Rotating nanoparticle array electrode for the kinetic study of reactions under mixed control

A method for the determination of the intrinsic electrocatalytic activity of metal nanoparticles for reactions under mixed diffusion-activation control is proposed. The working electrode consists of a nanoparticle array supported on a rotating disc of an inert conducting substrate. This electrode configuration reduces significantly the contribution of the reactant diffusion to the experimental current–potential curves and consequently, the kinetic parameters of the reaction can be evaluated more accurately. A model was developed for the diffusion process in the proposed configuration, which includes a parameter related to the degree of dispersion of the nanoparticles on the electrode surface (active area factor). It allows one to evaluate changes in the current–potential plot under conditions of constant particle diameter, which is essential for the appropriate analysis of the electrocatalytic activity of nanoparticles. On this basis the dependences of the current and current density for the hydrogen oxidation reaction on overpotential, rotation rate, particle size and active area factor were derived. The validity of these expressions was verified through the analysis of experimental results.