Influence of functionalization of terephthalate linker on the catalytic activity of UiO-66 for epoxide ring opening

Juan F. Blandez, Andrea Santiago-Portillo, Sergio Navalón, Mónica Giménez-Marqués, Mercedes Álvaro, Patricia Horcajada, Hermenegildo García

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A series of five isostructural zirconium terephthalate UiO-66 metal organic frameworks bearing different functional groups on the terephthalate linker (UiO-66-X; X = H, NH2, NO2, Br, Cl,) have been successfully prepared and characterized. UiO-66-X materials were evaluated as heterogeneous catalysts for the epoxide ring opening of styrene oxide by methanol, observing an increase in the initial reaction rate from UiO-66-H to UiO-66-Br, over one order of magnitude. The reactivity order, however, does not follow a linear relationship between the Hammett constant value of the substituent and the initial reaction rate. UiO-66-Br exhibits a wide scope, its activity depending on the structure of epoxide and nucleophile. The absence of Zr leaching to the solution together with the preservation of the UiO-66-X crystallinity confirms the stability of the framework under the reaction conditions. Nevertheless, UiO-66 undergoes a progressive deactivation upon reuse that was attributed to a strong adsorption of the reaction product.

Original languageEnglish
Pages (from-to)332-339
Number of pages8
JournalJournal of Molecular Catalysis A: Chemical
Publication statusPublished - 15 Dec 2016
Externally publishedYes


  • Epoxide ring opening
  • Heterogeneous catalysis
  • Metal organic frameworks
  • UiO-66

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