Engineering Surface Structure of Pt Nanoshells on Pd Nanocubes to Preferentially Expose Active Surfaces for ORR by Manipulating the Growth Kinetics

Synthesis of Pt nanoshells on substrates can increase the utilization efficiency of Pt atoms and reduce the amount of Pt used in the applications. However, it is still an enormous challenge in tailoring the required crystal facets of Pt nanoshells on a given substrate. In this work, we demonstrate a facile and convenient approach capable for generating Pt octahedral islands with tunable sizes and densities on Pd nanocubes by manipulating the deposition rate. The key to this synthesis is the fine control over the deposition rate of Pt on Pd seeds. Because of the different reactivities at the surface sites, the deposition of Pt can be controlled at a certain site by carefully tuning the deposition rate. With a low concentration of reductant (8.33 mg/mL of glucose), surface diffusion dominates the process, and thus the Pt cubic shells form on Pd cubic seeds. In contrast, when a higher amount of the reductant (16.67 mg/mL of glucose) is added, the deposition starts to dominate the growth of Pt shells. In this case, the deposition would be controlled at the corners, forming eight large Pt octahedra on a cubic Pd seed. Further increasing the deposition rate can induce much higher deposition rates, in which case, the deposition of Pt would likely take place not only at the corners, but also the edge and surface sites of the seeds. Not surprisingly, this growth habit can result in the formation of high-density octahedral islands on Pd cubic seeds. With the same amount of precursor supply, the higher the densities of Pt islands, the smaller the size of the octahedral islands on Pd nanocubes. Unlike other synthetic methods, the size of the octahedral islands on Pd seeds can be even controlled to be smaller than 3 nm by controlling the amount of the Pt precursor. Considering the excellent performance of {111} facets of Pt catalysts toward ORR, the Pt nanocages with small octahedral islands on the surfaces can exhibit a high activity with a mass activity 0.68 A/mg, as high as 5.2 times of that of commercial Pt/C.