Structural Evolution of Three-Component Nanoparticles in Polymer Nanoreactors

J Am Chem Soc. 2017 Jul 26;139(29):9876-9884. doi: 10.1021/jacs.7b03163. Epub 2017 Jul 12.

Abstract

Recent developments in scanning probe block copolymer lithography (SPBCL) enable the confinement of multiple metal precursors in a polymer nanoreactor and their subsequent transformation into a single multimetallic heterostructured nanoparticle through thermal annealing. However, the process by which multimetallic nanoparticles form in SPBCL-patterned nanoreactors remains unclear. Here, we utilize the combination of PEO-b-P2VP and Au, Ag, and Cu salts as a model three-component system to investigate this process. The data suggest that the formation of single-component Au, Ag, or Cu nanoparticles within polymer nanoreactors consists of two stages: (I) nucleation, growth, and coarsening of the particles to yield a single particle in each reactor; (II) continued particle growth by depletion of the remaining precursor in the reactor until the particle reaches a stable size. Also, different aggregation rates are observed for single-component particle formation (Au > Ag > Cu). This behavior is also observed for two-component systems, where nucleation sites have greater Au content than the other metals. This information can be used to trap nanoparticles with kinetic structures. High-temperature treatment ultimately facilitates the structural evolution of the kinetic particle into a particle with a fixed structure. Therefore, with multicomponent systems, a third stage that involves elemental redistribution within the particle must be part of the description of the synthetic process. This work not only provides a glimpse at the mechanism underlying multicomponent nanoparticle formation in SPBCL-generated nanoreactors but also illustrates, for the first time, the utility of SPBCL as a platform for controlling the architectural evolution of multimetallic nanoparticles in general.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Copper / chemistry*
  • Gold / chemistry*
  • Microscopy, Electron, Scanning Transmission
  • Molecular Structure
  • Nanoparticles / chemistry*
  • Particle Size
  • Polyethylene Glycols / chemical synthesis
  • Polyethylene Glycols / chemistry*
  • Polyvinyls / chemical synthesis
  • Polyvinyls / chemistry*
  • Salts / chemistry
  • Silver / chemistry*
  • Surface Properties

Substances

  • Polyvinyls
  • Salts
  • poly(2-vinylpyridine-block-ethylene oxide)
  • Silver
  • Polyethylene Glycols
  • Gold
  • Copper