The ligand shell as an energy barrier in surface reactions on transition metal nanoparticles

Jeremy G. Smith, Prashant Jain

Research output: Contribution to journalArticle

Abstract

Transition metal nanoparticles, including those employed in catalytic, electrocatalytic, and photocatalytic conversions, have surfaces that are typically coated with a layer of short or long-chain ligands. There is little systematic understanding of how much this ligand layer affects the reactivity of the underlying surface. We show for Ag nanoparticles that a surface-adsorbed thiol layer greatly impedes the kinetics of an ionic chemical reaction taking place on the Ag surface. The model reaction studied is the galvanic exchange of Ag with Au3+ ions, the kinetics of which is measured on individual thiol-coated nanoparticles using in situ optical scattering spectroscopy. We observe a systematic lowering of the reactivity of the nanoparticle as the chain length of the thiol is increased, from which we deduce that the ligand layer serves as an energy barrier to the transport of incoming/outgoing reactive ions. This barrier effect can be decreased by light irradiation, resulting from weakened binding of the thiol layer to the metal surface. We find that the influence of the surface ligand layer on reactivity is much stronger than factors such as nanoparticle size, shape, or crystallinity. These findings provide improved understanding of the role of ligand or adsorbates in colloidal catalysis and photocatalysis and have important implications for the transport of reactants and ions to surfaces and for engineering the reactivity of nanoparticles using surface passivation.

Original languageEnglish (US)
Pages (from-to)6765-6773
Number of pages9
JournalJournal of the American Chemical Society
Volume138
Issue number21
DOIs
StatePublished - Jun 1 2016

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Metal Nanoparticles
Metal nanoparticles
Energy barriers
Surface reactions
transition element
Nanoparticles
ligand
Transition metals
Sulfhydryl Compounds
Ligands
shell
thiol
energy
Ions
Ion Transport
ion
Catalysis
Spectrum Analysis
kinetics
Kinetics

ASJC Scopus subject areas

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

Cite this

The ligand shell as an energy barrier in surface reactions on transition metal nanoparticles. / Smith, Jeremy G.; Jain, Prashant.

In: Journal of the American Chemical Society, Vol. 138, No. 21, 01.06.2016, p. 6765-6773.

Research output: Contribution to journalArticle

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