Synthesis and High Electrocatalytic Performance of Hexagram Shaped Gold Particles Having an Open Surface Structure with Kinks

Hexagram shaped gold particles and their analogues enclosed by high index facets with kinks have been successfully synthesized by reducing HAuCl₄ with ascorbic acid (AA) in the presence of poly(diallyldimethylammonium chloride) at room temperature. By using electron microscopy, the surfaces of the hexagram shaped Au particle were found to be {541} planes, which contain high-density steps and kinks. In addition, it was found that hexagonal shield-like and other kind of particles present in the product were analogues of the hexagram shaped Au particles structure, in that they had the same surface structure. In order to confirm the surface structure of all the prepared particles, surface structure sensitive underpotential deposition of Pb was carried out, and the cyclic voltammetric profile was in accordance with the proposed {541} surface. Finally, structure–property relationships of the Au hexagrams were experimentally analyzed by employing the electrocatalytic oxidation of AA as a probe reaction. The electrocatalytic reactions of gold cubes with low-index {100} facets and gold trioctahedra with {221} facets were studied as references. The experimental results showed that the hexagram shaped Au particles and their analogues with exposed {541} facets have the highest catalytic activity among the three kinds of gold particles, owing to the high density of kink atoms. This study should motivate us to further explore methods for the preparation of other well-defined polyhedral metal nanocrystals enclosed by high index surfaces.