Journal of the American Chemical Society, Vol.129, No.5, 1089-1094, 2007
Controlled formation of ag nanoparticles by means of long-chain sodium polyacrylates in dilute solution
A new tool is presented to control formation of Ag nanoparticles. Small amounts of silver ions were added to dilute solutions of long-chain sodium polyacrylates (NaPA). Four NaPA samples covering a molar mass regime of 97 kD <= M-w <= 650 kD have been used. With amounts of added Ag+ as low as 1-2% of the COO- groups of the polyanionic chains, significant changes could already be induced in the NaPA coils with 650 kD. If the NaPA concentration was kept below 0.1 g/L, the coils with 650 kD exhibited a significant coil shrinking in stable solutions. At larger NaPA concentrations, addition of Ag+ initiates an aggregation of the polyacrylate coils toward compact structures. Coil shrinking and aggregation was revealed by means of time-resolved static light scattering. If exposed to UV-radiation, small Ag particles formed within the shrunken anionic polyacrylate coils. The Ag nanoparticles were identified by means of an enhanced light scattering and a characteristic plasmon absorption band around 410 nm. No such Ag particle formation could be observed even at 5 times larger concentrations of Ag+ and NaPA if the two smallest polyacrylate samples have been used under otherwise equal conditions. This molar mass sensitive response of NaPA to Ag+-addition suggests an interesting phenomenon: if the coil size of the NaPa chains, which act as Ag+ collectors, is large enough, local Ag+ concentration in these coil-shaped Ag+ containers exceeds a critical value, and irradiation with UV generates Ag nanoparticles.