Seed-mediated synthesis of Au@PtCu nanostars with rich twin defects as efficient and stable electrocatalysts for methanol oxidation reaction.

Pt-based nanocrystals with a twinned structure are highly desirable to achieve high performances in both catalytic activity and durability for methanol oxidation reaction (MOR). However, it still remains great challenge for producing such twinned nanocrystals due to the high internal strain energy of Pt. Here we present a seed-mediated approach to generate Au@PtCu nanostars with a five-fold twinned structure using Au decahedra as seeds. The composition of Pt/Cu in the nanocrystals was tuned by varying the molar ratio of Pt to Cu salt precursors with the amount of Au seeds being the same. Through composition optimization, Au@Pt 1.2 Cu nanostars achieved the highest specific (1.06 mA cm -2 ) and mass (0.18 mA mg Pt -1 ) activities for MOR, which were about 5.9 and 1.6 times higher than those of commercial Pt/C, respectively. After accelerated stability test (ADT) for 1500 cycles, such nanostars remained ∼95% of specific activity compared to a loss of ∼28% for commercial Pt/C, indicting their superior durability for MOR. We believed that this enhancement may arise from the unique twinned structure and possible synergetic effect between Pt and Cu components.