A reasonable approach for the generation of hollow icosahedral kernels in metal nanoclusters

Although the hollow icosahedral M₁₂ kernel has been extensively observed in metal nanoclusters, its origin remains a mystery. Here we report a reasonable avenue for the generation of the hollow icosahedron: the kernel collapse from several small nano-building blocks to an integrated hollow icosahedron. On the basis of the Au alloying processes from Ag₂₈Cu₁₂(SR)₂₄ to the template-maintained Au_xAg_28-xCu₁₂(SR)₂₄ and then to the template-transformed Au₁₂Cu_yAg_32-y(SR)₃₀, the kernel evolution/collapse from "tetrahedral Ag₄ + 4^∗Ag₃" to "tetrahedral Au₄ + 4^∗M₃ (M = Au/Ag)" and then to "hollow icosahedral Au₁₂" is mapped out. Significantly, the "kernel collapse" from small-sized nano-building blocks to large-sized nanostructures not only unveils the formation of hollow icosahedral M₁₂ in this work, but also might be a very common approach in constructing metallic kernels of nanoclusters and nanoparticles (not limited to the M₁₂ structure).