Structures and mechanisms in the growth of hybrid Ru-Cu ₂S nanoparticles: From cages to nanonets

Combining metal and semiconductor segments with well-defined morphologies on a single hybrid nanoparticle provides functionality benefiting from the joint and possibly also synergetic properties of the disparate components. We have recently reported the synthesis of a novel family of Ru nano-inorganic caged (NICed) copper(I) sulfide hybrid nanoparticles, which were grown through a mechanism of selective edge growth of the Ru on the copper(I) sulfide seeds. In this work we investigate the effect of reaction conditions on the Ru-Cu ₂S products. There is an extraordinary sensitivity to reaction temperature in which four product structures were discovered upon varying the reaction temperature from 190 to 220 °C. The products changed from homogeneous nuclei of Ru along with the free Cu ₂S seed at lower temperature, to Ru nano-inorganic caged copper(I) sulfide, to long thin Ru structures protruding from the seed surface at the higher temperature range. The resulting materials were imaged and characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), high-angle annular dark field-scanning TEM (HAADF-STEM), and powder Xray diffraction. Differential scanning calorimetric (DSC) analysis of the Cu ₂S template nanoparticles revealed an endothermic peak at the specific temperature for selective edge growth of Ru, and was assigned to a surface change on the seed particle. Competition between homogeneous nucleation of the secondary material Ru and heterogeneous nucleation on the seed Cu ₂S nanoparticle leading to a rich reaction landscape is discussed.