Nanostructured Gold and Alloys for Fuel Cell Catalysis

Gold 2003
Chuan-Jian Zhong, Mathew Maye, Jin Luo, Li Han, Nancy Kariuki,
Abstract Our work is aimed at the preparation, characterization and application of gold and its alloy nanoparticles as fuel cell catalysts. Fuel cells operating by electrochemical oxidation of hydrogen or methanol fuels at the anode and reduction of oxygen at the cathode are attractive commercial power sources due to their high conversion efficiencies, low pollution, and high power density. The poor catalytic activity and the requirement of Pt-group metals that have limited global supply and suffer from the propensity of surface poisoning are currently some of the series barriers to commercial applications of fuel cells. Gold and its alloy with other metals in the nanosize range (<10 nm) present new alternatives [1]. Such catalysts could generate unique bifunctional catalytic properties with hydrogenation/dehydrogenation sites and the ability to remove the poisonous CO under low temperature operations.

The ability to harness the large surface area-to-volume ratios and the unique binding surface sites of nanoparticles in <10 nm size range, especially in heterogeneous catalysis, constitutes a major driving force in fundamental research and practical applications of nanoparticle catalysts. It is this size range over which the metal particles undergo a transition from atomic to metallic properties. The understanding of factors controlling morphological and surface reconstitution associated with this size range is of fundamental importance to the ultimate exploration of the nanostructured catalysts. This presentation describes recent findings of an investigation of the interfacial structures and properties of gold and alloy nanoparticles in the electrocatalytic oxidation and reduction of methanol and oxygen, which are of fundamental interest to fuel cell technology. Built upon our initial findings of the preparation of nanoscale catalysts via core-shell assembled nanoparticles consisting of gold or alloy nanocrystal cores and organic monolayer shells with controllable size monodispersity, processibility, and stability towards size- and composition- tunable catalysts, we have expanded our investigation into the preparation of the nanoparticles on oxide and carbon support materials for the electrocatalytic oxidation of methanol and reduction of oxygen in fuel cells [2-8]. Gold and bimetallic (AuFe, AuPt, AuNi, etc) nanoparticles of 2-5 nm core size range on planar substrates and high surface area carbon materials are studied as a model system of the nanostructured catalyst.

Experimentally, the gold and alloy nanoparticles of controlled size and composition were prepared by a combination of the well-established two-phase synthesis protocol and the thermal processing protocol developed in our laboratory [9]. The carbon-supported gold or alloy nanoparticles were cast quantitatively onto a glassy carbon electrode. A Nafion film will be applied to fix the catalysts. The comparison of voltammetric peak potentials and currents provided the initial catalyst screening for CO oxidation, CH3OH oxidation, and O2 reduction reaction (ORR). The relative composition was controlled by the synthetic feed ratio and thermal processing parameters. Instead of detecting two distinctive waves corresponding to the catalytic activity of Pt and Au sites, a single catalytic wave was detected for these reactions at Au catalyst of different alloy compositions, implying the operation of the alloy in the catalytic reaction. The catalytic activity for methanol oxidation in acidic electrolyte at AuPt catalysts demonstrated new opportunities of the binary nanoparticle system, because previous studies of the bulk form of gold alloys have not shown such catalytic activity. For the ORR activity, the rotating disk electrode data revealed a mixed kinetic-diffusion control current, which is qualitatively similar to those known for other Pt-based nanoparticle catalysts. While a further investigation is in progress to delineate the reaction mechanism, the result suggests that the 4-electron reduction process can be manipulated by alloy composition. The bifunctional activity is believed to be operative, in which the alloyed Au leads to an effective removal of Pt-CO for the anode reaction and of the -Pt-OH for the cathode reaction.

Furthermore, the study of the nanostructured catalyst using surface spectroscopy (IR and XPS) and atomic force microscopy has provided important insights into the structural and morphological reconstitution of the nanostructured catalysts in the catalytic processes. Implications of the findings to the design, preparation and processing of highly-active nanostructured gold and alloy catalysts will be discussed. Further research exploring the gold-based nanotechnology in fuel cells and industrial applications using refined preparative and activation routes will also be discussed.

References:

[1]. (a) M. Haruta, M. Date, "Advances in the catalysis of Au nanoparticles", Applied Catalysis A, 2001, 222, 427. (b) G. C. Bond, D. T. Thompson, "Catalysis by Gold", Catal. Rev., 1999, 41, 319, and references therein.

[2]. C. J. Zhong, M. M. Maye, “Core-Shell Assembled Nanoparticles as Catalysts”, Adv. Mater., 2001, 13, 1507.

[3]. M.M. Maye, J. Luo, Y. Lin, M. H. Engelhard, M. Hepel, C. J. Zhong, "X-Ray Photoelectron Spectroscopic Study of the Activation of Molecularly-Linked Gold Nanoparticle Catalysts", Langmuir, 2003, 19, 125.

[4]. J. Luo, V. W. Jones, M. M. Maye, L. Han, N. N. Kariuki, C. J. Zhong, "Thermal Activation of Molecularly-Wired Gold Nanoparticles on a Substrate as Catalyst", J. Am. Chem. Soc., 2002, 124, 13988-13989.

[5]. J. Luo, M. M. Maye, Y. Lou, L. Han, M. Hepel, C. J. Zhong, "Catalytic Activation of Core-Shell Assembled Gold Nanoparticles as Catalyst for Methanol oxidation", Catalysis Today, 2002, 77, 127.

[6]. J. Luo, Y. Lou, M. M. Maye, C. J. Zhong, M. Hepel, "An EQCN Assessment of Electrocatalytic Oxidation of Methanol at Nanostructured Au Nanoparticles", Electrochem. Comm., 2001, 3, 172.

[7]. Y. Lou, M. M. Maye, L. Han, J. Luo, C. J. Zhong, "Gold Nanoparticle Assembly as Catalyst for Methanol Electrooxidation" Chem. Comm., 2001, 5, 473.

[8]. M. M. Maye, Y. Lou, C. J. Zhong, "Core-Shell Gold Nanoparticle Assembly as Novel Electrocatalyst of CO Oxidation", Langmuir, 2000, 16, 7520.

[9]. M. M. Maye, W. X. Zheng, F. L. Leibowitz, N. K. Ly, C. J. Zhong, "Heating-Induced Evolution of Thiolate-Encapsulated Gold Nanoparticles: A Strategy for Size and Shape Manipulations", Langmuir, 2000, 16, 490.

Keywords: Alloy, nanoparticles, Methanol oxidation, Oxygen reduction, Nanostructure, Electrocatalysis, catalyst, Fuel cell, Gold, nanotechnology
Full Access to Technical Paper
PDF version for $20.00
Other papers from Gold 2003
Search
Sort By:  Relevance
Showing results 1 - 50 of 101
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elma van der Lingen, Madeleine du Toit, Cristian Cretu, Lizelle Glaner
Keywords: hard, gold alloys, Strengthening, age hardening
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Inga Tuzovskaya, Alexey Pestryakov, Valery Gurin, Andrey Simakov, Miguel Avalos, Mario Farias
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Proceedings: Gold 2003
Keywords: gold-platinum alloys, ethylene glycol, Heat treatment, Electro-oxidation, Kirkendall effect, Cyclic Voltammetry
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Nina Bogdanchikova, Bernard E. Nieuwenhuys
Keywords: Oxidation, Methane, oxide, additive, Alkali, Hydrocarbons, propene
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Michael Cortie, Herman Schwarzer, Stephen Roberts, Gary Pattrick
Keywords: Gold Catalysis, Intermetallic compounds, AuAl2, CO oxidation
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Andreas Zielonka, Renate Freudenberger
Keywords: electroforming, electrodeposition/electroplating, implant, Gold, medical application
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Neil E Izatt, Steven R Izatt, Ronald L Bruening
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Jeanette Hohls, Cristian Cretu, Lesley Cornish, Daven Compton
Keywords: Fecraloy, oxidation resistance, Gold
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elma van der Lingen, Stella Valenzuela, Don Martin
Keywords: mesoporous, nanoporous, ultracapacitor
Year: 2003
Text
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Tim W Ellis
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Stephan Roberts, Elma van der Lingen, Herman Schwarzer
Keywords: spongy gold, selective catalytic reduction, NOx
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Shawn D. Lin, Bernard E. Nieuwenhuys
Keywords: nitrous oxide, Oxidation, Alkali, Ammonia, nitric oxide, Reduction, oxide, selectivity
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Ko-ichi Sugawara
Keywords: electron microscopy, nanoparticle, Morphology, Computer simulation, Image analysis, cluster science, Statistics
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Bob Stewart, Carel Wreesmann, Geoff Smith
Keywords: Plants, Induced hyperaccumulation, Gold, Phytomining, nanoparticles
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Prati Laura, Rossi Michele
Keywords: gold on carbon, liquid phase oxidation
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Uzi Landman
Keywords: gold nanoclusters, oxidation reactions, relativistic effects, nanocatalysis
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Masayuki Kanehara, Etsushi Kodzuka, Yasunori Oumi, Tsuneji Sano
Keywords: gold nanoparticle, self-assembly
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Suresh Bharagva, Martin Bennett
Keywords: Ab Initio Calculations, Gold Complexes, Cyclometallated, Heterovalent complexes, Carbon-carbon coupling, Binuclear
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Yutaka Okinaka
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Sandrine Arrii, Albert Renouprez
Keywords: supported catalysts, CO oxidation, support effects, Gold, laser vaporization
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elena Cerrada, Ana Ade, Maria Contel
Keywords: Dipolar cycloaddition, Gold, nitrones, organometallics
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Aalbert Zwijnenburg, Wim G Sloofs, Jacob A Moulijn
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Cris Kostmann, Gunter Stephani
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elma Van der Lingen, Michael Cortie
Keywords: Gold Catalysis, zinc oxide, CO oxidation
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Keywords: Cyclic Voltammetry, Surface Active Sites, Electrochemistry, Surface, Metastability, RHE, Electrocatalysis, Gold, Premonolayer Oxidation, Cyclic redox mediators, Active state electrochemistry, Protruding surface atoms, Metastable Surface States
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Peter CLAUS, Herbert HOFMEISTER, Christian MOHR
Keywords: nanoparticles, hydrogenation, indentification of active sites, catalysis by gold, real structure
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Uwe Manz
Keywords: Electroless, Plating, Barrel, Electronics
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): P Centomo, D Ferrari, W Meyer-Zaika, G Schmid
Year: 2003
Text
Summary: The preparation of a vapour compound sensor is reported. It is based on a vapochromic organometallic gold compound and optical fiber. The results are comapred with other reported VO«S sensor
Proceedings: Gold 2003
Author(s): Candido Bariain, Elena Cerrada, Julian Garrido, Ignacio R Matias, Mariano Laguna
Keywords: vapochromic, Gold, organometallic, environmental sensor
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Gilbert P. van Berkel, Bernard E. Nieuwenhuys
Keywords: chemisorption, Au(100), nitric oxide, phase transition
Year: 2003
Text
Proceedings: Gold 2003
Author(s): V. La Parola, B. Pawelec, J. L. G. Fierro
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Andrea Beck, Gabor Peto, Csaba Daroczi, Krisztina Frey
Keywords: Au/SiO2/Si(100), Size dependence, UPS, support effect, TEM, AFM, CO oxidation
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Fernando Canales, Silvia Canales, Olga Crespo, Antonio Laguna, Carmen Larraz
Keywords: aurophilic interactions, polynuclear, chalcogenide, Gold
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Keywords: plasmon resonance, colour, crystal structure, melting point, band gap, nanotechnology
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Christopher Corti
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): David James, Lucy Millard, Jane Greaves, Jorge Soares
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Mihaly Hegedus
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Kageeporn Wongpreedee, Alan M Russell
Keywords: Gold, interconnection wire, transformation, Kinetics, Composite, Dislocation
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Chih-Huey Lin, Hsin-Yen Tsai, Chih-Huey Lin, Hsin-Yen Tsai
Keywords: Au, Al2O3, Au, Al2O3, impregnation, NH4OH treatment, NH4OH treatment, impregnation
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Aya Kawamoto, Masakazu Date, Susumu Tsubota, Mitsutaka Okumura, Masatake Haruta
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Matthew Hall, Albert F Carley, Graham John Hutchings,
Keywords: XPS, Au - Fe catalysts, Low temperature CO oxidation
Year: 2003