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Title: Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction

Abstract

Optimizing the utilization of Pt to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) is of vital importance in proton exchange membrane fuel cells. One of the strategies is to spread Pt atoms over the surface of a substrate to increase the surface area. We report a facile method to synthesize Pd6CoCu@Pt/C core-shell nanoparticles with an ultralow amount of Pt. It was found that Pt-coated layer on Pd6CoCu cores plays a vital role in enhancing the ORR activity and the cycling stability. The half-wave potential of Pd6CoCu@Pt/C positively shifts about 50 mV and 17 mV relative to Pd6CoCu/C and Pt/C, respectively. The Pt mass activity on Pd6CoCu@Pt/C was calculated to be about 27 times higher than that on Pt/C catalysts at 0.9 V. Furthermore, the Pd6CoCu@Pt/C nanoparticles exhibit superior stability with almost no decay for the ORR polarization curves during 10,000 potential cycles and the core-shell structure remains with only a slight increase in the thickness of the Pt overlayer. Our findings provide a methodology for synthesizing highly efficient catalytic materials for the cathodic application in fuel cells.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Huazhong Univ. of Science and Technology, Wuhan (China). School of Chemistry and Chemical Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1336137
Report Number(s):
BNL-112611-2016-JA
Journal ID: ISSN 2211-2855; KC0403020
Grant/Contract Number:
SC00112704; SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 27; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; fuel cells; oxygen reduction reaction; Pd6CoCu/C nanoparticles; electrocatalysis; core-shell; Pt monolayer

Citation Formats

Liu, Sufen, Xiao, Weiping, Wang, Jie, Zhu, Jing, Wu, Zexing, Xin, Huolin, and Wang, Deli. Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction. United States: N. p., 2016. Web. doi:10.1016/j.nanoen.2016.07.038.
Liu, Sufen, Xiao, Weiping, Wang, Jie, Zhu, Jing, Wu, Zexing, Xin, Huolin, & Wang, Deli. Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction. United States. doi:10.1016/j.nanoen.2016.07.038.
Liu, Sufen, Xiao, Weiping, Wang, Jie, Zhu, Jing, Wu, Zexing, Xin, Huolin, and Wang, Deli. 2016. "Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction". United States. doi:10.1016/j.nanoen.2016.07.038. https://www.osti.gov/servlets/purl/1336137.
@article{osti_1336137,
title = {Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction},
author = {Liu, Sufen and Xiao, Weiping and Wang, Jie and Zhu, Jing and Wu, Zexing and Xin, Huolin and Wang, Deli},
abstractNote = {Optimizing the utilization of Pt to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) is of vital importance in proton exchange membrane fuel cells. One of the strategies is to spread Pt atoms over the surface of a substrate to increase the surface area. We report a facile method to synthesize Pd6CoCu@Pt/C core-shell nanoparticles with an ultralow amount of Pt. It was found that Pt-coated layer on Pd6CoCu cores plays a vital role in enhancing the ORR activity and the cycling stability. The half-wave potential of Pd6CoCu@Pt/C positively shifts about 50 mV and 17 mV relative to Pd6CoCu/C and Pt/C, respectively. The Pt mass activity on Pd6CoCu@Pt/C was calculated to be about 27 times higher than that on Pt/C catalysts at 0.9 V. Furthermore, the Pd6CoCu@Pt/C nanoparticles exhibit superior stability with almost no decay for the ORR polarization curves during 10,000 potential cycles and the core-shell structure remains with only a slight increase in the thickness of the Pt overlayer. Our findings provide a methodology for synthesizing highly efficient catalytic materials for the cathodic application in fuel cells.},
doi = {10.1016/j.nanoen.2016.07.038},
journal = {Nano Energy},
number = C,
volume = 27,
place = {United States},
year = 2016,
month = 8
}

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  • The ability to harness the metal-metal and metal-oxygen coordination structures of nanoalloy catalysts is critical for catalyzing the oxygen reduction reaction because such a detailed atomic-scale structure dictates the surface binding site and strength for molecular oxygen and oxygenated intermediate species in the electrocatalytic process. This report describes the results of an investigation of the metal-metal and metal-oxygen coordination structures of ternary nanoalloys and their manipulation to enhance the electrocatalytic activity for oxygen reduction reaction. The basic hypothesis is that such atomic-scale structure can be manipulated by oxidative-reductive thermal treatment to influence the binding site and strength of molecular oxygenmore » and oxygenated species on the nanoalloy surface. The results have revealed remarkable increases in both mass activity and specific activity for the catalysts processed by the oxidative-reductive treatment over those treated under non-reactive or low-degree oxidative atmospheres before the reductive treatment. In comparison with non-reactive-reductive treatment, an increased degree of heteroatomic alloying among the three metal components in the ternary catalysts and a decreased percentage of oxides (NiO and CoO) have been revealed by X-ray absorption fine structure spectroscopy for the catalysts treated by the oxidative-reductive treatment. An enrichment of surface Pt has also been detected by x-ray photoelectron spectroscopy for such catalysts. A combination of the increase in the heteroatomic alloying, the decrease in metal oxides, and the enrichment of surface Pt by the oxidative-reductive thermal treatment has therefore been concluded to be responsible for the enhanced electrocatalytic activity. The demonstration of this new approach to manipulating the metal-metal and metal-oxygen coordination structures forms the basis for an effective strategy in engineering ternary nanoalloy catalysts, and has provided new insights into the role of such structures in the enhancement of the electrocatalytic activity.« less
  • A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuelmore » cell applications.« less
  • In this study, carbon supported Pd 3V bimetallic alloy nanoparticles (Pd 3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H 2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd 3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd 3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd 3V/C nanoparticles. The catalytic activity and stability of the Pd 3V@Pt/C and Pt-Pd 3V/C catalystsmore » for the oxygen reduction reaction (ORR) are enhanced significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd 3V@Pt/C and Pt-Pd 3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd 3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.« less