科研之友
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摘要
On the way toward a carbon-neutral future, anthropogenic chemical recycling of captured carbon dioxide (CO2) into value-added chemicals and reusable materials provides an attractive and promising pathway. A multi- functional zeolitic imidazolate framework (ZIF-9-ImBr) consisting of electrophilic cobalt ions, CO2-philic nitrogen-rich units and nucleophilic imidazolium-based ionic liquids (ILs) was synthesized by simple substitution reaction of amino-functionalized ZIF (ZIF-9-NH2) with 1-(4-bromobutyl)-3-methylimidazolium bromide ([BrBMIM]Br). The obtained ZIF-9-ImBr was employed as heterogeneous catalyst for the solvent-free synthesis of cyclic carbonates from CO2 and epoxides in the absence of any cocatalyst. A certain amount of micropores and abundant nitrogen atoms could facilitate CO2 enrichment and its activation, while the mesopores could enhance the mass transfer of reactant and product molecules. Moreover, the synergistic effect between Lewis-acid cobalt and Lewis-base bromine ions of ZIF-9-ImBr made it promising in the CO2 cycloaddition reaction. As expected, ZIF-9-ImBr displayed good catalytic performance of 93.8 % yield and 98.9 % selectivity of propylene carbonate at 120 degrees C and 2.0 MPa for 3.5 h. Additionally, the reactions proceeded with a broad substrate scope and high selectivity to give the corresponding cyclic carbonates in good to excellent yields (77.9-95.8 %). Even for the challenging internal epoxide, cyclohexene oxide, a satisfactory 71.4 % yield was obtained by extending the reaction time to 24 h. More importantly, ZIF-9-ImBr can be easily recycled and maintains its reactivity and selectivity after five successive cycles. This work highlights the potential of functional ZIF-based materials for targeting CO2 capture and conversion.
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单位茂名学院; 中山大学; 南昌航空大学
