Size‐Controlled Synthesis of Sub‐10 nm PtNi3 Alloy Nanoparticles and their Unusual Volcano‐Shaped Size Effect on ORR Electrocatalysis

Dealloyed Pt bimetallic core–shell catalysts derived from low‐Pt bimetallic alloy nanoparticles (e.g, PtNi₃) have recently shown unprecedented activity and stability on the cathodic oxygen reduction reaction (ORR) under realistic fuel cell conditions and become today's catalyst of choice for commercialization of automobile fuel cells. A critical step toward this breakthrough is to control their particle size below a critical value (≈10 nm) to suppress nanoporosity formation and hence reduce significant base metal (e.g., Ni) leaching under the corrosive ORR condition. Fine size control of the sub‐10 nm PtNi₃ nanoparticles and understanding their size dependent ORR electrocatalysis are crucial to further improve their ORR activity and stability yet still remain unexplored. A robust synthetic approach is presented here for size‐controlled PtNi₃ nanoparticles between 3 and 10 nm while keeping a constant particle composition and their size‐selected growth mechanism is studied comprehensively. This enables us to address their size‐dependent ORR activities and stabilities for the first time. Contrary to the previously established monotonic increase of ORR specific activity and stability with increasing particle size on Pt and Pt‐rich bimetallic nanoparticles, the Pt‐poor PtNi₃ nanoparticles exhibit an unusual “volcano‐shaped” size dependence, showing the highest ORR activity and stability at the particle sizes between 6 and 8 nm due to their highest Ni retention during long‐term catalyst aging. The results of this study provide important practical guidelines for the size selection of the low Pt bimetallic ORR electrocatalysts with further improved durably high activity.