Twin-Directed Deposition of Pt on Pd Icosahedral Nanocrystals for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction

Platinum nanocrystals featuring a multiply twinned structure and uniform sizes below 5 nm are superb catalytic materials, but it is difficult to synthesize such particles owing to the high twin-boundary energy (166 mJ/m2) of Pt. Here, we report a simple route to the synthesis of such nanocrystals by selectively growing them from the vertices of Pd icosahedral seeds. The success of this synthesis critically depends on the introduction of Br– ions to slow the reduction kinetics of the Pt(II) precursor while limiting the surface diffusion of Pt adatoms by conducting the synthesis at 30 °C. Owing to the small size and multiply twinned structure of Pt dots, the as-obtained Pd–Pt nanocrystals show remarkably enhanced activity and durability toward oxygen reduction, with a mass activity of 1.23 A mg–1Pt and a specific activity of 0.99 mA cm–2Pt, which are 8.2 and 4.5 times as high as those of the commercial Pt/C.