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Hydrogen electrooxidation on PdAu supported nanoparticles: An experimental RDE and kinetic modeling study

Paper ID Volume ID Publish Year Pages File Format Full-Text
54998 47036 2013 9 PDF Available
Title
Hydrogen electrooxidation on PdAu supported nanoparticles: An experimental RDE and kinetic modeling study
Abstract

The influence of the apparent Pd coverage on Au nanoparticles on the kinetics of the hydrogen oxidation (HOR) reaction has been explored by combined experimental rotating disc and microkinetic modeling study. PdAu bimetallic electrodes with variable Pd coverage in the interval from 0.07 to 2 MLs were obtained by electrodeposition of Pd on carbon supported Au nanoparticles. The experimental rotating disc electrode curves have been analyzed with the help of a kinetic model, in order to shed light on the predominant HOR mechanism (Heyrovsky–Volmer vs. Tafel–Volmer), the nature of the rate determining step, and their dependence on the Pd coverage, and get an insight into the type of HOR intermediate. The kinetic modeling suggests that the Heyrovsky–Volmer mechanism can reproduce the experimental curves for the whole range of Pd coverages explored. However, the Tafel step cannot be fully discarded around the equilibrium potential, its eventual contribution increasing as the coverage of Pd is reduced. The results of this work support a weakly adsorbed Had intermediate in the HOR on Pd, its Gibbs energy of adsorption decreasing from positive to near-zero values with the decrease of the apparent Pd coverage, underlying the enhancement of the hydrogen oxidation activity of PdAu compared to pure Pd.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (141 K)Download as PowerPoint slideHighlights► A model for the HOR enhancement with the decrease of Pd coverage in PdAu is proposed. ► Heyrovsky–Volmer mechanism reproduces the data in a wide range of Pd coverage. ► The results of this work support a weakly adsorbed Had intermediate in the HOR on Pd. ► The Gibbs energy of Hads decreases from positive values as the Pd coverage goes down.

Keywords
Hydrogen oxidation reaction; Palladium–Gold electrodes; Heyrovsky–Volmer and Tafel–Volmer mechanisms
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Hydrogen electrooxidation on PdAu supported nanoparticles: An experimental RDE and kinetic modeling study
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Publisher
Database: Elsevier - ScienceDirect
Journal: Catalysis Today - Volume 202, 15 March 2013, Pages 70–78
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us