Tailored engineering of primary catalytic sites and secondary coordination spheres in metalloenzyme-mimetic MOF catalysts for boosting efficient CO conversion.

The fabrication of metalloenzyme-mimetic artificial catalyst is a promising approach to achieve maximum catalytic efficiency, but the rational integration of sophisticatedly optimized primary catalytic sites (PCS) and secondary coordination spheres (SCS) for specific transformation poses a grand challenge. Here in this work, we report the tailored engineering of Cu PCS and perfluoroalkyl SCS onto a zirconium-based framework [UiO-67-(BPY-Cu)-F ( = 3, 5, 7, 11)] [BPY = 2,2'-bipyridine-5,5'-dicarboxylate] that can be utilized in the highly efficient carboxylic cyclization reaction between propargylamines and flue gas CO. The perfluoroalkyl groups act as tunable SCS that can facilely adjust the surface electronegativity, hydrophobicity, as well as the CO affinity and water vapor-resistance by simply varying the chain length.