AbstractNowadays, hydrogen has become not only an extremely important chemical product but also a promising clean energy carrier for replacing fossil fuels. Production of molecular H2 through electrochemical hydrogen evolution reactions is crucial for the development of clean-energy technologies. The development of economically viable and efficient H2 production/oxidation catalysts is a key step in the creation of H2-based renewable energy infrastructure. Intrinsic limitations of both natural enzymes and synthetic materials have led researchers to explore enzyme-induced catalysts to realize a high current density at a low overpotential. In recent times, highly active widespread numerous electrocatalysts, both homogeneous or heterogeneous (immobilized on the electrode), such as transition metal complexes, heteroatom- or metal-doped nanocarbons, metal-organic frameworks, and other metal derivatives (calix [4] resorcinols, pectates, etc.), which are, to one extent or another, structural or functional analogs of hydrogenases, have been extensively studied as alternatives for Pt-based catalysts, demonstrating prospects for the development of a “hydrogen economy”. This mini-review generalizes some achievements in the field of development of new electrocatalysts for H2 production/oxidation and their application for fuel cells, mainly focuses on the consideration of the catalytic activity of M[P2N2]22+ (M = Ni, Fe) complexes and other nickel structures which have been recently obtained.
Synthetic models of hydrogenases based on framework structures containing coordinating P, N-atoms as hydrogen energy electrocatalysts – from molecules to materials