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

Title: Tuning the Catalytic Activity of Ru@Pt Core-Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness

Abstract

The kinetics of the oxygen reduction reaction (ORR) was investigated in acid solutions on Pt monolayers that were deposited on carbon-supported Ru nanoparticles using the rotating disk electrode technique. The Pt mass and specific ORR activities greatly depend on the number of Pt monolayers, and the optimum activity occurs with two Pt monolayers. Density functional theory calculations showed that Pt overlayers destabilize O* and OH* with respect to pure Pt, leading to more favorable hydrogenation kinetics. However, with only a single Pt overlayer, the destabilization is too much, and O–O bond breaking becomes rate limiting. Two to three Pt monolayers supported on the Ru core of our nanoparticles lead to increased activity. This work demonstrates that one can modulate the ORR activity of Pt monolayers supported on other metals by eliminating a part of the ligand effect by increasing the thickness of the Pt shell on top of the supporting metal surface.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1233811
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 117; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Yang, Lijun, Vukmirovic, Miomir B., Su, Dong, Sasaki, Kotaro, Herron, Jeffrey A., Mavrikakis, Manos, Liao, Shijun, and Adzic, Radoslav R. Tuning the Catalytic Activity of Ru@Pt Core-Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness. United States: N. p., 2013. Web. doi:10.1021/jp309990e.
Yang, Lijun, Vukmirovic, Miomir B., Su, Dong, Sasaki, Kotaro, Herron, Jeffrey A., Mavrikakis, Manos, Liao, Shijun, & Adzic, Radoslav R. Tuning the Catalytic Activity of Ru@Pt Core-Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness. United States. doi:10.1021/jp309990e.
Yang, Lijun, Vukmirovic, Miomir B., Su, Dong, Sasaki, Kotaro, Herron, Jeffrey A., Mavrikakis, Manos, Liao, Shijun, and Adzic, Radoslav R. Thu . "Tuning the Catalytic Activity of Ru@Pt Core-Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness". United States. doi:10.1021/jp309990e.
@article{osti_1233811,
title = {Tuning the Catalytic Activity of Ru@Pt Core-Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness},
author = {Yang, Lijun and Vukmirovic, Miomir B. and Su, Dong and Sasaki, Kotaro and Herron, Jeffrey A. and Mavrikakis, Manos and Liao, Shijun and Adzic, Radoslav R.},
abstractNote = {The kinetics of the oxygen reduction reaction (ORR) was investigated in acid solutions on Pt monolayers that were deposited on carbon-supported Ru nanoparticles using the rotating disk electrode technique. The Pt mass and specific ORR activities greatly depend on the number of Pt monolayers, and the optimum activity occurs with two Pt monolayers. Density functional theory calculations showed that Pt overlayers destabilize O* and OH* with respect to pure Pt, leading to more favorable hydrogenation kinetics. However, with only a single Pt overlayer, the destabilization is too much, and O–O bond breaking becomes rate limiting. Two to three Pt monolayers supported on the Ru core of our nanoparticles lead to increased activity. This work demonstrates that one can modulate the ORR activity of Pt monolayers supported on other metals by eliminating a part of the ligand effect by increasing the thickness of the Pt shell on top of the supporting metal surface.},
doi = {10.1021/jp309990e},
journal = {Journal of Physical Chemistry. C},
number = 4,
volume = 117,
place = {United States},
year = {Thu Jan 31 00:00:00 EST 2013},
month = {Thu Jan 31 00:00:00 EST 2013}
}