Tuning the catalytic properties for cycloaddition of CO2 to propylene oxide on zeolitic-imidazolate frameworks through variation of structure and chemical composition

A series of Zn- and Co containing zeolitic-imidazolate frameworks (ZIFs), such as ZIF-8(Zn)/ZIF-67(Co), MAF-5 (Zn)/MAF-5(Co), and MAF-6(Zn)/MAF-6(Co), were investigated as catalysts for the synthesis of propylene carbonate (PC) from propylene oxide (PO) and CO2. The effect of the chemical composition, textural, structural and physicochemical properties on their activity was investigated. It was found that the activity of Zn-containing materials was higher in comparison with Co-based materials. Moreover, the yield of a PC was decreased with increasing Co content in structure of mixed Zn,Co-ZIFs (ZIF-8/ZIF-67) that was related to the accessibility of active centers to reagents and the strength of their interaction with CO2 and propylene oxide. The catalytic performance of Zn-ZIFs was found to improve with increasing the size of pore aperture due to the guest molecule facile diffusion and accessibility of the active site for reagent. In general, based on the results of the present work, the Zn-ZIFs could be considered as promising catalysts for cycloaddition of CO2 to epoxides and thereby opens new paths for further research.

Automated summary

A series of Zn- and Co-containing zeolitic-imidazolate frameworks were investigated as catalysts for the synthesis of propylene carbonate. The activity of Zn-containing materials was found to be higher, and the catalytic performance of Zn-ZIFs improved with an increase in pore aperture size.