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 shu

Cycloaddition of CO₂ and propylene oxide by using M(HBTC)(4,4'-bipy)·3DMF (M=Ni, Co, Zn) metal-organic frameworks

a Division of Chemical and Biomolecular Engineering, Pusan National University, Busan 609-735, Korea;
b Korea Research Institute of Chemical Technology, Ulsan 681-802, Korea

Received Date: 25 November 2017
Revised Date: 25 December 2017

Fund Project: This work was supported by Korea Electric Power Corporation and National Research Foundation of Korea (2016-R1D1A1B-03931325).

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.
- M(HBTC)(4,4'-bipy)· 3DMF(M=Ni, Co, Zn),
- Microwave method,
- Carbon dioxide,
- Epoxide,
- Cyclic carbonate
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Cycloaddition of CO2 and propylene oxide by using M(HBTC)(4,4'-bipy)·3DMF (M=Ni, Co, Zn) metal-organic frameworks

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通讯作者: 陈斌, bchen63@163.com

Cycloaddition of CO₂ and propylene oxide by using M(HBTC)(4,4'-bipy)·3DMF (M=Ni, Co, Zn) metal-organic frameworks