Fitting Kinetics from Scanning Electrochemical Microscopy Images of Finite Circular Features

Scanning electrochemical microscopy (SECM) is a powerful technique for imaging the electrochemical reactivity of a surface. Unfortunately, SECM images are mainly used qualitatively. Kinetics of reactions at the surface are almost exclusively obtained from the microelectrode current as it approaches the surface, called an approach curve. The approach curve method is excellent when the reaction at the surface has the same kinetics everywhere, but was not designed to fit the kinetics of finite-sized reactive features. We propose a method for extracting kinetics, feature area, and microelectrode tip-to-substrate distance from SECM images by fitting with simulated images of reactive discs using the Levenberg-Marquardt algorithm. The area of experimental reactive features can be fit to within 10% if the underlying feature is roughly disc-shaped. When the reaction at simulated reactive features is activation-limited, the rate constant can be fit to within 15% of the true value. This work heralds the beginning of quantifying kinetics from SECM images.

Automated summary

This study proposes a method for extracting kinetics and feature parameters from SECM images by fitting with simulated images using the Levenberg-Marquardt algorithm. The method can accurately match disc-shaped reactive features and accurately fit rate constants under activation-limited conditions.