Linker‐Functionalized Zr‐Based UiO‐66 Metal‐Organic Frameworks: Tuning Acidity for Enhanced Catalytic Dimerization of Cyclohexanone

The precise manipulation of pore structure, organic linkers, and disposition of active and coactive sites in metal‐organic frameworks (MOFs)‐based materials allows the designing of materials with tailored catalytic properties. However, studies that address their kinetic, dynamic, and mechanistic roles in target reactions are scarce. The development of a new functionalization method to introduce acidity into MOFs is established for heterogeneous catalysis. Exploring the effect of ligand functionalization in MOF type UiO‐66(Zr) impacts its ability to catalyze the dimerization reaction of cyclohexanone. Upon treatment with a series of linkers and the addition of HCl, chemically stable MOF structures such as UiO‐66 can be protonated, resulting in an acidic group attached to aromatic terephthalate linkers in the structure. A general synthetic strategy has been developed to produce functionalized UiO‐66‐FG compounds [FG = NH 2 , NO 2 , Br, OH, and (OH) 2 ]. The functionalized acidic frameworks present enhanced catalytic activity toward the self‐condensation of cyclohexanone. Investigating these aspects can provide valuable insights into how the functionalization of MOFs performs in real‐world self‐condensation scenarios and help in optimizing their practical applications.