Oxygen Reduction Reaction Catalyzed by Carbon-Supported Platinum Few-Atom Clusters: Significant Enhancement by Doping of Atomic Cobalt.

Oxygen reduction reaction (ORR) plays an important role in dictating the performance of various electrochemical energy technologies. As platinum nanoparticles have served as the catalysts of choice towards ORR, minimizing the cost of the catalysts by diminishing the platinum nanoparticle size has become a critical route to advancing the technological development. Herein, first-principle calculations show that carbon-supported Pt9 clusters represent the threshold domain size, and the ORR activity can be significantly improved by doping of adjacent cobalt atoms. This is confirmed experimentally, where platinum and cobalt are dispersed in nitrogen-doped carbon nanowires in varied forms, single atoms, few-atom clusters, and nanoparticles, depending on the initial feeds. The sample consisting primarily of Pt2~7 clusters doped with atomic Co species exhibits the best mass activity among the series, with a current density of 4.16 A mgPt -1 at +0.85 V vs. RHE that is almost 50 times higher than that of commercial Pt/C.