A guanidinium bromide covalently was anchored to a CO2-absorbent metal–organic framework via a two-step postsynthetic modification process and successfully used as a catalyst for the synthesis of cyclic carbonates through cycloaddition of CO2 to epoxides under mild conditions without utilizing any cocatalyst or organic solvent. In this protocol, the synergistic and cooperative effect was anticipated between the catalyst part and the support part to increase the reaction efficiency. Three key factors which are essential for carbon dioxide stabilization reaction were integrated simultaneously in this catalytic system including high CO2 absorption capability of MOF, availability of Lewis acidic centers in MIL-101­(Cr) as a cocatalyst, and presence of guanidinium salt as an efficient catalyst. This method demonstrated a high potential for recycling homogeneous catalysts by maintaining their initial performances.

A novel porous functionalized metal-organic framework (MOF) as a non-heme iron-based enzyme mimic system was achieved via two-step post-synthetic modification of the MIL-101(Cr)-NH 2 , and characterized by FT-IR, PXRD, TGA, SEM, EDS, CHN, BET surface area, and ICP-OES analyses. This new modified MOF (MIL-101(Cr)-guanidine-Fe) has been demonstrated to be a highly efficient, active, and reusable catalyst for oxidation of various organic substrates, including alcohols, alkenes and alkyl arenes at room temperature using H 2 O 2 as an oxidant.

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