The role of trace Ag in the synthesis of Au nanorods†
One of the more useful syntheses of single crystalline, uniform Au nanorods from Au spherical seeds relies on the addition of trace Ag ions, yet the role that Ag+ plays has remained both elusive and controversial, due in part to lack of knowledge of how the Ag distribution in the nanorod evolves over time. In this work, we fill in this knowledge gap by correlating the spatial distribution of Ag within Au nanorods with nanorod anisotropic growth through time-course X-ray absorption spectroscopy (XAFS)-derived atomic-level elemental coordination paired with electron microscopy for nanoscale morphological analysis. Using this method, a plausible pathway for the conversion of spherical seeds into Au nanorods is proposed. Evidence shows that the nanorod anisotropic growth is directly related to the Ag surface coverage. Anisotropy is induced early in the reaction when Ag first deposits onto the nanoparticle surface, but growth occurs more isotropically as the reaction progresses and Ag diffuses into the nanorod bulk. The results of this investigation and methods employed should be extendable to many anisotropic nanoparticle syntheses that make use of trace elemental species as shape-control additives.