Binuclear iron(II) cage complexes as electrocatalysts of hydrogen evolution reaction in different hydrogen-producing systems

• Fe(II) oximehydrazonate bis-clathrochelates are electrocatalysts for H2 production.
• Dependence of electrocatalytic 2H+/H2 process on pKa of H-acid is observed.
• General kinetic scheme of 2H+/H2 process persists irrespective of source of H+ ions.
• Protonation of two electrochemically generated iron(I) centers is rate-limiting stage.

The kinetic study of the electrocatalytic hydrogen evolution reaction (HER) in the presence of the α-oximehydrazonate iron(II) bis-clathrochelates in different media (including aqueous solutions) with various H-acids as the source of H+ ions showed that the rate-limiting stage of such electrocatalytic 2H+/H2 reaction is the protonation of two encapsulated electrochemically generated iron(I) metallocenters and the general kinetic scheme of this process persists irrespective of a source of H+ ions.

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