Autocatalyzed Kinetics of 6-Electron Electroreduction of Iodic Acid Studied by Rotating Disk Electrode Technique

The 6-electron electrochemical reduction of IO3− to I− represents a breakthrough for the development of next-generation redox flow batteries, offering substantially higher energy densities for oxidizer storage. Our study reveals that on a glassy carbon (GC) electrode in acidic electrolytes, HIO3 undergoes an autocatalyzed electrochemical reduction to I−. This process is mediated by the formation of a thin iodine layer on the electrode, acting as an intermediate and a catalyst. Under steady-state conditions, the iodine layer forms via a comproportionation reaction (HIO3 + I− + 5H+ = I2 (s) + 3H2O). Initially, the iodine layer is generated through the slow direct electrochemical reduction of HIO3 on pristine GC. Once established, this layer significantly enhances the rate of iodate reduction. On voltammetry curves, it is clearly observable as a step-wise current surge to reach a plateau. The limiting current density on the GC seemingly aligns with the Levich equation, varying with the RDE rotation rate. Earlier, we demonstrated the electrochemical oxidation of I− back to HIO3 using an H2/HIO3 flow cell, showcasing a full cycle that underpins the feasibility of this approach for energy storage. This study advances the understanding of iodate electroreduction and underscores its role in enhancing the capacity of next-generation energy storage systems.