摘要
Controlled syntheses of PtNi metal nanocrystals with unique structures for catalyzing oxygen reduction reactions （ORRs） have attracted great interest. Here, we report the one-step synthesis of single-crystal PtNi octahedra with in situ-developed highly concave features and self-confined composition that are optimal for ORR. Detailed studies revealed that the Pt-rich seeding, subsequent Pt/Ni co-reduction, and Pt-Ni interfusion resulted in uniform single-crystal PtNi octahedra, and that the combination of Ni facet segregation and oxygen etching of a Ni-rich surface led to the concavity and confined Ni content. The concave PtNi nanocrystals exhibited much higher ORR performance than the commercially available Pt/C catalyst in terms of both specific activity （29.1 times higher） and mass activity （12.9 times higher） at 0.9 V （vs. reversible hydrogen electrode （RHE））. The performance was also higher than that of PtNi octahedra without concavity, confirming that the higher activity was closely related to its morphology. Moreover, the concave octahedra also exhibited remarkable stability in ORR （93% mass activity remained after 10,000 cycles between 0.6 and 1.1 V vs. RHE） owing to the passivation of the unstable sites.
Controlled syntheses of PtNi metal nanocrystals with unique structures for catalyzing oxygen reduction reactions （ORRs） have attracted great interest. Here, we report the one-step synthesis of single-crystal PtNi octahedra with in situ-developed highly concave features and self-confined composition that are optimal for ORR. Detailed studies revealed that the Pt-rich seeding, subsequent Pt/Ni co-reduction, and Pt-Ni interfusion resulted in uniform single-crystal PtNi octahedra, and that the combination of Ni facet segregation and oxygen etching of a Ni-rich surface led to the concavity and confined Ni content. The concave PtNi nanocrystals exhibited much higher ORR performance than the commercially available Pt/C catalyst in terms of both specific activity （29.1 times higher） and mass activity （12.9 times higher） at 0.9 V （vs. reversible hydrogen electrode （RHE））. The performance was also higher than that of PtNi octahedra without concavity, confirming that the higher activity was closely related to its morphology. Moreover, the concave octahedra also exhibited remarkable stability in ORR （93% mass activity remained after 10,000 cycles between 0.6 and 1.1 V vs. RHE） owing to the passivation of the unstable sites.
基金
We acknowledge support from the National Science Foundation （NSF） through award DMR-1437263 on catalysis studies and the Office of Naval Research （ONR） under award N00014-15-1-2146 for synthesis efforts. X. F. D. acknowledges support from the U.S. Department of Energ34 Office of Basic Energy Sciences, Division of Materials Science and Engineering through award DE-SC0008055. E. B. Z. received additional support from China Scholarship Council （CSC） scholarships. We also thank the Electron Imaging Center of Nanomachines at CNSI for TEM support.
