A comparison of the change from inhibiting to enhancing anions in the electrochemical oxidations of ethylene glycol and formaldehyde

Techniques dealing with inhibiting anions have previously been employed to measure their properties. The present approach is to change the behavior of inhibiting anions. Anions, which have long been considered to inhibit reactions, are shown to enhance some electrochemical reaction rates. Fluoroborate, nitrate, and (hydrogen) sulfate are separately shown to increase the current response of the electrochemical oxidation of formaldehyde. The reaction rate of the oxidation of ethylene glycol is increased but for a restrictive set of conditions. Experimental data, as well as theoretical considerations lead to the conclusion that adsorption of the added anions is the slow step of the process that increases the reaction rate. The differences in the response of ethylene glycol and formaldehyde follow well-documented changes of surface CO. These observations are consistent with general properties of the step in the part of the mechanism on the electrode surface that enhances the reaction rate.

Research highlights
► Anions known as inhibitors are shown to enhance the oxidation of formaldehyde.
► Anions with greater adsorption strength produce a greater reaction rate.
► Oxidation of ethylene glycol is enhanced by only one anion, fluoroborate.
► Reaction sites form when surface bonded anions cause perchlorate to leave surface.