Citation:
Seol-Hee Kim, Robin Babu, Dong-Woo Kim, Wonjoo Lee, Dae-Won Park. Cycloaddition of CO2 and propylene oxide by using M(HBTC)(4,4'-bipy)·3DMF (M=Ni, Co, Zn) metal-organic frameworks[J]. Chinese Journal of Catalysis,
;2018, 39(8): 1311-1319.
doi:
10.1016/S1872-2067(17)63005-5
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Three pillar-layered metal-organic frameworks (MOFs) based on M(HBTC)(4,4'-bipy)·3DMF (M=Ni, Co, and Zn; HBTC=1,3,5-benzenetricarboxylic acid, 4,4'-bipy=4,4'-bipyridine) were synthesized using a solvothermal method. Zn(HBTC)(4,4'-bipy)·3DMF was synthesized for the first time using both a solvothermal and microwave method, and subsequently characterized by various physicochemical methods. The structure of M(HBTC)(4,4'-bipy)·3DMF consisted of honeycomb grid layers of M2+ ions and BTC units, which were further linked by the 4,4'-bipy pillars to form a three-dimensional highly porous framework. All the MOFs displayed excellent synergistic catalytic properties with alkyl ammonium halides (TBAX) in the solventless fixation of CO2 with epoxides to produce cyclic carbonates. The catalytic activities of these MOFs followed the trend Zn > Co > Ni, which was explained by the acid-base bifunctional properties. The microwave-synthesized Zn(HBTC)(4,4'-bipy)·3DMF material exhibited physical, chemical, and catalytic properties that were similar to those of the catalyst obtained using a conventional solvothermal synthesis. The scope of various parameters, including recyclability, was studied, and a plausible reaction mechanism was suggested.
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