Modeling steady-state experiments with a scanning electrochemical microscope involving several independent diffusing species using the boundary element method

The BEM algorithm developed earlier for steady-state experiments in the scanning electrochemical microscopy (SECM) feedback mode has been expanded to allow for the treatment of more than one independently diffusing species. This allows the treatment of substrate-generation/tip-collection SECM experiments. The simulations revealed the interrelation of sample layout, local kinetics, imaging conditions, and the quality of the obtained SECM images. Resolution in the SECM SG/TC images has been evaluated, and it depends on several factors. For most practical situations, the resolution is limited by the diffusion profiles of the sample. When a dissolved compound is converted at the sample (e.g., oxygen reduction or enzymatic reaction at the sample), the working distance should be significantly larger than in SECM feedback experiments (ca. 3 r(T) for RG = 5) in order to avoid diffusional shielding of the active regions on the sample by the UME body. The resolution ability also depends on the kinetics of the active regions. The best resolution can be expected if all the active regions cause the same flux. In one simulated example, which might mimic a possible scenario of a low-density protein array, considerable compromises in the resolving power, were noted when the flux from two neighboring spots differs by more than a factor of 2.