Oxygen Reduction Reaction on Pt and Pt Bimetallic Surfaces: A Selective Review

In this review we selectively summarize recent progress, primarily from our laboratory, in the development of the oxygen reduction reaction (ORR) catalysis on well-defined surfaces. The focus is on two type of metallic surfaces: platinum single crystals and bimetallic surfaces based on platinum. The single crystal results provide insight into the effects of the platinum structure on the kinetics of the ORR, and create a fundamental link between the specific activity of Pt (rate per unit area) and particle size (for various particle shapes). The results show that the structure sensitive kinetics of the ORR arise primarily due to structure sensitive adsorption of anions. In the absence of specific adsorption, such as in Nafion polymer electrolyte, no particle size effect is expected. The knowledge of the electrocatalysis of the ORR on model bimetallic surfaces on Pt-Ni and Pt-Co bulk alloys was used to resolve the enhanced ORR kinetics on supported Pt-Ni and Pt-Co catalysts. Finally, we show that the ORR on platinum modified with pseudomorphic Pd metal film in alkaline solution is the best catalysts ever used in O2 reduction. For both bimetallic systems, we demonstrated that the ability to make a controlled and well characterized arrangement of two elements in the electrode surface region presage a new era of advances in the ORR electrocatalysis.