Challenges in the determination of reactive oxygen species evolving during membrane water electrolysis for in situ ozone production

Abstract

The treatment of ultrapure water with electrochemically produced O3 is a common means for disinfection yet leads to the formation of a variety of reactive oxygen species (ROS). The present study draws a comprehensive comparison between three commonly used photometric and fluorometric assays for ROS analysis and quantifies the individual signal responses for dissolved O3, ·OH and H2O2, respectively, to account for cross-sensitivities. By calibrating all combinations of assays and analytes, we developed a quantification procedure to reliably determine the actual ROS composition in ultrapure water environments for different operation conditions of a membrane water electrolyzer with PbO2 anodes down to concentrations of 0.97 μg L−1. While the ·OH formation rate can be described linearly over the observed current density range, substantial O3 evolution is only found for current densities of 0.75 A cm−2 and above (up to 3.7 μmol h−1 for J = 1.25 A cm−2). The formation of H2O2 is only observed when an organic carbon source is introduced into the solution. We further quantify the interference of H2O2 with the reading of the oxidation-reduction potential as a common water parameter and elaborate on its validity to monitor the peroxone process when both H2O2 and O3 are present simultaneously.