In situ activation of COOH-functionalized ZIF-90-enabled reductive CO 2 N -formylation.

A heterogeneous ZIF-90-based catalyst functionalized with COOH and with a porous structure was facilely prepared for efficient CO 2 adsorption and activation to undergo reductive N -formylation with a wide range of amines (15 examples) to furnish N -formamides (78-94% yields). The -COO - species generated by an in situ interaction with amine acts as a key species for activating hydrosilane to capture CO 2 , and remarkably facilitates a cascade C-N coupling and hydrogenation process. Our findings show a facile strategy for the rational construction of robust active sites for reductive CO 2 valorization.