LAUSR

An effective approach for tuning CO2 adsorption, activation and transformations of various epoxides in CO2 fixation reactions is introducing functional groups into the pores of metal‐organic frameworks (MOFs) through ligand modification. Herein, a novel ionic ligand, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene‐biphenyl‐4,4′‐dicarboxylic acid (H2BPDC−[TBD]+Br−), was synthesized to construct derivatives of the cationic guanidinium‐containing Zr‐MOF (UiO67‐[TBD]+Br−) with free bromide ions, as multifunctional heterogeneous catalysts. The materials were characterized comprehensively by multiple techniques such as PXRD, FTIR, TGA, SEM, EDS, 1H NMR, 13C NMR, mass spectrometry (MS), elemental analysis, as well as N2 and CO2 adsorption measurements. The synthesized UiO67‐[TBD]+Br− exhibits an efficient heterogeneous catalytic performance in the CO2 fixation reaction with epoxides, with high yield and selectivity, under mild conditions (0.1 MPa CO2, 80 °C, without co‐catalyst and solvent). In addition, these catalysts display good thermal stability, recyclability and could be reused at least five times without a significant decrease in their catalytic performance.