Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox-Active Fe(II/III) Sites in a Metal−Organic Framework

Ah Reum Kim, Sol Ahn, Tae Ung Yoon, Justin M. Notestein, Omar K. Farha, Youn Sang Bae

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

MIL-100(Fe), a metal−organic framework containing coordinatively unsaturated iron sites, was prepared by a solvothermal method and utilized in cyclohexane oxidation. Interestingly, the composition and fraction of redox-active Fe(II/III) sites in MIL-100(Fe) could be tuned by using different pretreatment temperatures. The obtained materials were characterized by means of field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (PXRD), N2 adsorption-desorption isotherms, and X-ray photoelectron spectroscopy (XPS). Due to the presence of redox-active coordinatively unsaturated sites (CUS) at the iron atoms, MIL-100(Fe) exhibited good performance for cyclohexane oxidation under mild reaction conditions. Oxidation rates were significantly enhanced when reduced FeII sites were generated by high-temperature pretreatments. In either high-temperature or low-temperature pretreatment, the isolated Fe(II/III) sites in MIL-100 were far more reactive in cyclohexane oxidation than were bulk iron oxide materials. Finally, possible reaction pathways were proposed based on radical, Haber-Weiss routes.

Original languageEnglish
Pages (from-to)5650-5656
Number of pages7
JournalChemCatChem
Volume11
Issue number22
DOIs
Publication statusPublished - Nov 21 2019

Keywords

  • Cyclohexane
  • Metal−organic frameworks (MOFs)
  • Oxidation
  • Redox-active sites

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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