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.

Current research fields of metal-organic frameworks (MOFs), which are being developed in the last 5-10 years by Russian scientific institutions and universities, are generalized. The review encompasses the design, synthesis, topological description, and prediction of MOF properties, the development of methods for their chemical engineering and modification, their investigation by modern physicochemical techniques, and the creation of functional materials based on porous frameworks (heterogeneous catalysts, highly efficient and highly selective sorbents of the new generation, conducting materials, systems for the target drug delivery).

This Perspective article surveys recent advances in the synthesis of mesoporous transition-metal-containing silicate materials and their use for the liquid-phase selective oxidation of organic compounds (alkanes, alkenes, aromatics, S-compounds, etc.) with environmentally friendly oxidants – molecular oxygen, hydrogen peroxide and organic hydroperoxides. A selection of the most relevant results reported thus far in the literature is provided, with particular attention paid to the issues of the nature of catalysis, catalyst stability and reusability. Approaches elaborated in recent years to create hydrothermally stable mesoporous metal silicates are considered, and the scope and limitations of such catalysts in liquid-phase oxidations are discussed.

Iron tetrasulfophthalocyanine (FePcS) has been irreversibly inserted into nanocages of the metal organic framework MIL-101 to give a hybrid material FePcS/MIL-101 which demonstrated a superior catalytic performance in the selective oxidation of aromatic substrates with ^tBuOOH than homogeneous FePcS.