Compressively Strained and Interconnected Platinum Cones with Greatly Enhanced Activity and Durability toward Oxygen Reduction

The synthesis of cone-shaped Pt nanoparticles featuring compressively-strained {111} facets by depositing Pt atoms on the vertices of Pd icosahedral nanocrystals, followed by selective removal of the Pd template via wet etching, is reported. By controlling the lateral dimensions down to ca. 3 nm, together with a thickness of ca. 2 nm, the Pt cones show greatly enhanced specific and mass activities toward oxygen reduction, with values being 2.8 and 6.4 times those of commercial Pt/C, respectively. Both the strain field and the observed activity trend are rationalized using density functional theory calculations. With the formation of ultrathin linkers among the Pt cones derived from the same Pd icosahedral seed, the interconnected Pt cones acquire stronger interactions with the carbon support, preventing them from detachment and aggregation during the catalytic reaction. Even after 20 000 cycles of accelerated durability test, the Pt cones still show a mass activity 5.3 times higher than the initial value of the Pt/C. The synthesis of cone-shaped Pt nanoparticles featuring compressively-strained {111} facets, the optimal feature for oxygen reduction, by depositing Pt atoms on the vertices of Pd icosahedra, followed by selective removal of the Pd template via wet etching, is reported. The dimensions of Pt cones are controlled down to ca. 2 nm, and the Pt cones are interconnected by ultrathin linkers, which prevent them from migration and aggregation during catalytic reactions. image