Scanning electrochemical microscopy. 47. Imaging electrocatalytic activity for oxygen reduction in an acidic medium by the tip generation-substrate collection mode.

The oxygen reduction reaction (ORR) in acidic medium was studied on different electrode materials by scanning electrochemical microscopy (SECM) operating in a new variation of the tip generation-substrate collection mode. An ultramicroelectrode tip placed close to the substrate electrode oxidizes water to oxygen at a constant current. The substrate is held at a potential where the tip-generated oxygen is reduced and the resulting substrate current is measured. By changing the substrate potential, it is possible to obtain a polarization (current-potential) curve, which depends on the electrocatalytic activity of the substrate material. The main difference between this mode and the classical feedback SECM mode of operation is that the feedback diffusion process is not required for the measurement, allowing its application for studying the ORR in acidic solutions. Activity-sensitive images of heterogeneous surfaces, e.g., with Pt and Au electrodes, were obtained from the substrate current when the x-y plane was scanned with the tip. The usefulness of this technique for imaging electrocatalytic activity of smooth metallic electrodes and of highly dispersed fuel cell-type electrocatalysts was demonstrated. The application of this method to the combinatorial chemical analysis of electrode materials and electrocatalysts is discussed.