Formation of Star-Like and Core-Shell AuAg Nanoparticles during Two- and Three-Step Preparation in Batch and in Microfluidic Systems

Regular dendrit-like metal nanoparticles and core-shell nanoparticles were formed by the reduction of mixtures of tetrachloroaurate and silver nitrate solutions with ascorbic acid at room temperature in two- and three-step procedures. The formation of these particles was found in batch experiments as well as in micro flow-through processes using static micromixers. The characteristic diameters of 4-branched star particles were in the range between 60 and 100 nm. The typical particles consist of four metal cores which are embedded in a common shell. Additionally, particles with five and more metallic cores were formed, to some extent, and aggregates of the 4-branched particles also were formed. Larger aggregates and network-like structures of connected star particles were formed after sedimentation. The properties of the formed particles are dependent on the educt concentrations as well as on the order of mixing steps and on the time interval between them. Obviously, the relation of nucleation and particle growth in relation to the concentrations of metal ions determines the composition and the properties of formed nanoparticles. So, star-like particles are observed in case of nucleation of Au in absence of silver ions but with silver deposition after short nucleation time. Spherical core shell particles are formed in case of silver salt addition after complete reduction of tetrachloroaurate in flow-through experiments with sufficient residence time between both mixing steps. Polymer layers are always found in the form of a second outer shell even if the polymer solutions are added in an early stage of particle formation.