Boosting CO chemical fixation over MOF-808 by the introduction of functional groups and defective Zr sites.

CO cycloaddition has emerged as a promising approach for producing value-added cyclocarbonates and mitigating greenhouse gas emissions. Although MOF-808 serves as a stable catalyst for cycloaddition, its limited activity constrains broader applications. Through the modification with a fluoride group a ligand exchange method, F-MOF-808-1.5 exhibits exceptional performance, achieving a 98.8% conversion with 97.8% selectivity to epichlorohydrin carbonate-marking a substantial 100% improvement compared to pristine MOF-808. The defective Zr sites and the electron-withdrawing groups synergistically promote the ring opening of epoxides. Furthermore, the catalyst demonstrates high stability over multiple reaction cycles. Notably, without adding solvents and co-catalysts, F-MOF-808-1.5 outperforms most reported MOF-based catalysts.