General Method for Fitting Kinetics from the SECM Images of Reactive Sites on Flat Surfaces.

Scanning electrochemical microscopy (SECM) is a technique for imaging electrochemical reactions at a surface. The interaction between electrochemical reactions occurring at the sample and scanning electrode tip is quite complicated and requires computer modeling to obtain quantitative information from SECM images. Often, existing computer models must be modified, or a new model must be created from scratch to fit kinetic parameters for different reactive features. This work presents a method that can simulate the SECM image of a reactive feature of any shape on a flat surface which is coupled to a computer program which effectuates the automated fitting of kinetic information from these images. This fitting program is evaluated along with several methods for estimating the shapes of reactive features from their SECM images. Estimates of the reactive feature shape from SECM images were not sufficiently accurate and produced median relative errors for the surface rate constant that were >50%. Fortunately, more precise techniques for imaging the reactive features such as optical microscopy can supply sufficiently accurate shapes for the fitting procedure to produce accurate results. Fits of simulated SECM images using the actual shape from the simulation produced median relative errors for the surface rate constant that were <10% for the smallest reactive features tested. This method was applied to the SECM images of aluminum alloy AA7075 which revealed diffusion-limited kinetics for ferrocene methanol reduction over inclusions in the surface of the alloy.