Synergistic Hybrid Electrocatalysts of Platinum Alloy and Single-Atom Platinum for an Efficient and Durable Oxygen Reduction Reaction

Abstract

Pt single-atom materials possess an ideal atom economy but suffer from limited intrinsic activity and side reaction of producing H₂O₂ in catalyzing the oxygen reduction reaction (ORR); platinum alloys have higher intrinsic activity but weak stability. Here, we demonstrate that anchoring platinum alloys on single-atom Pt-decorated carbon (Pt-SAC) surmounts their inherent deficiencies, thereby enabling a complete four-electron ORR pathway catalysis with high efficiency and durability. Pt₃Co@Pt-SAC demonstrates an exceptional mass and specific activities 1 order of magnitude higher than those of commercial Pt/C. They are durable throughout 50000 cycles, showing only a 10 mV decay in half-wave potential. An <i>in situ</i> Raman analysis and theoretical calculations reveal that Pt₃Co core nanocrystals modulate electron structures of the adjacent Pt single atoms to facilitate the intermediate absorption for fast kinetics. The superior durability is attributed to the shielding effect of the Pt-SAC coating, which significantly mitigates the dissolution of Pt₃Co cores. The hybridizing strategy might promote the development of highly active and durable ORR catalysts.