Electrochemistry of the bis(1,4,7-triazacyclodecane) cobalt(III) complex and its role in the catalytic reduction of hydrogen

The electrochemistry of the bis(1,4,7-triazacyclodecane) cobalt(III) complex at a mercury electrode, HMDE, in aqueous Britton-Robinson buffer solutions was investigated using cyclic voltammetry, double-potential-step chronoamperometry and chronocoulometry. The cyclic voltammetric data were analyzed by digital simulation to confirm and to measure the heterogeneous and homogeneous parameters for the suggested electrode mechanism. Generally, the complex is electrochemically reduced giving rise to two cyclic voltammetric waves. The first wave is a diffusion-controlled reversible wave. It is assigned to the stable Co(III)/Co(II) redox couple. The second one is found to he irreversible and corresponding to a reduction of Co(II) to Co(I) species. The monovalent cobalt, highly unstable, is rapidly protonated, and then forms cobalt hydride. The hydride decomposes to hydrogen molecules and regenerates Co(II) species following a disproportionation pathway. The overall reduction mechanism is concluded to be an EECC kinetics. (C) 1998 Elsevier Science Ltd. All rights reserved.