functionalized UiO‐66 Framework: An Experimental and Theoretical Study on the Cycloaddition of CO2 and Epoxides. Issue 5 (7th February 2019)

• Record Type: Journal Article
• Authors: Kurisingal, Jintu Francis; Rachuri, Yadagiri; Pillai, Renjith S.; Gu, Yunjang; Choe, Youngson; Park, Dae‐Won
• Is Part Of: ChemSusChem. Volume 12:Issue 5(2019)
• Page Start: 1033
• Page End: 1042
• Publication Date: 2019-02-07
• Subjects: carbon dioxide fixation -- cycloaddition -- heterogeneous catalysis -- ionic liquids -- metal–organic frameworks; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201802838
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: A facile approach for modifying the UiO‐66‐NH2 metal–organic framework by incorporating imidazolium‐based ionic liquids (ILs) to form bifunctional heterogeneous catalysts for the cycloaddition of epoxides to CO2 is reported. Methylimidazolium‐ and methylbenzimidazolium‐based IL units (ILA and ILB, respectively) were introduced into the pore walls of the UiO‐66‐NH2 framework through a condensation reaction to generate ILA@U6N and ILB@U6N catalysts, respectively. The resultant heterogeneous catalysts, especially ILA@U6N, exhibited excellent CO2 adsorption capability, which makes them effective for cycloaddition reactions producing cyclic carbonates under mild reaction conditions in the absence of any cocatalyst or solvent. The significantly enhanced activity of ILA@U6N is attributed to the synergism between the coordinately unsaturated Lewis acidic Zr 4+ centers and Br − ions in the bifunctional heterogeneous catalysts. The size effect of the ILs on coupling between the epoxide and CO2 was also studied for ILA@U6N and ILB@U6N. A periodic DFT study was performed to provide evidence of possible intermediates, transition states, and pathways, as well as to gain deeper insight into the mechanism of the ILA@U6N‐catalyzed cycloaddition reaction between epichlorohydrin and CO2 . Abstract : IL@MOF catalysts : Metal–organic framework (MOF) UiO‐66‐NH2 is modified by incorporating imidazolium‐based ionic liquids (ILs) into the pore walls to form heterogeneous catalyst for cycloaddition of epoxides to CO2 under mild conditions in the absence of cocatalyst or solvent. The enhanced catalytic activity is attributed to synergism between the coordinately unsaturated Lewis acidic Zr 4+ centers and Br − ions in the bifunctional catalysts.