Voltammetry at porous electrodes: A theoretical study

•Chronoamperometry and cyclic voltammetry at porous electrodes is simulated.•Electrodes are considered to be a series of interconnected spherical voids.•Diffusion within the voids and bulk diffusion is considered to be decoupled.•A new approach to estimate heterogeneous rate constants is proposed.

Theory is presented to simulate both chronoamperometry and cyclic voltammetry at porous electrodes fabricated by means of electro-deposition around spherical templates. A theoretical method to extract heterogeneous rate constants for quasireversible and irreversible systems is proposed by the approximation of decoupling of the diffusion within the porous electrode and of bulk diffusion to the electrode surface.