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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]
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  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)
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:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
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.
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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. https://doi.org/10.1039/C8CP06756B
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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. https://doi.org/10.1039/C8CP06756B. https://www.osti.gov/servlets/purl/1497382.
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@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},
number = 12,
volume = 21,
place = {United States},
year = {2019},
month = {2}
}
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https://doi.org/10.1039/C8CP06756B
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