Nanoelectrochemical approach to detecting short-lived intermediates of electrocatalytic oxygen reduction.

Development of better catalysts for the oxygen reduction reaction (ORR) and other electrocatalytic processes requires detailed knowledge of reaction pathways and intermediate species. Here we report a new methodology for detecting charged reactive intermediates and its application to the mechanistic analysis of ORR. A nanopipette filled with an organic phase that is immiscible with the external aqueous solution was used as a tip in the scanning electrochemical microscope to detect and identify a short-lived superoxide (O2(●-)) intermediate and to determine the rate of its generation at the catalytic Pt substrate and its lifetime in neutral aqueous solution. The voltammogram of the O2(●-) anion transfer to the organic phase provides a unique signature for unambiguous identification of superoxide. The extremely short attainable separation distance between the pipette tip and substrate surface (∼1 nm) makes this technique suitable for detecting and identifying charged intermediates of catalytic processes with a lifetime of a few nanoseconds.