Oxidation reactions metal-organic frameworks

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. 

Generation of nanoparticles in systems with confined void spaces such as inside the zeolites [82,88], carbonaceous materials [89], metal oxides [90,91], polymers [92,93], minerals [94,95] or metal-organic frameworks [96] is a sound approach of preventing aggregation with the kinetic control of catalytic reactions. 

Xiao B, Hou H, Fan Y. A cobalt(II)-containing metal-organic framework showing catalytic activity in oxidation reactions. J Organomet Chem 2007 692 2014-20. 

Very recently, an alternative route was being researched in 2015, where it seems possible to produce ethanol directly from ethane via the use of a new type of Metal Organic Framework catalyst and N2O. This reaction can be performed at 75°C and makes the direct conversion of ethane into ethanol possible at mild conditions for the first time. This also opens the way for making better use of ethane which is present in natural gas and/or can be produced from methane via oxidative coupling. 

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