Issue 32, 2020

Metalated-bipyridine-based porous hybrid polymers with POSS-derived Si–OH groups for synergistic catalytic CO2 fixation

Abstract

Herein, we construct a new series of N-heterocyclic ligand bipyridine-based porous hybrid polymers (denoted Bpy-PHPs) from the Heck reaction of a rigid building unit octavinylsilsesquioxane (VPOSS) and 5,5′-dibromo-2,2′-bipyridine. Surprisingly, the typical sample Bpy-PHP-4 was found to be a metal-/halogen-free heterogeneous catalyst in the cycloaddition reaction of CO2 with a few epoxides under atmospheric pressure. After coordination with ZnBr2, the resultant ZnBr2@Bpy-PHP-4 afforded largely enhanced heterogeneous catalytic activities upon the conversion of carbon dioxide (CO2) and various epoxides into cyclic carbonates without using any co-catalysts under mild conditions. The moderate catalytic activities of Bpy-PHP-4 may be due to the presence of hydrogen bond donors (HBDs), i.e., polyhedral oligomeric silsesquioxane (POSS)-derived Si–OH groups and N active sites from Bpy linkers. In comparison, the high catalytic efficiency of ZnBr2@Bpy-PHP-4 should be attributed to the synergistic catalysis of Si–OH groups, N active atoms, and Bpy-coordinated ZnBr2. Moreover, the catalyst ZnBr2@Bpy-PHP-4 can be easily recovered and reused ten times without any significant loss of catalytic activities. This work affords an efficient metal-based porous hybrid polymer heterogeneous catalyst for the cycloaddition reaction of CO2 and epoxides under mild and co-catalyst-free conditions.

Graphical abstract: Metalated-bipyridine-based porous hybrid polymers with POSS-derived Si–OH groups for synergistic catalytic CO2 fixation

Supplementary files

Article information

Article type
Paper
Submitted
08 May 2020
Accepted
20 Jul 2020
First published
20 Jul 2020

Dalton Trans., 2020,49, 11300-11309

Metalated-bipyridine-based porous hybrid polymers with POSS-derived Si–OH groups for synergistic catalytic CO2 fixation

Y. Zhang, N. Luo, J. Xu, K. Liu, S. Zhang, Q. Xu, R. Huang, Z. Long, M. Tong and G. Chen, Dalton Trans., 2020, 49, 11300 DOI: 10.1039/D0DT01667E

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