Origin of bulklike structure and bond length disorder of Pt37 and Pt6Ru31 clusters on carbon: Comparison of theory and experiment

Lin Lin Wang, Sanjay V. Khare, Valeriu Chirita, D. D. Johnson, Angus A. Rockett, Anatoly I. Frenkel, Nathan H. Mack, Ralph G. Nuzzo

Research output: Contribution to journalArticlepeer-review


We describe a theoretical analysis of the structures of self-organizing nanoparticles formed by Pt and Ru-Pt on carbon support. The calculations provide insights into the nature of these metal particle systems-ones of current interest for use as the electrocatalytic materials of direct oxidation fuel cells- and clarify complex behaviors noted in earlier experimental studies. With clusters deposited via metalloorganic Pt or PtRu5 complexes, previous experiments [Nashner et al. J. Am. Chem. Soc. 1997, 119, 7760; Nashner et al. J. Am. Chem. Soc. 1998, 120, 8093; Frenkel et al. J. Phys. Chem. B 2001, 105, 12689] showed that the Pt and Pt-Ru based clusters are formed with fcc(111)-stacked cuboctahedral geometry and essentially bulklike metal-metal bond lengths, even for the smallest (few atom) nanoparticles for which the average coordination number is much smaller than that in the bulk, and that Pt in bimetallic [PtRu5] clusters segregates to the ambient surface of the supported nanoparticles. We explain these observations and characterize the cluster structures and bond length distributions using density functional theory calculations with graphite as a model for the support. The present study reveals the origin of the observed metal-metal bond length disorder, distinctively different for each system, and demonstrates the profound consequences that result from the cluster/carbon-support interactions and their key role in the structure and electronic properties of supported metallic nanoparticles.

Original languageEnglish (US)
Pages (from-to)131-142
Number of pages12
JournalJournal of the American Chemical Society
Issue number1
StatePublished - Jan 11 2006

ASJC Scopus subject areas

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


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