Anisotropic Growth of Silver Nanoparticles Is Kinetically Controlled by Polyvinylpyrrolidone Binding

Zhifeng Chen, Ji Woong Chang, Choumini Balasanthiran, Scott Thomas Milner, Robert Martin Rioux, Jr.

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Polyvinylpyrrolidone (PVP) is used in the synthesis of Ag nanoparticles (NPs) with controlled shape, most commonly producing cubes. The mechanism for shape control is unclear but believed by many to be caused by preferential binding of PVP to Ag(100) facets compared to Ag(111) facets and assumed by most to be the result of thermodynamic control, whereby facets with lower interfacial free energy predominate. To investigate this mechanism, we measured adsorption isotherms of PVP on different-shaped Ag NPs, to determine the thermodynamics of PVP adsorption to Ag(100) and Ag(111) facets. The equilibrium adsorption constant is independent of PVP molecular weight and depends only weakly on NP shape (and thus Ag facet). The equilibrium adsorption constant for PVP on Ag(111) (2.8 M -1 ) is about half that on Ag(100) (5 M -1 ). From a Wulff construction, this difference is not nearly enough to produce cubes via thermodynamic control. This result indicates the importance of kinetic control of the Ag nanoparticle shape by PVP, as has recently been proposed.

Original languageEnglish (US)
Pages (from-to)4328-4337
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number10
DOIs
StatePublished - Mar 13 2019

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Povidone
Silver
Nanoparticles
Thermodynamics
Adsorption
Growth
Adsorption isotherms
Free energy
Molecular weight
Kinetics
Molecular Weight

All Science Journal Classification (ASJC) codes

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

Cite this

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title = "Anisotropic Growth of Silver Nanoparticles Is Kinetically Controlled by Polyvinylpyrrolidone Binding",
abstract = "Polyvinylpyrrolidone (PVP) is used in the synthesis of Ag nanoparticles (NPs) with controlled shape, most commonly producing cubes. The mechanism for shape control is unclear but believed by many to be caused by preferential binding of PVP to Ag(100) facets compared to Ag(111) facets and assumed by most to be the result of thermodynamic control, whereby facets with lower interfacial free energy predominate. To investigate this mechanism, we measured adsorption isotherms of PVP on different-shaped Ag NPs, to determine the thermodynamics of PVP adsorption to Ag(100) and Ag(111) facets. The equilibrium adsorption constant is independent of PVP molecular weight and depends only weakly on NP shape (and thus Ag facet). The equilibrium adsorption constant for PVP on Ag(111) (2.8 M -1 ) is about half that on Ag(100) (5 M -1 ). From a Wulff construction, this difference is not nearly enough to produce cubes via thermodynamic control. This result indicates the importance of kinetic control of the Ag nanoparticle shape by PVP, as has recently been proposed.",
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Anisotropic Growth of Silver Nanoparticles Is Kinetically Controlled by Polyvinylpyrrolidone Binding. / Chen, Zhifeng; Chang, Ji Woong; Balasanthiran, Choumini; Milner, Scott Thomas; Rioux, Jr., Robert Martin.

In: Journal of the American Chemical Society, Vol. 141, No. 10, 13.03.2019, p. 4328-4337.

Research output: Contribution to journalArticle

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AU - Rioux, Jr., Robert Martin

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