Unraveling Structural Information of Turkevich Synthesized Plasmonic Gold-Silver Bimetallic Nanoparticles

For the synthesis of gold-silver bimetallic nanoparticles, the Turkevich method has been the state-of-the-art method for several decades. It is presumed that this procedure results in a homogeneous alloy, although this has been debatable for many years. In this work, it is shown that neither a full alloy, nor a perfect core-shell particle is formed but rather a core-shell-like particle with altering metal composition along the radial direction. In-depth wet-chemical experiments are performed in combination with advanced transmission electron microscopy, including energy-dispersive X-ray tomography, and finite element method modeling to support the observations. From the electron tomography results, the core-shell structure can be clearly visualized and the spatial distribution of gold and silver atoms can be quantified. Theoretical simulations are performed to demonstrate that even though UV-vis spectra show only one plasmon band, this still originates from core-shell type structures. The simulations also indicate that the core-shell morphology does not so much affect the location of the plasmon band, but mainly results in significant band broadening. Wet-chemistry experiments provide the evidence that the synthesis pathway starts with gold enriched alloy cores, and later on in the synthesis mainly silver is incorporated to end up with a silver enriched alloy shell.