An Exceptionally Stable Metal-Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation

Hyunho Noh, Yuexing Cui, Aaron W. Peters, Dale R. Pahls, Manuel A. Ortuno, Nicolaas A. Vermeulen, Christopher J. Cramer*, Laura Gagliardi, Joseph T. Hupp, Omar K. Farha

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

199 Scopus citations


Molybdenum(VI) oxide was deposited on the Zr6 node of the mesoporous metal-organic framework NU-1000 via condensed-phase deposition where the MOF is simply submerged in the precursor solution, a process named solvothermal deposition in MOFs (SIM). Exposure to oxygen leads to a monodisperse, porous heterogeneous catalyst, named Mo-SIM, and its structure on the node was elucidated both computationally and spectroscopically. The catalytic activity of Mo-SIM was tested for the epoxidation of cyclohexene. Near-quantitative yields of cyclohexene oxide and the ring-opened 1,2-cyclohexanediol were observed, indicating activity significantly higher than that of molybdenum(VI) oxide powder and comparable to that of a zirconia-supported analogue (Mo-ZrO2) prepared in a similar fashion. Despite the well-known leaching problem of supported molybdenum catalysts (i.e., loss of Mo species thus causes deactivation), Mo-SIM demonstrated no loss in the metal loading before and after catalysis, and no molybdenum was detected in the reaction mixture. In contrast, Mo-ZrO2 led to significant leaching and close to 80 wt % loss of the active species. The stability of Mo-SIM was further confirmed computationally, with density functional theory calculations indicating that the dissociation of the molybdenum(VI) species from the node of NU-1000 is endergonic, corroborating the experimental data for the Mo-SIM material.

Original languageEnglish (US)
Pages (from-to)14720-14726
Number of pages7
JournalJournal of the American Chemical Society
Issue number44
StatePublished - Nov 9 2016

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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