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Successful using of cage metal complexes (clathrochelates) and the functional hybrid materials based on them as promising electro- and (pre)catalysts for hydrogen and syngas production is highlighted in this microreview. The designed polyaromatic-terminated iron, cobalt and ruthenium clathrochelates, adsorbed on carbon materials, were found to be the efficient electrocatalysts of the hydrogen evolution reaction (HER), including those in polymer electrolyte membrane (PEM) water electrolysers. The clathrochelate-electrocatalayzed performances of HER 2H + /H 2  in these semi-industrial electrolysers are encouraging being similar to those for the best known to date molecular catalysts and for the promising non-platinum solid-state HER electrocatalysts as well. Electrocatalytic activity of the above clathrochelates was found to be affected by the number of the terminal polyaromatic group(s) per a clathrochelate molecule and the lowest Tafel slopes were obtained with hexaphenanthrene macrobicyclic complexes. The use of suitable carbon materials of a high surface area, as the substrates for their efficient immobilization, allowed to substantially increase an electrocatalytic activity of the corresponding clathrochelate-containing carbon paper-based cathodes. In the case of the reaction of dry reforming of methane (DRM) into syngas of a stoichiometry CO/H 2  1:1, the designed metal(II) clathrochelates with terminal polar groups are only the precursors (precatalysts) of single atom catalysts, where each of their catalytically active single sites is included in a matrix of its former encapsulating ligand. Choice of their designed ligands allowed an efficient immobilization of the corresponding cage metal complexes on the surface of a given highly porous ceramic material as a substrate and caused increasing of a surface concentration of the catalytically active centers (and, therefore, that of the catalytic activity of hybrid materials modified with these clathrochelates). Thus designed cage metal complexes and hybrid materials based on them operate under the principals of “green chemistry” and can be considered as efficient alternatives to some classical inorganic and molecular (pre)catalysts of these industrial processes.

New types of the hybrid functional materials based on cage metal complexes for (electro) catalytic hydrogen production