Two-Step Reshaping of Acicular Gold Nanoparticles

Anisometric plasmonic nanoparticles find applications in various fields, from photocatalysis to biosensing. However, exposure to heat or to specific chemical environments can induce their reshaping, leading to loss of function. Understanding this process is therefore relevant both for the fundamental understanding of such nano-objects and for their practical applications. We followed in real time the spontaneous reshaping of gold nanotetrapods in solution via optical absorbance spectroscopy, revealing a two-step kinetics (fast tip flattening into {110} facets, followed by slow arm shortening) with characteristic times a factor of 6 apart but sharing an activation energy around 1 eV. Synchrotron-based X-ray scattering confirms this time evolution, which is much faster in solution than in the dry state, highlighting the importance of the aqueous medium and supporting a dissolution-redeposition mechanism or facilitated surface diffusion. High-temperature transmission electron microscopy of the dry particles validates the solution kinetics.