Mesoporous metal–organic frameworks Cr- and Fe-MIL-101 are highly efficient, true heterogeneous and recyclable catalysts for solvent-free selective oxidation of cyclohexane with molecular oxygen and/or tert-butyl hydroperoxide under mild conditions.

In this short review paper, we survey our recent findings in the catalytic applications of mesoporous metal–organic frameworks of the MIL-101 family (Fe- and Cr-MIL-101) and demonstrate their potential in two types of liquid-phase processes: (i) selective oxidation of hydrocarbons with green oxidants—O2 and tert-butyl hydroperoxide—and (ii) coupling reaction of organic oxides with CO2. A comparison with conventional single-site catalysts is made with special attention to issues of the catalyst's resistance to metal leaching and the nature of catalysis.