Electrochemical-driven hydrogen evolution from acetic acid and water catalyzed by a mixed-valent CoII–CoI complex with high turnover frequency

Abstract

The reaction of 2,3-bis(2-hydroxybenzylideneimino)-2,3-butenedinitrile (H2L1) and CoCl2·6H2O affords a mixed-valent dinuclear CoII–CoI complex [CoIL(py)3][CoIIL2] 1 (L = 2-(2-hydroxybenzylideneimino)-butenedinitrile ion), a new molecular electrocatalyst, which has been determined by X-ray crystallography and XPS spectrum. Electrochemical studies indicate that the catalyst is the first CoII–CoI complex species, that is among the most rapid homogeneous water-reduction catalysts, with a turnover frequency (TOF) of 2387 mol of hydrogen per mole of catalyst per hour at an overpotential of 787 mV vs SHE (pH 7.0). Sustained proton reduction catalysis occurs at glassy carbon (GC) to give H2 over a 46 h electrolysis period with 97% Faradaic yield and no observable decomposition of the catalyst.