Production of Pd nanoparticles in microemulsions. Effect of reaction rates on the particle size

Abstract

In the synthesis of metallic nanoparticles in microemulsions, we hypothesized that the particle size is controlled by the reaction rate and not by the microemulsion size. Thus, the changes observed in the particle sizes as reaction conditions, such as concentrations, temperatures, the type of surfactant used, etc., are varied which should not be correlated directly to the modification of these conditions but indirectly to the changes they produce in the reaction rates. In this work, the microemulsions were formulated with benzene and water as continuous and dispersed phases, respectively, using n-dodecyltrimethylammonium bromide (DTAB) and n-octanol as the surfactant and cosurfactant. Using time-resolved UV-vis spectroscopy, we measured the reaction rates in the production of palladium (Pd) nanoparticles inside the microemulsions at different reactant concentrations and temperatures, keeping all the other parameters constant. The measured reaction rates were then correlated with the particle sizes measured by transmission electron microscopy (TEM). We found that the nanoparticle size increases linearly as the reaction rate increases, independently of the actual reactant concentration or temperature. We proposed a simple model for the observed kinetics where the reaction rate is controlled mainly by the diffusion of the reducing agent. With this model, we predicted that the particle size should depend indirectly, via the reaction kinetics, on the micelle radius, the water volume and the total microemulsion volume. Some of these predictions were indeed observed and reported in the literature.