Physicochemical properties of ultrasmall colloidal silver nanoparticles: an experimental and computational approach

Silver nanoparticles (AgNPs) exhibit very interesting properties that have been employed in several kinds of applications spanning from antibacterial activity to plasmon-polaritons generation. Nanoparticle size strongly influences these applications. However, the characterization of ultrasmall AgNPs (particle diameter < 10 nm) encompassing different aspects such as average size, polydispersion, shape (anisotropy), concentration, and density remains a challenging task. To address these challenges, we combined TEM measurements with a computational framework based on Mie-Gans theory. This allowed us to describe the aforementioned AgNP features accurately. The synthesis of AgNPs in an aqueous medium involved the use of silver nitrate as a chemical precursor and sodium borohydride as a reducing agent, with polyvinylpyrrolidone acting as a stabilizing agent. Our outcomes showed that increasing the concentration of the precursor and reducing agent with a fixed 1 : 2 molar ratio tends to yield ultrasmall AgNPs with low to moderate polydispersion, a nearly spherical shape (low anisotropy), concentration in the nanomolar range and density close to silver bulk. Also, we established an analytical expression that correlates the extinction molar absorptivity to AgNP size considering the nanoparticle shape. Notably, the computational framework proved to be highly effective in extracting crucial information about the AgNPs from UV-vis spectroscopy data. In conclusion, our study sheds light on the unique properties of ultrasmall AgNPs and presents a comprehensive approach for properly characterizing these nanoparticles, paving the way for further advancements in their applications.