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Highly Porous Metalloporphyrin Covalent Ionic Frameworks with Well‐Defined Cooperative Functional Groups as Excellent Catalysts for CO 2 Cycloaddition
Author(s) -
Liu Jiahui,
Zhao Guoying,
Cheung Ocean,
Jia Lina,
Sun Zhenyu,
Zhang Suojiang
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201900992
Subject(s) - catalysis , cycloaddition , chemistry , propylene oxide , covalent bond , synergistic catalysis , nucleophile , ionic bonding , porphyrin , yield (engineering) , propylene carbonate , lewis acids and bases , inorganic chemistry , polymer chemistry , organic chemistry , materials science , ion , polymer , ethylene oxide , electrode , copolymer , electrochemistry , metallurgy
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 (C 2 H 5 Br) or dibromoethane (C 2 H 4 Br 2 ) and then metalization with Zn or Co. The resulting CIFs showed high efficiency in catalyzing the cycloaddition of propylene oxide (PO) with CO 2 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 C 2 H 4 Br 2 and metalized with Zn (Zn‐CIF2‐C 2 H 4 ) exhibited the highest catalytic activity among the synthesized catalysts. The high catalytic performance of Zn‐CIF2‐C 2 H 4 is related to its high porosity (577 m 2 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‐C 2 H 4 is sufficiently stable that greater than 94 % PC yield could be obtained even after six cycles. In addition, Zn‐CIF2‐C 2 H 4 could catalyze the cycloaddition of several other epoxides with CO 2 . These highly porous materials are promising multifunctional and efficient catalysts for industrially relevant reactions.