Correlated Optical Spectroscopy and Electron Microscopy Studies of the Slow Ostwald-Ripening Growth of Silver Nanoparticles under Controlled Reducing Conditions

Metallic nanoparticles display distinct localized surface plasmon resonance (LSPR) properties that depend on their size, shape, and composition and that can be monitored to characterize their growth. Utilizing LSPR properties, we report the first investigation of ambient temperature formation of trioctylamine (TOA)-stabilized spherical silver nanoparticles (AgNPs) of ∼3.0-nm diameter by mild reduction of AgClO4 with the weak reducing agent heptamethyltrisiloxane in organic solvent. The appropriate choice of experimental conditions caused slow reduction, which allowed the study of the nanoparticle growth process by time-resolved UV–visible spectroscopy and transmission electron microscopy (TEM). The linear nanoparticle growth kinetics from 50 min to end of the reaction derived from LSPR changes, the absence of a bimodal size distribution during the initial stage of the reduction process from TEM analysis, and the single crystallinity of the resulting AgNPs suggested a diffusion-controlled Ostwald-ripening growth process. It was also found that in addition to its stabilizing ability, TOA acted as a catalyst and facilitated Ag+ reduction. Furthermore, a modest increase in reaction temperature caused a substantial enhancement in the AgNP formation rate, and low concentration of stabilizing ligand yielded an increase in size and dispersity.