Synthesis of Gold Clusters and Nanoparticles Using Cinnamon Extract-A Mechanism and Kinetics Study.

In this work, UV-Vis spectrophotometry, High Resolution Scanning Transmission Electron Microscopes and selected experimental conditions were used to screen the colloidal system. The obtained results complement the established knowledge regarding the mechanism of nanoparticle formation. The process of gold nanoparticles formation involves a two-step reduction of Au ions to Au(0); atom association and metastable cluster formation; autocatalytic cluster growth; ultra-small particle formation (1-2 nm, in diameter); particle growth and larger particles formation; and further autocatalytic crystal growth (D > 100 nm). As a reductant of Au(III) ions, a cinnamon extract was used. It was confirmed that eugenol as one of the cinnamon extract compounds is responsible for fast Au(III) ion reduction, whereas cinnamaldehyde acts as a gold-particle stabilizer. Spectrophotometry studies were carried out to track kinetic traces of gold nanoparticle (D > 2 nm) formation in the colloidal solution. Using the Watzky-Finke model, the rate constants of nucleation and autocatalytic growth were determined. Moreover, the values of energy, enthalpy and entropy of activation for stages related to the process of nanoparticle formation (Index 1 relates to nucleation, and Index 2 relates to the growth) were determined and found to be E1 = 70.6 kJ, E2 = 19.6 kJ, ΔH1 = 67.9 kJ/mol, ΔH2 = 17 kJ/mol, ΔS1 = -76.2 J/(K·mol), ΔS2 = -204.2 J/(K·mol), respectively. In this work the limitation of each technique (spectrophotometry vs. HRSTEM) as a complex tool to understand the dynamic of the colloidal system was discussed.