Stability, surface features, and atom leaching of palladium nanoparticles: Toward prediction of catalytic functionality

Hadi Ramezani-Dakhel, Peter A. Mirau, Rajesh R. Naik, Marc Knecht, Hendrik Heinz

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Surfactant-stabilized metal nanoparticles have shown promise as catalysts although specific surface features and their influence on catalytic performance have not been well understood. We quantify the thermodynamic stability, the facet composition of the surface, and distinct atom types that affect rates of atom leaching for a series of twenty near-spherical Pd nanoparticles of 1.8 to 3.1 nm size using computational models. Cohesive energies indicate higher stability of certain particles that feature an approximate 60/20/20 ratio of {111}, {100}, and {110} facets while less stable particles exhibit widely variable facet composition. Unique patterns of atom types on the surface cause apparent differences in binding energies and changes in reactivity. Estimates of the relative rate of atom leaching as a function of particle size were obtained by the summation of Boltzmann-weighted binding energies over all surface atoms. Computed leaching rates are in good qualitative correlation with the measured catalytic activity of peptide-stabilized Pd nanoparticles of the same shape and size in Stille coupling reactions. The agreement supports rate-controlling contributions by atom leaching in the presence of reactive substrates. The computational approach provides a pathway to estimate the catalytic activity of metal nanostructures of engineered shape and size, and possible further refinements are described.

Original languageEnglish
Pages (from-to)5488-5492
Number of pages5
JournalPhysical Chemistry Chemical Physics
Volume15
Issue number15
DOIs
StatePublished - Apr 21 2013

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surface stability
Palladium
leaching
Leaching
palladium
Nanoparticles
Atoms
nanoparticles
predictions
atoms
flat surfaces
Binding energy
catalytic activity
Catalyst activity
binding energy
Metal nanoparticles
estimates
Chemical analysis
Surface-Active Agents
metals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

Stability, surface features, and atom leaching of palladium nanoparticles : Toward prediction of catalytic functionality. / Ramezani-Dakhel, Hadi; Mirau, Peter A.; Naik, Rajesh R.; Knecht, Marc; Heinz, Hendrik.

In: Physical Chemistry Chemical Physics, Vol. 15, No. 15, 21.04.2013, p. 5488-5492.

Research output: Contribution to journalArticle

Ramezani-Dakhel, Hadi ; Mirau, Peter A. ; Naik, Rajesh R. ; Knecht, Marc ; Heinz, Hendrik. / Stability, surface features, and atom leaching of palladium nanoparticles : Toward prediction of catalytic functionality. In: Physical Chemistry Chemical Physics. 2013 ; Vol. 15, No. 15. pp. 5488-5492.
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