A novel zirconium-based metal-organic framework covalently modified by methyl pyridinium bromide for mild and co-catalyst free conversion of CO2 to cyclic carbonates

Jia-Hui Xu; Shuai-Feng Peng; Yu-Kun Shi; Shan Ding; Guang-Sheng Yang; Yu-Qi Yang; Yan-Hong Xu; Chun-Jie Jiang; Zhong-Min Su

doi:10.1039/d2dt03507c

A novel zirconium-based metal-organic framework covalently modified by methyl pyridinium bromide for mild and co-catalyst free conversion of CO₂ to cyclic carbonates

Dalton Trans. 2023 Jan 17;52(3):659-667. doi: 10.1039/d2dt03507c.

Authors

Jia-Hui Xu¹, Shuai-Feng Peng¹, Yu-Kun Shi¹, Shan Ding¹, Guang-Sheng Yang¹, Yu-Qi Yang¹, Yan-Hong Xu², Chun-Jie Jiang¹, Zhong-Min Su³

Affiliations

¹ School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, P. R. China. yanggs693@nenu.edu.cn.
² Key Laboratory of Preparation and Applications of Environmental Friendly Materials, Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education (Jilin Normal University), Ministry of Education, Changchun, 130103, China. xuyh198@163.com.
³ State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, P. R. China.

PMID: 36537538
DOI: 10.1039/d2dt03507c

Abstract

Building metal-organic frameworks (MOFs) covalently modified by onium halides is a promising approach to develop efficient MOF-based heterogeneous catalysts for the cycloaddition of CO₂ to epoxides (CCE) into cyclic carbonates. Herein, we report a novel zirconium-based MOF covalently modified by methyl pyridinium bromide, Zr₆O₄(OH)₄(MPTDC)_2.2(N-CH₃-MPTDC)_3.8Br_3.8 ((Br-)CH3-Pyridinium-MOF-1), where MPTDC denotes 3-methyl-4-pyridin-4-yl-thieno[2,3-b] thiophene-2,5-dicarboxylate. The structure and composition of this complex were fully characterized with PXRD, NMR, XPS, TEM and so on. CO₂ adsorption experiments show that (Br-)CH3-Pyridinium-MOF-1 has a higher affinity for CO₂ than its electrically neutral precursor, which should be attributed to the fact that charging frameworks containing pyridinium salt have stronger polarization to CO₂. (Br-)CH3-Pyridinium-MOF-1 integrated reactive Lewis acid sites and Br^- nucleophilic anions and exhibited efficient catalytic activity for CCE under ambient pressure in the absence of co-catalysts and solvents. Furthermore, (Br-)CH3-Pyridinium-MOF-1 was recycled after five successive cycles without substantial loss in catalytic activity. The corresponding reaction mechanism also was speculated.