Numerical Correction of In Situ AFM-SECM Measurements

Mass-transport-limited catalysis and membrane transport can be characterized by concentration profiles surrounding active surfaces. Scanning electrochemical microscopy (SECM) is a tool that has been used to measure concentration profiles; however, the presence and geometry of the tip can distort these profiles due to hindered diffusion, which in turn alters chemical behavior at the catalytic surface. To fully characterize the behavior of surface features such as catalytic sites, it is essential to account for and analytically remove the effect of tip presence. In this work, atomic force microscopy-based SECM (AFM-SECM) measurements over poly(tetrafluoroethylene) (PTFE) and gold electrode surfaces are used to measure negative and positive-feedback approach curves, respectively. By inversely fitting these approach curves with a finite element method (FEM) model, we derive kinetic and geometric tip parameters that characterize the effect of tip presence. Tip effects may be removed in the model to estimate concentration profiles and reaction properties for the case where no tip is present. A maximum 120% increase in the concentration at one tip radii above the surface is observed due to the presence of the tip, where the concentration field is compressed vertically, in proportion to surface feature size and tip separation. Conical AFM-SECM tips, with a higher ratio of tip height to the base size, introduce less concentration distortion than disk-shaped AFM-SECM tips.