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Issue 7, 2015
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The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts

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Abstract

Recently Debe et al. reported that Pt3Ni7 leads to extraordinary Oxygen Reduction Reaction (ORR) activity. However, several reports show that hardly any Ni remains in the layers of the catalysts close to the surface (“Pt-skin effect”). This paradox that Ni is essential to the high catalytic activity with the peak ORR activity at Pt3Ni7 while little or no Ni remains close to the surface is explained here using large-scale first-principles-based simulations. We make the radical assumption that processing Pt–Ni catalysts under ORR conditions would leach out all Ni accessible to the solvent. To simulate this process we use the ReaxFF reactive force field, starting with random alloy particles ranging from 50% Ni to 90% Ni and containing up to ∼300 000 atoms, deleting the Ni atoms, and equilibrating the resulting structures. We find that the Pt3Ni7 case and a final particle radius around 7.5 nm lead to internal voids in communication with the exterior, doubling the external surface footprint, in fair agreement with experiment. Then we examine the surface character of these nanoporous systems and find that a prominent feature in the surface of the de-alloyed particles is a rhombic structure involving 4 surface atoms which is crystalline-like but under-coordinated. Using density-functional theory, we calculate the energy barriers of ORR steps on Pt nanoporous catalysts, focusing on the Oad-hydration reaction (Oad + H2Oad → OHad + OHad) but including the barriers of O2 dissociation (O2ad → Oad + Oad) and water formation (OHad + Had → H2Oad). We find that the reaction barrier for the Oad-hydration rate-determining-step is reduced significantly on the de-alloyed surface sites compared to Pt(111). Moreover we find that these active sites are prevalent on the surface of particles de-alloyed from a Pt–Ni 30 : 70 initial composition. These simulations explain the peak in surface reactivity at Pt3Ni7, and provide a rational guide to use for further optimization of improved catalytic and nanoporous materials.

Graphical abstract: The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts

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Publication details

The article was received on 08 Mar 2015, accepted on 22 Apr 2015 and first published on 29 Apr 2015


Article type: Edge Article
DOI: 10.1039/C5SC00840A
Chem. Sci., 2015,6, 3915-3925
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts

    A. Fortunelli, W. A. Goddard III, L. Sementa, G. Barcaro, F. R. Negreiros and A. Jaramillo-Botero, Chem. Sci., 2015, 6, 3915
    DOI: 10.1039/C5SC00840A

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