Controlling the Deposition of Pd on Au Nanocages: Outer Surface Only versus Both Outer and Inner Surfaces

When a metal precursor is reduced in the presence of Au nanocages with a hollow interior and porous walls, in principle the resultant metal atoms can be deposited onto both the outer and inner surfaces or just the outer surface. Here we demonstrate that these two different scenarios of metal deposition can be deterministically achieved by controlling the reduction kinetics of the precursor. Specifically, if PdCl₄^2- is employed as the precursor, its fast reduction kinetics favors the solution reduction pathway, in which the resultant Pd atoms are deposited only onto the outer surface for the generation of Au@Pd double-shelled nanocages. When the precursor is switched to PdBr₄^2- to slow down the reduction, the precursor can readily diffuse into the interior of the Au nanocages prior to its reduction to elemental Pd. As such, both the outer and inner surfaces of the nanocages become coated with Pd for the generation of Pd@Au@Pd triple-shelled nanocages. This study not only offers a new synthetic approach to metal nanocages with diverse compositions and structures but also demonstrates the necessity of controlling the relative rates of reduction and bulk diffusion of a metal precursor when nanostructures with a hollow interior and porous walls are used for seed-mediated growth.