Oxidative Etching of Pd Decahedral Nanocrystals with a Penta-twinned Structure and Its Impact on Their Growth Behavior

We report a systematic study of the oxidative etching of penta-twinned Pd decahedral nanocrystals by O2/I– under different conditions and its impact on their subsequent growth behavior. Analysis by transmission electron microscopy shows significant rounding of the decahedral structure. More specifically, the etching is found to begin at the equatorial vertices, due to their high surface free energy, and proceed along the adjacent, equatorial edges through the dissolution of low-coordination atoms. Comparison of the etching behaviors under different conditions reveals the critical role of a reductive environment for the initiation of oxidative etching, possibly due to the presence of a protective oxide layer on the surface of Pd decahedra. Overgrowth on the seeds with a rounded profile generates penta-twinned Pd nanorods with an asymmetric, tapered structure as a result of simultaneous axial and radial growth. In comparison, the original decahedral seeds only show axial growth, leading to the formation of penta-twinned nanorods with a uniform size along the axial direction. A good understanding of the etching and growth behaviors of Pd decahedral nanocrystals will be useful for the successful adoption of these nanomaterials in real-world applications, including their use as catalysts and as a platform for the development of more complex nanostructures.