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Corresponding Author

Chuanjian Zhong(cjzhong@binghamton.edu)

Abstract

Proton exchange membrane fuel cell represents an important electrochemical energy conversion device with many attractive features in terms of efficiency of energy conversion and minimization of environmental pollution. However, the large overpotential for oxygen reduction reaction at the cathode and the low activity, poor durability and high cost of platinum-based catalysts in the fuel cells constitute a focal point of major barriers to the commercialization of fuel cells. The development of nanostructured catalysts shows promises to addresses some of the challenging problems. The ability to engineer the composition and nanostructure of nanoalloy catalysts is important for developing active, robust and low-cost catalysts for fuel cell applications. This article highlights some of the recent insights into the catalytic properties of ternary nanoalloy catalysts prepared by molecularly-engineered synthesis and thermochemically-controlled processing, focusing on oxygen reduction reaction in fuel cells. This approach has demonstrated the abilities to control size, composition, and nanoscale alloying of binary and ternary nanoalloys. A highly-active ternary nanoalloy catalyst consisting of platinum, nickel and cobalt that is supported on carbon (PtNiCo/C) will be discussed as an example, highlighting the importance of nanoscale tuning of structures and composition for the design of fuel cell catalysts. The mass activity of selected PtNiCo/C catalysts has been shown much higher electrocatalytic activity than those observed for their binary counterparts and commercial Pt/C catalysts. Selected examples will also be shown that the catalytic activity can be tuned by the ternary composition. The structural and synergistic properties of the ternary nanoalloy catalysts for the enhancement of the electrocatalytic activity will also be discussed.

Graphical Abstract

Keywords

ternary nanoalloys, nanocatalysts, electrocatalytic activity, oxygen reduction reaction, fuel cells

Publication Date

2012-12-28

Online Available Date

2012-08-15

Revised Date

2012-08-11

Received Date

2012-07-13

References

[1] Brandon N P, Skinner S, Steele B C H. Recent advances in materials for fuel cells, Annual Review of Materials Research, 2003, 33: 183-213.

[2] Adler S B. Factors governing oxygen reduction in solid oxide fuel cell cathodes, Chemical Reviews, 2004, 104(10): 4791-4843.

[3] Casado-Rivera E, Volpe D J, Alden L, Lind C, Downie C, Vazquez-Alvarez T, Angelo A C D, DiSalvo F J, Abruna H D. Electrocatalytic activity of ordered intermetallic phases for fuel cell applications, Journal of The American Chemical Society, 2004, 126(12): 4043-4049.

[4] Sasaki K, Wang J X, Balasubramanian M, McBreen J, Uribe F, Adzic R R. Ultra-low platinum content fuel cell anode electrocatalyst with a long-term performance stability, Electrochimica Acta, 2004, 49(22-23): 3873-3877.

[5] Mallouk T E, Smotkin E S. in Handbook of Fuel Cells – Fundamentals, Technology and Application, ed. W. Vielstich, A. Lamm, and H. A. Gasteiger, John Wiley & Sons. 2003.

[6] Liu R, Smotkin E S. Array membrane electrode assemblies for high throughput screening of direct methanol fuel cell anode catalysts, Journal of Electroanalytical Chemistry, 2002, 535(1-2): 49-55.

[7] Strasser P, Fan Q, Devenney M, Weinberg W H, Liu P, Norskov J K. High throughput experimental and theoretical predictive screening of materials - A comparative study of search strategies for new fuel cell anode catalysts, Journal of Physical Chemistry B, 2003, 107(40): 11013-11021.

[8] He T, Kreidler E, Xiong L, Luo J., Zhong C J. Alloy Electrocatalysts: Combinatorial Discovery and Nanosynthesis, Journal of The Electrochemical Society, 2006, 153(9): A1637-A1643.

[9] Stamenkovic V R, Mun B S, Arenz M, Mayrhofer K J J, Lucas C A, Wang G F, Ross P N, Markovic N M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces, Nature Materials, 2007, 6(3): 241-247.

[10] Paulus U A, Wokaun A, Scherer G G, Schmidt T J, Stamenkovic V, Radmilovic V, Markovic N M, Ross P N. Oxygen reduction on carbon-supported Pt-Ni and Pt-Co alloy catalysts, Journal of Physical Chemistry B, 2002, 106(16): 4181-4191.

[11] Greeley J, Stephens I E L, Bondarenko A S, Johansson T P, Hansen H A, Jaramillo T F, Rossmeisl J, Chorkendorff I, Norskov J K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts, Nature Chemistry, 2009, 1(7): 552-556.

[12] Stamenkovic V R, Fowler B, Mun B S, Wang G F, Ross P N, Lucas C A, Markovic N M. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability, Science, 2007, 315(5811): 493-497.

[13] Stamenkovic V, Schmidt T J, Ross P N, Markovic N M. Surface composition effects in electrocatalysis: Kinetics of oxygen reduction on well-defined Pt3Ni and Pt3Co alloy surfaces, Journal of Physical Chemistry B, 2002, 106(46): 11970-11979.

[14] Mukerjee S, Srinivasan S, Soriaga M P, McBreen J. Role of structural and ekectronic-properties of Pt and Pt alloys on electrocatalysis of oxygen reduction - an in-situ XANES and EXAFS investigation, Journal of The Electrochemical Society, 1995, 142(5): 1409-1422.

[15] Wei Z D, Feng Y C, Li L, Liao M J, Fu Y, Sun C X, Shao Z G, Shen P K. Electrochemically synthesized Cu/Pt core-shell catalysts on a porous carbon electrode for polymer electrolyte membrane fuel cells, Journal of Power Sources, 2008, 180(1): 84-91.

[16] Mani P, Srivastava R, Strasser P. Dealloyed binary PtM3 (M = Cu, Co, Ni) and ternary PtNi3M (M = Cu, Co, Fe, Cr) electrocatalysts for the oxygen reduction reaction: Performance in polymer electrolyte membrane fuel cells, Journal of Power Sources, 2011, 196(2): 666-673.

[17] Seo A, Lee J, Han K, Kim H. Performance and stability of Pt-based ternary alloy catalysts for PEMFC, Electrochimica Acta, 2006, 52(4): 1603-1611.

[18] Yu P, Pemberton M, Plasse P. PtCo/C cathode catalyst for improved durability in PEMFCs, Journal of Power Sources, 2005, 144(1): 11-20.

[19] Rao C R K, Trivedi D C. Chemical and electrochemical depositions of platinum group metals and their applications, Coordination Chemistry Reviews, 2005, 249(5-6): 613-631.

[20] Russell A E, Rose A. X-ray absorption Spectroscopy of low temperature fuel cell catalysts, Chemical Reviews, 2004, 104(10): 4613-4635.

[21] Bond G C, Thompson D T. Catalysis by gold, Catalysis Reviews – Science and Engineering, 1999, 41(3-4): 319-388.

[22] Campbell C T. The active site in nanopaticle gold catalysis, Science, 2004, 306(5694): 234-235.

[23] Chen M S, Goodman D W. The structure of catalytically active gold on titania, Science, 2004, 306(5694): 252-255.

[24] Davis R J. All that glitters is not Au-0, Science, 2003, 301(5635): 926-927.

[25] Haruta M, Date M. Advances in the catalysis of Au nanoparticles, Applied Catalysis A - General, 2001, 222(1-2): 427-437.

[26] Rolison D R. Catalytic nanoarchitectures - The importance of nothing and the unimportance of periodicity, Science, 2003, 299(5613): 1698-1701.

[27] Luo J, Njoki P, Lin Y, Wang L, Mott D, Zhong C J. Activity-Composition Correlation of AuPt Alloy Nanoparticle Catalysts in Electrocatalytic Reduction of Oxygen, Electrochemistry Communications, 2006, 8: 581-587.

[28] Luo J, Njoki P, Lin Y, Mott D, Wang L, Zhong C J. Characterization of Carbon-Supported AuPt Nanoparticles for Electrocatalytic Methanol Oxidation Reaction, Langmuir, 2006, 22: 2892-2898.

[29] Luo J, Kariuki N, Han L, Wang L, Zhong C J, He T. Preparation and Characterization of Carbon-supported PtVFe Electrocatalysts, Electrochimica Acta, 2006, 51(23): 4821-4827.

[30] Luo J, Wang L Y, Mott D, Njoki P N, Kariuki N, Zhong C J, He T. Ternary Alloy Nanoparticles with Controllable Sizes and Composition and Electrocatalytic Activity, Journal of Materials Chemistry, 2006, 16: 1665-1673.

[31] Wang L, Luo J, Schadt M J, Zhong C J. Thin Film Assemblies of Molecularly-Linked Metal Nanoparticles and Multifunctional Properties, Langmuir, 2010, 26: 618-632.

[32] Wanjala B N, Luo J, Loukrakpam R, Fang B, Mott D, Njoki P N, Engelhard M, Naslund H R, Wu J K, Wang L C, Malis O, Zhong C J. Nanoscale Alloying, Phase-Segregation, and Core-Shell Evolution of Gold-Platinum Nanoparticles and Their Electrocatalytic Effect on Oxygen Reduction Reaction, Chemistry of Materials, 2010, 22: 4282-4294.

[33] Wanjala B N, Luo J, Fang B, Mott D, Zhong C J. Gold-Platinum Nanoparticles: Alloying or Phase Segregation, Journal of Materials Chemistry, 2011, 21: 4012- 4020.

[34] Wanjala B N, Loukrakpam R, Luo J, Njoki P N, Mott D, Zhong C J, Shao M H, Protsailo L, Kawamura T. Thermal Treatment of PtNiCo Electroatalysts: Effects of Nanoscale Strain and Structure on Activity and Stability for Oxygen Reduction Reaction, Journal of Physical Chemistry C, 2010, 114: 17580-17590.

[35] Loukrakpam R, Luo J, He T, Chen Y, Xu Z, Njoki P N, Wanjala B N, Fang B, Mott D, Yin J, Klar J, Powell B, Zhong C J. Nanoengineered PtCo and PtNi Catalysts for Oxygen Reduction Reaction: An Assessment of the Structural and Electrocatalytic Properties, Journal of Physical Chemistry C, 2011, 115: 1682-1694.

[36] Loukrakpam R, Chang P, Luo J, Fang B, Mott D, Bae I T, Naslund H R, Engelhard M H, Zhong C J. Chromium-Assisted Shape Control of Pt-based Nanoparticle Electrocatalysts, Chemical Communications, 2010, 46: 7184-7186.

[37] Fang B, Luo J, Chen Y, Wanjala B N, Loukrakpam R, Hong J, Yin J, Hu X, Hu P, Zhong C J. Nanoengineered PtVFe/C Cathode Electrocatalysts in PEM Fuel Cells: Catalyst Activity and Stability, ChemCatChem, 2011, 3(3): 583-593.

[38] Fang B, Wanjala B N, Hu X A, Last J, Loukrakpam R, Yin J, Luo J, Zhong C J. PEM Fuel Cells with Nanoengineered AuPt Catalysts at the Cathode, Journal of Power Sources, 2011, 196: 659-665.

[39] Fang B, Luo J, Njoki P N, Loukrakpam R, Wanjala B, Hong J, Yin J, Hu X, Last J, Zhong C J. Nanoengineered PtVFe Catalysts in Proton Exchange Membrane Fuel Cells: Electrocatalytic Performance, Electrochimica Acta, 2010, 55: 8230-8236.
[40] Fang B, Luo J, Njoki P N, Loukrakpam R, Mott D, Wanjala B, Hu X, Zhong C J. Nanostructured PtVFe Catalysts: Electrocatalytic Performance in Proton Exchange Membrane Fuel Cells, Electrochemistry Communications, 2009, 11: 1139-1141.
[41] Luo J, Han L, Kariuki N N, Wang L Y, Mott D, Zhong C J, He T. Phase Properties of Carbon-Supported Gold-Platinum Nanoparticles with Different Bimetallic Compositions, Chemistry of Materials, 2005, 17: 5282-5290.
[42] Klabunde K J. Nanoscale Materials in Chemistry, New York: John Wiley & Sons, Inc. 2001.
[43] Feldheim D L, Foss Jr C A. Metal Nanoparticles: Synthesis, Characterization, and Applications, New York: Marcel Dekker, Inc. 2002.
[44] Raja R, Khimyak T, Thomas J M, Hermans S, Johnson B F G. Single-step, highly active, and highly selective nanoparticle catalysts for the hydrogenation of key organic compounds, Angewandte Chemie International Edition, 2001, 40(24): 4638.
[45] Schmidt T J, Gasteiger H A, Behm R J. Methanol electrooxidation on a colloidal PtRu-alloy fuel-cell catalyst, Electrochemistry Communications, 1999, 1(1): 1-4.
[46] Waszczuk P, Lu G Q, Wieckowski A, Lu C, Rice C, Masel R I. UHV and electrochemical studies of CO and methanol adsorbed at platinum/ruthenium surfaces, and reference to fuel cell catalysis, Electrochimica Acta, 2002, 47(22-23): 3637-3652.
[47] Luo J, Fang B, Wanjala B N, Njoki P N, Loukrakpam R, Yin J, Mott D, Lim S, Zhong C J. Chapter 7 in Inorganic Nanoparticles: Synthesis, Applications, and Perspectives, Claudia Altavilla Ed., CRC Press, Taylor & Francis, 2010.
[48] Suarez-Alcantara K, Rodr?guez-Castellanos A, Dante R, Solorza-Feria O. RuxCrySez electrocatalyst for oxygen reduction in a polymer electrolyte membrane fuel cell, Journal of Power Sources, 2006, 157(1): 114-120.
[49] Guha A, Zawodzinski Jr T A, Schiraldi D A. Evaluation of electrochemical performance for surface-modified carbons as catalyst support in polymer electrolyte membrane (PEM) fuel cells, Journal of Power Sources, 2007, 172(2): 530.
[50] Zhang J, Sasaki K, Sutter E, Adzic R R. Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters, Science, 2007, 315(5809): 220-222.
[51] Chen S, Gasteiger H A, Hayakawa K, Tada T, Shao-Horn Y. Platinum-Alloy Cathode Catalyst Degradation in Proton Exchange Membrane Fuel Cells: Nanometer-Scale Compositional and Morphological Changes, Journal of The Electrochemical Society, 2010, 157(1): A82-A97.
[52] Schulenburg H, Muller E, Khelashvili G, Roser T, Bonnemann H, Wokaun A, Scherer G G, Heat-Treated PtCo3 Nanoparticles as Oxygen Reduction Catalysts, Journal of Physical Chemistry C, 2009, 113(10): 4069–4077.
[53] Liu Z, Yu C, Rusakova I A., Huang D, Strasser P. Synthesis of Pt(3)Co Alloy Nanocatalyst via Reverse Micelle for Oxygen Reduction Reaction in PEMFCs, Topics in Catalysis, 2008, 49(3-4): 241–250.
[54] Wang C, Chi M, Li D, Strmcnik D, van der Vliet D, Wang G, Komanicky V, Chang K-C, Paulikas A P, Tripkovic D, Pearson J, More K L, Markovic N M, Stamenkovic V R, Design and Synthesis of Bimetallic Electrocatalyst with Multilayered Pt-Skin Surfaces, Journal of The American Chemical Society, 2011, 133(36): 14396–14403.
[55] Wang C, van der Vliet D, Chang K-C, You H, Strmcnik D, Schlueter J A, Markovic N M, Stamenkovic V R. Monodisperse Pt3Co Nanoparticles as a Catalyst for the Oxygen Reduction Reaction: Size-Dependent Activity, Journal of Physical Chemistry C, 2009, 113(45): 19365–19368.
[56] van der Vliet D, Strmcnik D S, Wang C, Stamenkovic V R, Markovic N M, Koper M T M. On the importance of correcting for the uncompensated Ohmic resistance in model experiments of the Oxygen Reduction Reaction, Journal of Electroanalytical Chemistry, 2010, 647(1): 29-34.
[57] Zhong C J, Luo J, Fang B, Wanjala B, Njoki P, Loukrakpam R, Yin J, Nanostructured Catalysts in Fuel Cells, Nanotechnology, 2010, 21: 062001.
[58] Wanjala B N, Fang B, Loukrakpam R, Chen Y, Engelhard M, Luo J, Yin J, Yang L, Shan S, Zhong C J. Role of Metal Coordination Structures in Enhancement of Electrocatalytic Activity of Ternary Nanoalloys for Oxygen Reduction Reaction, ACS Catalysis, 2012, 2(5): 795–806.
[59] Stamenkovic V, Mun B S, Mayrhofer K J J, Ross P N, Markovic N M, Rossmeisl J, Greeley J, Norskov J K. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure, Angewandte Chemie International Edition, 2006, 45(18): 2897-2901.
[60] Xu Y, Ruban A V, Mavrikakis M. Adsorption and dissociation of O-2 on Pt-Co and Pt-Fe alloys, Journal of The American Chemical Society, 2004, 126(14): 4717-4725.
[61] Xu Q, Kreidler E, He T. Performance and durability of PtCo alloy catalysts for oxygen electroreduction in acidic environments, Electrochimica Acta, 2010, 55(26): 7551–7557.
[62] Wang C, Van der Vliet D, Chang K C, Markovic N M, Stamenkovic V R. Monodisperse Pt3Co nanoparticles as electrocatalyst: the effects of particle size and pretreatment on electrocatalytic reduction of oxygen, Physical Chemistry Chemical Physics, 2010, 12(26): 6933-6939.
[63] Koh S, Yu C, Mani P, Srivastava R, Strasser P. Activity of ordered and disordered Pt-Co alloy phases for the electroreduction of oxygen in catalysts with multiple coexisting phases, Journal of Power Sources, 2007, 172(1): 50-56.
[64] Wanjala B, Fang B, Luo J, Chen Y, Yin J, Engelhard M, Loukrakpam R, Zhong C J. Correlation between Atomic Coordination Structure and Enhanced Electrocatalytic Activity for Trimetallic Alloy Catalysts, Journal of The American Chemical Society, 2011, 133: 12714-12727.
[65] Loukrakpam R, Wanjala B N, Yin J, Fang B, Luo J, Chen Y, Petkov V, Zhong C J, Shao M, Protsailo L, Kawamura T. Structural and Electrocatalytic Properties of Nanoengineered PtIrCo Catalysts for Oxygen Reduction Reaction, ACS Catalysis, 2011, 1: 562–572.
[66] Fang B, Wanjala B N, Yin J, Loukrakpam R, Luo J, Hu X, Last J, Zhong C J. Electrocatalytic Performance of Pt-based Trimetallic Nanoparticle Catalysts in Proton Exchange Membrane Fuel Cells, International Journal of Hydrogen Energy, 2012, 37: 4627-4632.
[67] Chen G, You G, Zheng L, Li Y, Yang L, Cai F, Cai J, Zhong C J, Chen B H. Carbon-Supported PtAu Alloy Nanoparticle Catalysts for Enhanced Electrocatalytic Oxidation of Formic Acid, Journal of Power Sources, 2011, 196: 8323– 8330.
[68] Chen G, Liao M, Li Y, Wang D, You G, Zhong C J, Chen B H. Pt-Decorated PdAu/C Nanocatalysts with Ultralow Pt Loading for Formic Acid Electrooxidation, International Journal of Hydrogen Energy, 2012, 37: 9959–9966.

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