Heterogeneous nucleation and shape transformation of multicomponent metallic nanostructures

To be able to control the functions of engineered multicomponent nanomaterials, a detailed understanding of heterogeneous nucleation at the nanoscale is essential. Here, by using in situ synchrotron X-ray scattering, we show that in the heterogeneous nucleation and growth of Au on Pt or Pt-alloy seeds the heteroepitaxial growth of the Au shell exerts high stress (∼2 GPa) on the seed by forming a core/shell structure in the early stage of the reaction. The development of lattice strain and subsequent strain relaxation, which we show using atomic-resolution transmission electron microscopy to occur through the slip of {111} layers, induces morphological changes from a core/shell to a dumbbell structure, and governs the nucleation and growth kinetics. We also propose a thermodynamic model for the nucleation and growth of dumbbell metallic heteronanostructures. The detailed nucleation and growth kinetics and the crystal structure of catalytically relevant CoPt 3 /Au, FePt/Au and Pt/Au metal dumbbell nanoparticles have been obtained by in situ synchrotron small- and wide-angle X-ray scattering techniques.