Simultaneous Mapping of Oxygen Reduction Activity and Hydrogen Peroxide Generation on Electrocatalytic Surfaces

Electrochemical scanning probe microscopies have become valuable experimental tools, owing to their capability of capturing topographic features in addition to mapping the electrochemical activity of nanoscale oxygen reduction catalysts. However, most scanning probe techniques lack the ability to correlate topographic features with the electrochemical oxygen reduction and peroxide formation in real time. In this report, we show that it is indeed possible to construct high-resolution catalytic current maps at an electrified solid–liquid interface by placing a specially made Au-coated SiO₂ Pt atomic force microscopy and scanning electrochemical microscopy (AFM–SECM) dual electrode tip approximately 4–8 nm above the reaction center. The catalytic current measured every 16 nm and high collection efficiency (≈90 %) of the reverse current of peroxide byproducts was also demonstrated with the help of the dual electrode tip. Simultaneous oxygen reduction and intermediate peroxide oxidation current mapping was demonstrated using this Au-coated SiO₂ Pt probe on two model surfaces, namely highly oriented pyrolytic graphite and Pt nanoparticles (NPs) supported on a glassy carbon surface.