Synthesis of octahedral gold tip-blobbed nanoparticles and their dielectric sensing properties.

Site-selective synthesis of nanostructures is an important topic in the nanoscience community. Normally, the difference between seeds and deposition atoms in terms of crystallinity triggers the deposition atoms to grow initially at the specific site of nucleation. It is more challenging to control the deposition site of atoms that have the same composition as the seeds because the atoms tend to grow epitaxially, covering the whole surface of the seed nanoparticles. Gold (Au) nano-octahedrons used as seeds in this study possess obvious hierarchical surface energies depending on whether they are at vertices, edges, or terraces. Although vertices of Au nano-octahedrons have the highest surface energy, it remains a challenge to selectively deposit Au atoms at the vertices but not at the edges and faces; this selectivity is required to meet the ever-increasing demands of engineered nanomaterial properties. This work demonstrates an easy and robust method to precisely deposit Au nanoparticles at the vertices of Au nano-octahedrons via wet-chemical seed-mediated growth. The successful synthesis of octahedral Au tip-blobbed nanoparticles (Oh Au TBPs) benefited from the cooperative use of thin silver (Ag) layers at the surface of Au nano-octahedron seeds and iodide ions in the Au growth solution. As-synthesized Au nanostructures (i.e., Au TBPs) gave rise to hybrid optical properties, as evidenced from the UV-vis-NIR extinction spectra, in which a new extinction peak appeared after Au nanoparticles were formed at the vertices of Au nano-octahedrons. A sensitivity evaluation toward dielectric media of a mixture of dimethyl sulfoxide and water suggested that Au TBPs were more optically sensitive compared to the original Au nano-octahedrons. The method demonstrated in this work is promising in the synthesis of advanced Au nanostructures with hybrid optical properties for versatile applications, by engineering the surface energy of vertex-bearing Au nanostructures to trigger site-selective overgrowth of congener Au atoms.