Testing the predictive power of theory for PdxIr(100−x)alloy nanoparticles for the oxygen reduction reaction

Hongyu Guo, Jamie A. Trindell, Hao Li, Desiree Fernandez, Simon M. Humphrey, Graeme Henkelman, Richard M. Crooks

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)


In this report, density functional theory (DFT) calculations of O and OH binding energies on triatomic surface ensembles of PdxIr(100−x)nanoalloys successfully predicted the overall trend in experimental oxygen reduction reaction (ORR) activity as a function of nanoparticle (NP) composition. Specifically, triatomic Pd3ensembles were found to possess optimal O and OH binding energies and were predicted to be highly active sites for the ORR, rivaling that of Pt(111). However, DFT calculations suggest that the O binding energy increases at active sites containing Ir, thereby decreasing ORR activity. PdxIr(100−x)nanoalloys were synthesized using a microwave-assisted method and their activity towards the ORR was tested using rotating disk voltammetry (RDV). As predicted, the bimetallic electrocatalysts exhibited worse catalytic activity than the Pd-only NPs. The strong qualitative correlation between the theoretical and experimental results demonstrates that the activity of individual active sites on the surface of NPs can serve as a proxy for overall activity. This is a particularly useful strategy for applying DFT calculations to electrocatalysts that are too large for true first-principle analysis.

Original languageEnglish
Pages (from-to)8421-8429
Number of pages9
JournalJournal of Materials Chemistry A
Issue number17
Publication statusPublished - 2020 May 7
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)


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