The role of surface nonuniformity in controlling the initiation of a galvanic replacement reaction.

The use of silver nanocrystals--asymmetrically truncated octahedrons and nanobars--characterized by a nonuniform surface as substrates for a galvanic replacement reaction was investigated. As the surfaces of these nanocrystals contain facets with a variety of different areas, shapes, and atomic arrangements, we were able to examine the roles of these parameters in different stages of the galvanic replacement reaction with HAuCl(4) (e.g., pitting, hollowing, pit closing, and pore formation), and thus obtain a deeper understanding of the reaction mechanism than is possible with silver nanocubes. We found that the most important of these parameters was the atomic arrangement, that is, whether the surface was capped by a {100} or {111} facet, and that the area and shape of the facet had essentially no effect on the initiation of the reaction. Interestingly, through the reaction with asymmetrically truncated octahedrons, we were also able to demonstrate that even when pitting occurred over a large area, this region would be sealed through a combination of atomic diffusion and deposition during the intermediate stages of the reaction. Consequently, even if pitting occurred across a large percentage of the nanocrystal surface, it was still possible to maintain the morphology of the template throughout the reaction.