Studies on chemical activators for electrode I: Electrochemical activation of deactivating cathode for oxalic acid reduction

Electrosynthesis of glyoxylic acid by electroreduction of oxalic acid has long been well known. However, attempts to commercialize the process have encountered problems due to rapid deactivation of the cathode. The cathode activity can be continuously restored by adding small amounts of chemical activators to the catholyte. In this paper the structural effect of chemical activator on electrode reaction is studied. The results show that (1) It is the cation of the chemical activator, but not the anion that affects the current efficiency and the reaction selectivity. (2) The more symmetrical the cation, or the shorter the longest alkyl chain, the higher the current efficiency and the reaction selectivity become. (3) Mechanism of the activation is discussed. Adsorption of the cations of the activator on the cathode surface protects the electrode. (4) Quantitative characterization of the activator molecule is given using some topological indices, with which the activation ability can be predicted, and screening of the proper activator is made possible.