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

Suprita Jharimune, Rueben Pfukwa, Zhifeng Chen, Justin Anderson, Bert Klumperman, Robert M. Rioux

Research output: Contribution to journalArticlepeer-review

Abstract

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 (Cm) and molecular weight (Mw) demonstrated end groups of PVP impact the final Ag product. Measured rates of the initial Ag+ reduction at different PVP Cm and Mw 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.

Original languageEnglish (US)
Pages (from-to)184-195
Number of pages12
JournalJournal of the American Chemical Society
Volume143
Issue number1
DOIs
StatePublished - Jan 13 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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