skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Unusual Strain Effect of Pt-Based L10 Face-Centered Tetragonal Core in Core/Shell Nanoparticles for Oxygen Reduction Reaction

Abstract

Here, nanoparticles with low-Pt content core and a few-layer Pt skin are attractive catalysts toward the oxygen reduction reaction (ORR) not only for its low cost, but also because its activity can be enhanced by judiciously choosing the core alloy. Achieving optimal ORR performance would require fine tuning of the core composition and structure. Previous work studying the enhancement effects has primarily focused on core alloys with a cubic structure, (i.e. disordered alloy or L12 ordered structure) which limits the tuning to composition alone. In this work, using ab initio calculations, we have systemically investigated a new class of Pt0.5M0.5 (M=V, Cr, Fe, Co, Ni and Cu) core alloy that has a face-centered tetragonal L10 intermetallic structure. We have calculated the adsorption energies of O, OH, and OOH on various Pt skins and the underlying tetragonal structured alloys, which allows us to not only predict the optimal number of pure Pt skin layers but also tune the activity of the catalysts toward the peak of the ORR volcano plot. More importantly, using adsorption energies on intermediate structures, we are able to decompose the enhancement factor into ligand, normal and shear strain effects, and reveal the significant contribution of the shearmore » strain that is only possible with a tetragonal core but not a cubic one. Our results point to a new direction in designing tetragonal structured intermetallic core-shell nanoparticles for ORR applications.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1497382
Alternate Identifier(s):
OSTI ID: 1498185
Report Number(s):
BNL-211308-2019-JAAM
Journal ID: ISSN 1463-9076
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 21; Journal Issue: 12; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; ORR; Pt-based alloy; core-shell; fct; DFT

Citation Formats

Liu, Mingjie, Xin, Huolin, and Wu, Qin. Unusual Strain Effect of Pt-Based L10 Face-Centered Tetragonal Core in Core/Shell Nanoparticles for Oxygen Reduction Reaction. United States: N. p., 2019. Web. doi:10.1039/C8CP06756B.
Liu, Mingjie, Xin, Huolin, & Wu, Qin. Unusual Strain Effect of Pt-Based L10 Face-Centered Tetragonal Core in Core/Shell Nanoparticles for Oxygen Reduction Reaction. United States. doi:10.1039/C8CP06756B.
Liu, Mingjie, Xin, Huolin, and Wu, Qin. Fri . "Unusual Strain Effect of Pt-Based L10 Face-Centered Tetragonal Core in Core/Shell Nanoparticles for Oxygen Reduction Reaction". United States. doi:10.1039/C8CP06756B.
@article{osti_1497382,
title = {Unusual Strain Effect of Pt-Based L10 Face-Centered Tetragonal Core in Core/Shell Nanoparticles for Oxygen Reduction Reaction},
author = {Liu, Mingjie and Xin, Huolin and Wu, Qin},
abstractNote = {Here, nanoparticles with low-Pt content core and a few-layer Pt skin are attractive catalysts toward the oxygen reduction reaction (ORR) not only for its low cost, but also because its activity can be enhanced by judiciously choosing the core alloy. Achieving optimal ORR performance would require fine tuning of the core composition and structure. Previous work studying the enhancement effects has primarily focused on core alloys with a cubic structure, (i.e. disordered alloy or L12 ordered structure) which limits the tuning to composition alone. In this work, using ab initio calculations, we have systemically investigated a new class of Pt0.5M0.5 (M=V, Cr, Fe, Co, Ni and Cu) core alloy that has a face-centered tetragonal L10 intermetallic structure. We have calculated the adsorption energies of O, OH, and OOH on various Pt skins and the underlying tetragonal structured alloys, which allows us to not only predict the optimal number of pure Pt skin layers but also tune the activity of the catalysts toward the peak of the ORR volcano plot. More importantly, using adsorption energies on intermediate structures, we are able to decompose the enhancement factor into ligand, normal and shear strain effects, and reveal the significant contribution of the shear strain that is only possible with a tetragonal core but not a cubic one. Our results point to a new direction in designing tetragonal structured intermetallic core-shell nanoparticles for ORR applications.},
doi = {10.1039/C8CP06756B},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 12,
volume = 21,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on February 15, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Structurally ordered intermetallic platinum�cobalt core�shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts
journal, October 2012

  • Wang, Deli; Xin, Huolin L.; Hovden, Robert
  • Nature Materials, Vol. 12, Issue 1, p. 81-87
  • DOI: 10.1038/nmat3458

Projector augmented-wave method
journal, December 1994


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Electrolysis of water on (oxidized) metal surfaces
journal, December 2005


Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability
journal, January 2007

  • Stamenkovic, V. R.; Fowler, B.; Mun, B. S.
  • Science, Vol. 315, Issue 5811, p. 493-497
  • DOI: 10.1126/science.1135941

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Towards the computational design of solid catalysts
journal, April 2009

  • N�rskov, J.; Bligaard, T.; Rossmeisl, J.
  • Nature Chemistry, Vol. 1, Issue 1, p. 37-46
  • DOI: 10.1038/nchem.121

Alloys of platinum and early transition metals as oxygen reduction electrocatalysts
journal, September 2009

  • Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.
  • Nature Chemistry, Vol. 1, Issue 7, p. 552-556
  • DOI: 10.1038/nchem.367