Halide Anions as Shape-Directing Agents for Obtaining High-Quality Anisotropic Gold Nanostructures

The fundamental role of halide anions in the seed-mediated synthesis of anisotropic noble metal nanostructures has been a subject of debate within the nanomaterials community. Herein, we systematically investigate the roles of chloride, bromide and iodide anions in mediating the growth of anisotropic Au nanostructures. A high-purity surfactant solution of hexadecyltrimethylammonium bromide (CTABr) is used to reliably probe the role of each halide anion without interference from impurities. Our investigation reveals that bromide anions are required for the formation of Au nanorods, while the controlled combination of both bromide and iodide anions are necessary for the production of high-quality Au nanoprisms. Chloride anions, however, are ineffective at promoting anisotropic architectures and are detrimental to nanorod and/or nanoprism growth at high concentrations. We examine the seed structure and propose a growth model based on facet-selective adsorption on low-index Au facets to rationalize the nanostructures obtained by these methods. Our approach provides a facile synthesis of anisotropic Au nanostructures by way of a single growth solution and yields the desired morphologies with high purity. These results demonstrate that appropriate combinations of halide anions provide a versatile paradigm for manipulating the morphological distribution of Au nanostructures.