Highly Porous Metalloporphyrin Covalent Ionic Frameworks with Well-Defined Cooperative Functional Groups as Excellent Catalysts for CO2 Cycloaddition

Jiahui Liu; Guoying Zhao; Ocean Cheung; Lina Jia; Zhenyu Sun; Suojiang Zhang

doi:10.1002/chem.201900992

Highly Porous Metalloporphyrin Covalent Ionic Frameworks with Well-Defined Cooperative Functional Groups as Excellent Catalysts for CO₂ Cycloaddition

Chemistry. 2019 Jul 5;25(38):9052-9059. doi: 10.1002/chem.201900992. Epub 2019 Jun 5.

Authors

Jiahui Liu^{1

2}, Guoying Zhao², Ocean Cheung³, Lina Jia², Zhenyu Sun¹, Suojiang Zhang²

Affiliations

¹ State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 1000029, P. R. China.
² Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
³ Nanotechnology and Functional Materials Division, Department of Engineering Sciences, The Ångström Laboratory, Uppsala University, Box 534, 75121, Uppsala, Sweden.

PMID: 30997700
DOI: 10.1002/chem.201900992

Abstract

The development of multifunctional heterogeneous catalysts with high porosity and remarkable catalytic activity still remains a challenge. Herein, four highly porous metalloporphyrin covalent ionic frameworks (CIFs) were synthesized by coupling 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin (TNPP) with 3,8-diamino-6-phenylphenanithridine (NPPN) or 5,5'-diamino-2,2'-bipyridine (NBPy) followed by ionization with bromoethane (C₂ H₅ Br) or dibromoethane (C₂ H₄ Br₂ ) and then metalization with Zn or Co. The resulting CIFs showed high efficiency in catalyzing the cycloaddition of propylene oxide (PO) with CO₂ to form propylene carbonate (PC). All of the Zn-containing CIF catalysts were able to catalyze the cycloaddition reaction with a PC yield greater than 97 %. The TNPP/NBPy (CIF2) catalyst ionized with C₂ H₄ Br₂ and metalized with Zn (Zn-CIF2-C₂ H₄ ) exhibited the highest catalytic activity among the synthesized catalysts. The high catalytic performance of Zn-CIF2-C₂ H₄ is related to its high porosity (577 m² g^-1 ), high Br:metal ratio (1:3.89), and excellent synergistic action between the Lewis acidic Zn sites and the nucleophilic Br^- ions. Zn-CIF2-C₂ H₄ is sufficiently stable that greater than 94 % PC yield could be obtained even after six cycles. In addition, Zn-CIF2-C₂ H₄ could catalyze the cycloaddition of several other epoxides with CO₂ . These highly porous materials are promising multifunctional and efficient catalysts for industrially relevant reactions.

Keywords: carbon dioxide; covalent ionic frameworks; cycloaddition; heterogeneous catalysis; porphyrins.

Abstract

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