Shape Control of Silver Nanoparticles by Stepwise Citrate Reduction

Growth of silver nanoparticles by the citrate reduction of silver nitrate under the range of pH from 5.7 to 11.1 was investigated systematically and quantitatively. Reduction of the silver precursor (Ag+) was promoted with increased pH, attributed to the higher activity of the citrate reductant under high pH value. Under high pH, the product was composed of both spherical and rod-like silver nanoparticles as a result of the fast reduction rate of the precursor. Under low pH, the product was mainly dominated by triangle or polygon silver nanoparticles due to the slow reduction rate of the precursor. The product that is dominated by spherical silver nanoparticles cannot be acquired by the one-step citrate reduction method in the range of pH investigated, indicating the poor balance between the nucleation and growth processes in the reactions. On the basis of the results of quantitative analyses, a stepwise reduction method, in which the nucleation and growth processes were carried out at high and low pH, respectively, was proposed for the syntheses of spherical silver nanoparticles.