Chemical Identity of Poly(N-vinylpyrrolidone) End Groups Impact Shape Evolution During the Synthesis of Ag Nanostructures

Ag nanocubes (AgNCs) are predominantly synthesized by the polyol method, where the solvent (ethylene glycol) is considered the reducing agent and poly(N-vinylpyrrolidone) (PVP) the shape-directing agent. An experimental phase diagram for the formation of Ag nanocubes as a function of PVP monomer concentration (C_m) and molecular weight (M_w) demonstrated end groups of PVP impact the final Ag product. Measured rates of the initial Ag⁺ reduction at different PVP C_m and M_w confirmed the reducing effect originates from end-groups. PVP with well-defined aldehyde and hydroxyl end groups lead to the formation of Ag nanocubes and nanowires respectively, indicating the faster reducing agent formed kinetically preferred nanowires. We demonstrate PVP end-groups induce initial reduction of Ag⁺ to form seeds followed by autocatalytic reduction of Ag⁺ by ethylene glycol (and not solvent oxidation products) to form Ag nanostructures. The current study enabled a quantitative description of the role of PVP in nanoparticle shape-control and demonstrates a unique opportunity to design nanostructures by combining nanoparticle synthesis with polymer design to introduce specific physicochemical properties.