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Research Papers

Electroless Deposition and Characterization of PtxRu1x Catalysts on Pt/C Nanoparticles for Methanol Oxidation

[+] Author and Article Information
William E. Mustain

Department of Chemical, Materials, and Biomolecular Engineering, University of Connecticut, Storrs, CT 06268

Hyea Kim, Vijai Narayanan, Tyler Osborn

School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332

Paul A. Kohl

School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332kohl@gatech.edu

J. Fuel Cell Sci. Technol 7(4), 041013 (Apr 08, 2010) (7 pages) doi:10.1115/1.4000675 History: Received December 08, 2008; Revised July 23, 2009; Published April 08, 2010; Online April 08, 2010

The electroless deposition of PtxRu1x catalysts using hydrazine dihydrochloride or formic acid as the reducing agent in a modified Leaman bath was investigated. The effect of potential on the PtxRu1x composition was investigated by potentiostatically depositing PtxRu1x thin films on gold from acidic chloride electrolytes at potentials between −0.46 V and 0.34 V (versus normal hydrogen electrode). The physical characteristics and elemental composition of the deposits were determined. An empirical model for the deposition process was developed, taking into account reactant concentration, temperature, and surface potential. The model accurately characterized the deposit composition over a wide Pt/Ru range. The surface potential was estimated to be 0.15 V during electroless deposition using formic acid as the reducing agent based on the empirical model. Deviations from the model were found when hydrazine was used as the reducing agent due to the formation of solution phase ruthenium complexes with hydrazine.

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Copyright © 2010 by American Society of Mechanical Engineers
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Figures

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Figure 1

Relative contributions to the observed current of Pt and Ru during electrodeposition as a function of potential at 23°C and CPt/CRu=1.6

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Figure 2

Anode catalyst layer (a) before and (b) after the electroless deposition of PtRu at 11,000× and 60,000× magnifications, respectively

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Figure 3

Agreement between the proposed deposition model at a surface potential of 0.4 V and experimental data for the spontaneous, electroless deposition of PtxRu1−x with a hydrazine dihydrochloride reducing agent at various bath compositions (23°C).

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Figure 4

Model and experimental results for the electroless deposition of PtxRu1−x with hydrazine dihydrochloride reducing agent and various bath compositions (90°C)

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Figure 5

Model and experimental results for the electroless deposition of PtxRu1−x with formic acid reducing agent and various bath compositions (70°C)

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Figure 6

EDX map for Pt (◼) and Ru (◻) in the Pt0.48Ru0.52/C–SiO2 composite catalyst layer

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Figure 7

SEM/backscatter SEM for PtRu catalyst layer, 125 k× magnification (100 nm marker shown)

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