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This content will become publicly available on December 22, 2018

Title: Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shape enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established onmore » conceptual catalytic models in practical nanoscale catalysts.« less
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  1. Northeastern Univ., Boston, MA (United States)
  2. Univ. of California, Los Angeles, CA (United States)
  3. Johns Hopkins Univ., Baltimore, MD (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 1530-6984
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 18; Journal Issue: 2; Journal ID: ISSN 1530-6984
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
36 MATERIALS SCIENCE; acid dissolution; density functional theory; in situ XAS; kinetic Monte Carlo; Mo−PtNi; ORR
OSTI Identifier: