Peroxide Formation in a Zero-Gap Chlor-Alkali Cell with an Oxygen-Depolarized Cathode

The effects of various factors on the undesired generation of hydrogen peroxide in a zero-gap oxygen-depolarized chlor-alkali cell employing carbon-supported platinum catalysts were studied. The rate of peroxide generation was found to decrease with platinum loading and increase with current density. The quantity of peroxide generated also increased with electrolysis time, and reached a steady state value after a few 100 h of cell operation at 10 kA m⁻². The steady-state peroxide to hydroxide molar ratio was found to increase with brine concentration. This phenomenon is believed to originate from a decrease of water activity at the reaction site that accompanies the brine concentration increase. No correlation between chloride crossover and the concentration of peroxide generated was detected. It is postulated that carbon particles are predominantly responsible for the partial oxygen reduction and that their contribution increases with electrolysis time as a result of processes that render the carbon surface more hydrophilic.