Hydroxyl-Imidazolium Ionic Liquid-Functionalized MIL-101(Cr): A Bifunctional and Highly Efficient Catalyst for the Conversion of CO₂ to Styrene Carbonate

Abstract

Considerable attention has been focused on the development of catalysts for the coupling reaction of carbon dioxide (CO 2 ) and epoxides due to the distinct advantages and importance of this reaction. To develop high-performance and easy-to-recycle catalyst is still a hot topic, especially for candidates with excellent activity under moderate conditions. A new heterogeneous catalyst, MIL-101-ImEtOH, is reported by post-synthesis modification, in which 2-(1-imidazol-1yl) ethanol (Im-EtOH) is immobilized on MIL-101(Cr). In the absence of solvent and co-catalyst, MIL-101-ImEtOH exhibits high activity for the cycloaddition of CO 2 and styrene oxide. A 95.6% yield is achieved under 0.5 MPa CO 2 pressure and 90 °C by utilization of 50 mg of catalyst for 3 h. Moreover, MIL-101-ImEtOH is easily separated from the catalytic system by simple filtration. To elucidate the influence of hydroxyl group and porous structure on catalysis, other two supported ionic liquids, MIL-101-EtIm and PS-ImEtOH, are prepared and used to catalyze the title reaction under the same conditions. The contribution of each active component is determined by density functional theory along with noncovalent interaction analysis.

De novo assembly of frustrated Lewis pair bearing metal‐organic frameworks for atmospheric CO2 cycloaddition

“…It can be seen that the substrates with smaller substituents (methyl, -CH 2 Br,-CH 2 Cl) can be converted with excellent yields even at room temperature (25 C), which exceeds existing catalysts (Figure 3B). With increasing size of the substituents of epoxides, the steric hindrance of the reactant molecules increased and the reactivity of β-carbon atoms on epoxides decreased, 56,57 thus making the ring-opening of epoxides becoming difficult. As a result, the conversion rates of 1, 2-epoxy- that the crystal structure of FMOF-EIL and FMOF-FIL is consistent with MIL-101(Cr).…”

Pyrazolium ionic liquids with multiple active sites immobilized on mesoporous MCM-41 for chemical fixation of CO2 under mild conditions

“…Various porous materials have been reported for immobilizing ionic liquids to facilitate their separation and recovery. These materials include metal-organic frameworks (MOFs), 9,10 graphitic carbon nitride (g-C 3 N 4 ), 11,12 porous organic polymers, [13][14][15][16] nitrogen-rich polymeric ionic networks (IPNs-CSUs), 17 silica (SiO 2 ), 18,19 aluminosilicate Zeolite Socony Mobil-5 (ZSM-5), 20 and mesoporous silica such as Santa Barbara Amorphous-15 (SBA-15) 21 and Mobil Composition of Matter number 41 (MCM-41). 22 In particular, MCM-41, as an important mesoporous material, has attracted extensive attention in supporting ILs due to its ordered hexagonal array of uniform pores, enabling high surface area and tunable pore sizes.…”

One-Step Encapsulation of TBAB in ZIF-8 for CO2 Fixation: Revealing the Synergistic Mechanism between TBAB and ZIF-8

“…34 MOFs were widely used as carriers of active components because of their easily regulated pore structure and multiple active sites. For example, Liu et al 38 fixed 2-(1imidazol-1yl) ethanol (Im-EtOH) on MIL-101(Cr) to catalyze the cycloaddition reaction of CO 2 and styrene oxides. MIL-101-ImEtOH showed a very high activity due to its unique pore structure and hydroxyl group.…”