Precise Seed-Mediated Growth and Size-Controlled Synthesis of Palladium Nanoparticles Using a Green Chemistry Approach

In this paper, we present a “green” and size-controlled seed-mediated growth method by which differently sized palladium (Pd) nanoparticles, spanning from 3.4 to 7.6 nm, with an increment of 1.4 nm, were synthesized. Monodisperse Pd nanoparticles (ca. 3.4 nm, standard deviation = 0.7 nm) were first synthesized and stabilized in an aqueous solution at 95 °C using nontoxic ascorbic acid and sodium carboxymethyl cellulose (CMC) as reducing agent and capping agent, respectively. These Pd nanoparticles were subsequently employed as seeds on the surface of which fresh Pd ²⁺ ions were reduced by the weak reducing agent ascorbic acid. Optimal conditions were determined that favored the homogeneous and sequential accumulation of Pd atoms on the surface of the Pd seeds, rather than the formation of new nucleation sites in the bulk growth solution, thereby achieving atomic-level control over particle sizes. The adsorbed CMC molecules did not inhibit the addition of Pd atoms onto the seeds during the growth but provided stabilization of the Pd nanoparticles in aqueous solution after the growth. Potential mechanisms that underpin this seed-mediated growth process are provided and discussed. One advantage of this seed growth process is that it provides stoichiometric control over the size of the Pd nanoparticles by simply varying Pd²⁺ added during the growth stage. Furthermore, the use of ecologically friendly reagents, such as water (solvent), CMC (capping agent), and ascorbic acid (reducing agent), in both the seed synthesis and subsequent seed-mediated growth provides both “green” and economic attributes to this process.