Application of SECM in tracing of hydrogen peroxide at multicomponent non-noble electrocatalyst films for the oxygen reduction reaction

Abstract The redox competition mode of scanning electrochemical microscopy (RC-SECM) was used to study the electrocatalytic activity of three different non-noble metal O 2 reduction catalysts at a pH value of 7.4, namely; multi-walled carbon nanotubes (MWCNTs), cobalt protoporphyrin (CoP) and a composite of MWCNTs/CoP. The collection efficiency of a scanning electrochemical microscopy (SECM) tip for the H 2 O 2 generated by the reduction of O 2 at the catalyst layer was almost 100%. Consequently, SECM experiments in a combined redox competition and generator/collector mode could be applied for the determination of the number of electrons exchanged during O 2 reduction, leading to improved understanding of the intrinsic features of catalyst activity. This approach avoids the typical limitations encountered with rotating ring disk electrode (RRDE) voltammetry, notably, the variation of the quantity of H 2 O 2 in the proximity of the electrode with the speed of electrode rotation or the chemical decomposition of reaction intermediates on the Pt ring, which often introduce inconsistencies and errors in the measured values of the number of exchanged electrons. It is commonly assumed that the O 2 reduction reaction on most non-noble metal catalysts proceeds via formation of H 2 O 2 as an intermediate. The follow-up reaction of H 2 O 2 , typically chemical decomposition or electrochemical reduction, influences the overall number of electrons exchanged during O 2 reduction. In this study, we have confirmed by comparing the rate of electrochemical reduction of H 2 O 2 using rotating disk electrode (RDE) measurements with its rate of chemical decomposition studied using a positioned SECM tip, that for the MWCNTs/CoP catalyst, chemical decomposition is predominantly determining the overall number of exchanged electrons per O 2 molecule.