Effect of Redox Mediators on Corrosion Behavior and Scanning Electrochemical Microscopy Response

Scanning electrochemical microscopy (SECM) is widely used to measure local electrochemical reactivity of corroding surfaces. A major criticism of using SECM in feedback mode for corrosion studies is the requirement of an external redox mediator (RM) as it could react with the metal and affect the Nernst potential at the metal-solution interface. Consequently, it becomes challenging to differentiate the interference caused by the RM from the local reactivity of the metal. Herein, a multiscale electrochemical approach is presented to investigate the effect of RM choice on the corroding substrate. Two common RMs, ferrocenemethanol and hexaammineruthenium(III) chloride, were used to perform SECM over copper and aluminum. It was found during macroscale electrochemical measurements that Ru(NH)₆³⁺ acted as an oxidant and promoted corrosion. The SECM feedback behavior varied for copper depending on the RM used, suggesting that the corrosion reactions controlled the negative feedback mechanism, not the formation of an insulating passive film. The passivated aluminum surface consistently exhibited negative feedback, regardless of the RM used. SECM approach curves also displayed a distortion in the steady state current, which was caused by the deposition of substrate-generated species on the microelectrode. These deviations in feedback response were accounted for during analysis through incorporation into a finite element model to accurately extract the RM kinetic rate constants. The importance of understanding these processes is highlighted to avoid misinterpretation of passive behavior and advances toward a more quantitative use of SECM for corrosion studies.