Interactive Competition Between Individual Diffusion Layers during Cyclic Voltammetry at Random Arrays of Band and Disk Electrodes: A Thorough Analysis Based on Global Simulations

This work validates a posteriori the use of the theory developed ca. 40 years ago by Amatore and Saveant for regular arrays of electroactive band or disk electrodes. This theory has been profitably used and widely applied in more than 900 research papers for the treatment of the voltammetric responses of arrays of nanoelectroactive objects that were necessarily random by construction. In this work we show that competitive diffusion interaction between the active sites enforce redistribution of individual diffusion layer which homogenize dimensions of the solution volumes 'feeding' each active site. For arrays of nanodisk electrodes, it also validates the corresponding approximation assuming that its voltammetric behavior is to that afforded by identical independent cylindrical unit cells performing in parallel.

Automated summary

This study validates the theory developed by Amatore and Saveant 40 years ago for arrays of electroactive band or disk electrodes, demonstrating that competitive diffusion interaction between active sites leads to redistribution of diffusion layers and homogenization of solution volumes. The study also confirms the approximation that the voltammetric behavior of arrays of nanodisk electrodes is similar to that of independent cylindrical unit cells operating in parallel.