Oxidation of Alkanes to Give Alcohols or Ketones

The encapsulation of metalloporphyrins in the cavities of an indium imidazoledicarboxylate-based rho-zeolite-like metal-organic framework (rho-ZMOF) has been reported by Eddaoudi and coworkers [71]. The catalytic activity of this material was assessed by cyclohexane oxidation with TBHP as the oxidant, with cyclohexane conversion reaching 91.5% after 24 h at 65 °C. Cyclohexanol and cyclohexanone were the only observed products, suggesting that the investigated oxidation reaction is selective toward the desired products. Furthermore, upon reuse of the catalyst, no loss of crystaUinity, reactivity, and selectivity in up to 11 cycles was observed, while no leaching of the encapsulated metalloporphyrin into the product solution was detected by the UV-vis spectra. 

The authors thus demonstrated that the encapsulation of MPc in MIL-101 allows an activity increase of approximately one order of magnitude. They attributed this increase in activity to the dispersion of the molecular complexes as isolated monomers in the nanopore cavities and/or from the confinement eSects provided by the host porous structure. 

The functionalized MOF materials exhibit superior yields with respect to their molecular analogs and also with regard to functionalized MCM-NH2 material. It has to be pointed out that the difference in yields according to the substrates results 

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