Copper Template Design for the Synthesis of Bimetallic Copper–Rhodium Nanoshells through Galvanic Replacement

Galvanic replacement reactions are widely used in the synthesis of bimetallic nanoshells. Essential to these syntheses is the design of template materials with electrochemical potentials that are low enough to facilitate the replacement of a wide variety of metals. While Cu is an attractive template from this standpoint, it has only rarely been used due to its propensity for oxidation and the associated difficulties in achieving chemically stable colloids. Here, a synthetic scheme is demonstrated for the design of supported Cu templates and their subsequent replacement with Rh where the detrimental influences of oxidation are not only mitigated but used to place shape and compositional controls on the reaction product. It is shown that the CuRh nanoshells can be produced that are shaped as substrate‐truncated nanocubes or cuboctahedrons depending upon the degree of exposure that the Cu templates have to dissolved oxygen. Moreover, it is demonstrated that the intentional surface oxidation of the Cu template followed by Cu2O removal results in galvanic replacement reactions yielding porous nanoshells with far greater Rh replacement. The study forwards the design of Cu templates for galvanic replacement reactions and presents opportunities for their use in other template‐mediated syntheses.