Generating and optimizing the catalytic activity in UiO-66 for aerobic oxidation of alkenes by post-synthetic exchange Ti atoms combined with ligand substitution

Andrea Santiago-Portillo, Sergio Navalón, Mercedes Álvaro, Hermenegildo García

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The catalytic activity for the aerobic epoxidation of cyclooctene of UiO-66 has been introduced by post-synthetic ion exchange of Zr4+ by Ti4+ at the nodes and the performance optimized by nitro substitution in the terephthalate ligand. In this way a TON value of 16,600 (1660 considering Zr + Ti content) was achieved, comparing favorably with the highest catalytic activity reported in homogeneous for the same reaction (10,000 for γ-SiW10{Fe3+(OH2)}2O38 6−). Kinetic studies have shown that the most likely reactive oxygen species involved in the oxidation is superoxide, with hydroxyl radicals also contributing to the reaction. UiO-66(Zr5.4 Ti0.6)-NO2 is stable under catalytic conditions, being used six times without any change in the conversion temporal profile and in the X-ray diffractogram. The scope of UiO-66(Zr5.4 Ti0.6)-NO2 promoted aerobic oxidation of alkenes was expanded by including smaller rings cycloalkenes, as well as acyclic and aryl conjugated alkenes.

Original languageEnglish
Pages (from-to)450-463
Number of pages14
JournalJournal of Catalysis
Publication statusPublished - Sept 2018
Externally publishedYes


  • Aerobic oxidation of alkenes
  • Heterogeneous catalysis
  • Metal-organic frameworks
  • UiO-66

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