Nanostructured Pt-alloy electrocatalysts for PEM fuel cell oxygen reduction reaction.

In this critical review, we present the current technological advances in proton exchange membrane (PEM) fuel cell catalysis, with a focus on strategies for developing nanostructured Pt-alloys as electrocatalysts for the oxygen reduction reaction (ORR). The achievements are reviewed and the major challenges, including high cost, insufficient activity and low stability, are addressed and discussed. The nanostructured Pt-alloy catalysts can be grouped into different clusters: (i) Pt-alloy nanoparticles, (ii) Pt-alloy nanotextures such as Pt-skins/monolayers on top of base metals, and (iii) branched or anisotropic elongated Pt or Pt-alloy nanostructures. Although some Pt-alloy catalysts with advanced nanostructures have shown remarkable activity levels, the dissolution of metals, including Pt and alloyed base metals, in a fuel cell operating environment could cause catalyst degradation, and still remains an issue. Another concern may be low retention of the nanostructure of the active catalyst during fuel cell operation. To facilitate further efforts in new catalyst development, several research directions are also proposed in this paper (130 references).

[1]  A. Shukla,et al.  Carbon-supported Pt–Fe alloy as a methanol-resistant oxygen-reduction catalyst for direct methanol fuel cells , 2004 .

[2]  P. Balbuena,et al.  Adsorption of O, OH, and H2O on Pt-Based Bimetallic Clusters Alloyed with Co, Cr, and Ni , 2004 .

[3]  B. Popov,et al.  Development of method for synthesis of Pt-Co cathode catalysts for PEM fuel cells , 2007 .

[4]  S. Ball,et al.  Mechanisms of Activity Loss in PtCo Alloy Systems , 2007 .

[5]  M. S. Hegde,et al.  An XPS study on binary and ternary alloys of transition metals with platinized carbon and its bearing upon oxygen electroreduction in direct methanol fuel cells , 2001 .

[6]  Lei Zhang,et al.  The effect of heat treatment on nanoparticle size and ORR activity for carbon-supported Pd–Co alloy electrocatalysts , 2007 .

[7]  A. Manthiram,et al.  Influence of atomic ordering on the electrocatalytic activity of Pt–Co alloys in alkaline electrolyte and proton exchange membrane fuel cells , 2004 .

[8]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode , 2004 .

[9]  A. Anderson,et al.  Cobalt concentration effect in Pt1−xCox on the reversible potential for forming OHads from H2Oads in acid solution , 2005 .

[10]  Younan Xia,et al.  Template-Engaged Replacement Reaction: A One-Step Approach to the Large-Scale Synthesis of Metal Nanostructures with Hollow Interiors , 2002 .

[11]  K. Yasuda,et al.  Platinum-Iridium Alloys as Oxygen Reduction Electrocatalysts for Polymer Electrolyte Fuel Cells , 2005, ECS Transactions.

[12]  Younan Xia,et al.  Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction , 2009, Science.

[13]  Bongjin Simon Mun,et al.  Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. , 2007, Nature materials.

[14]  M. Shao,et al.  Platinum monolayer on nonnoble metal-noble metal core-shell nanoparticle electrocatalysts for O2 reduction. , 2005, The journal of physical chemistry. B.

[15]  M. Mavrikakis,et al.  Platinum Monolayer Fuel Cell Electrocatalysts , 2007 .

[16]  Z. Wang,et al.  Transmission Electron Microscopy of Shape-Controlled Nanocrystals and Their Assemblies , 2000 .

[17]  Ermete Antolini,et al.  The stability of Pt–M (M = first row transition metal) alloy catalysts and its effect on the activity in low temperature fuel cells: A literature review and tests on a Pt–Co catalyst , 2006 .

[18]  H. Gasteiger,et al.  Oxygen reduction on platinum low-index single-crystal surfaces in sulfuric acid solution. Rotating ring - Pt(hkl) disk studies , 1995 .

[19]  M. El-Sayed,et al.  Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability. , 2005, The journal of physical chemistry. B.

[20]  Gongxuan Lu,et al.  Facile Synthesis of Platinum Nanofiber/Nanotube Junction Structures at Room Temperature , 2008 .

[21]  Peidong Yang,et al.  Morphological control of catalytically active platinum nanocrystals. , 2006, Angewandte Chemie.

[22]  E. Antolini Formation, microstructural characteristics and stability of carbon supported platinum catalysts for low temperature fuel cells , 2003 .

[23]  S. Zignani,et al.  Evaluation of the stability and durability of Pt and Pt-Co/C catalysts for polymer electrolyte membrane fuel cells , 2008 .

[24]  M. Neurock,et al.  Insights into the overpotential for oxygen reduction on Pt and Pt skin alloys: A comparison of theory and experiment , 2005 .

[25]  E. Antolini Platinum-based ternary catalysts for low temperature fuel cells Part I. Preparation methods and structural characteristics , 2007 .

[26]  Shouheng Sun,et al.  Recent Advances in Chemical Synthesis, Self‐Assembly, and Applications of FePt Nanoparticles , 2006 .

[27]  A. Anderson,et al.  Potential Shift for OH(ads) Formation on the Pt Skin on Pt3Co ( 111 ) Electrodes in Acid Theory and Experiment , 2005 .

[28]  I. Yamashita,et al.  Synthesis of CoPt and FePt3 Nanowires Using the Central Channel of Tobacco Mosaic Virus as a Biotemplate , 2007 .

[29]  G. Somorjai,et al.  Pt nanocrystals: shape control and Langmuir-Blodgett monolayer formation. , 2005, The journal of physical chemistry. B.

[30]  Younan Xia,et al.  Synthesis and characterization of metal nanostructures with hollow interiors , 2003, SPIE Optics + Photonics.

[31]  Younan Xia,et al.  Facile synthesis of highly faceted multioctahedral Pt nanocrystals through controlled overgrowth. , 2008, Nano letters.

[32]  E. Gonzalez,et al.  Structure and Activity of Carbon-Supported Pt−Co Electrocatalysts for Oxygen Reduction , 2004 .

[33]  Piotr Zelenay,et al.  A class of non-precious metal composite catalysts for fuel cells , 2006, Nature.

[34]  Hong Yang,et al.  Designer platinum nanoparticles: Control of shape, composition in alloy, nanostructure and electrocatalytic property , 2009 .

[35]  G. Jackson,et al.  Enhanced CO tolerance for hydrogen activation in Au-Pt dendritic heteroaggregate nanostructures. , 2006, Journal of the American Chemical Society.

[36]  Junliang Zhang,et al.  Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on Pd(111) and on carbon-supported Pd nanoparticles , 2004 .

[37]  Weijiang Zhou,et al.  Carbon-Supported Pseudo-Core–Shell Pd–Pt Nanoparticles for ORR with and without Methanol , 2008 .

[38]  T. C. Green,et al.  Shape-Controlled Synthesis of Colloidal Platinum Nanoparticles , 1996, Science.

[39]  G. Somorjai,et al.  Mechanism of catalysis of hydrocarbon reactions by platinum surfaces , 1975, Nature.

[40]  M. El-Sayed,et al.  Chemistry and properties of nanocrystals of different shapes. , 2005, Chemical reviews.

[41]  Younan Xia,et al.  Shape-controlled synthesis of platinum nanocrystals for catalytic and electrocatalytic applications , 2009 .

[42]  Junliang Zhang,et al.  Mixed-metal pt monolayer electrocatalysts for enhanced oxygen reduction kinetics. , 2005, Journal of the American Chemical Society.

[43]  Younan Xia,et al.  Hollow nanostructures of platinum with controllable dimensions can be synthesized by templating against selenium nanowires and colloids. , 2003, Journal of the American Chemical Society.

[44]  D. Stevens,et al.  Studies of Transition Metal Dissolution from Combinatorially Sputtered, Nanostructured Pt1 − x M x (M = Fe, Ni; 0 < x < 1 ) Electrocatalysts for PEM Fuel Cells , 2005 .

[45]  Z. Kiraly,et al.  Size-Selective Synthesis of Cubooctahedral Palladium Particles Mediated by Metallomicelles , 2003 .

[46]  Masahiro Watanabe,et al.  Activity and Stability of Ordered and Disordered Co‐Pt Alloys for Phosphoric Acid Fuel Cells , 1994 .

[47]  Hubert A. Gasteiger,et al.  Kinetics of oxygen reduction on Pt(hkl) electrodes : Implications for the crystallite size effect with supported Pt electrocatalysts , 1997 .

[48]  P. Balbuena,et al.  Surface segregation of core atoms in core–shell structures , 2008 .

[49]  S. Srinivasan,et al.  Effect of Preparation Conditions of Pt Alloys on Their Electronic, Structural, and Electrocatalytic Activities for Oxygen Reduction-XRD, XAS, and Electrochemical Studies , 1995 .

[50]  Jin Luo,et al.  Activity-composition correlation of AuPt alloy nanoparticle catalysts in electrocatalytic reduction of oxygen , 2006 .

[51]  P. Bruce,et al.  Nanostructured materials for advanced energy conversion and storage devices , 2005, Nature materials.

[52]  C. Brinker,et al.  Controlled synthesis of 2-D and 3-D dendritic platinum nanostructures. , 2004, Journal of the American Chemical Society.

[53]  A. Alivisatos,et al.  Synthesis, self-assembly, and magnetic behavior of a two-dimensional superlattice of single-crystal ε-Co nanoparticles , 2001 .

[54]  Jaemin Kim,et al.  A general strategy for synthesizing FePt nanowires and nanorods. , 2007, Angewandte Chemie.

[55]  A. Barrero,et al.  A method for making inorganic and hybrid (organic/inorganic) fibers and vesicles with diameters in the submicrometer and micrometer range via sol-gel chemistry and electrically forced liquid jets. , 2003, Journal of the American Chemical Society.

[56]  Frédéric Jaouen,et al.  Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells , 2009, Science.

[57]  Thomas Bligaard,et al.  The nature of the active site in heterogeneous metal catalysis. , 2008, Chemical Society reviews.

[58]  Sun,et al.  Monodisperse FePt nanoparticles and ferromagnetic FePt nanocrystal superlattices , 2000, Science.

[59]  A. Kuzume,et al.  Oxygen reduction on stepped platinum surfaces in acidic media , 2007 .

[60]  Younan Xia,et al.  Pt Nanoparticles Surfactant‐Directed Assembled into Colloidal Spheres and used as Substrates in Forming Pt Nanorods and Nanowires , 2006 .

[61]  Paul F. Mutolo,et al.  Synthesis, Characterization, and Electrocatalytic Activity of PtBi and PtPb Nanoparticles Prepared by Borohydride Reduction in Methanol , 2006 .

[62]  Younan Xia,et al.  Use of electrospinning to directly fabricate hollow nanofibers with functionalized inner and outer surfaces. , 2004, Small.

[63]  Peidong Yang,et al.  Shaping binary metal nanocrystals through epitaxial seeded growth. , 2007, Nature materials.

[64]  Zhong Lin Wang,et al.  A new catalytically active colloidal platinum nanocatalyst: the multiarmed nanostar single crystal. , 2008, Journal of the American Chemical Society.

[65]  Edward Sacher,et al.  Template‐ and Surfactant‐free Room Temperature Synthesis of Self‐Assembled 3D Pt Nanoflowers from Single‐Crystal Nanowires , 2008 .

[66]  Héctor R. Colón-Mercado,et al.  Stability of platinum based alloy cathode catalysts in PEM fuel cells , 2006 .

[67]  N. Marković,et al.  Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt3Ni and Pt3Co Alloy Surfaces , 2002 .

[68]  H. Abruña,et al.  Electrocatalytic activity of ordered intermetallic phases for fuel cell applications. , 2004, Journal of the American Chemical Society.

[69]  Lei Zhang,et al.  Effect of synthetic reducing agents on morphology and ORR activity of carbon-supported nano-Pd–Co alloy electrocatalysts , 2007 .

[70]  Ping Liu,et al.  Electrodeposition of Pt onto RuO2(110) Single-Crystal Surface , 2007 .

[71]  J. Clavilier,et al.  Electrochemical behaviour of the (110) orientation of a platinum surface in acid medium: the role of anions , 1989 .

[72]  Jens K Nørskov,et al.  Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. , 2006, Angewandte Chemie.

[73]  J. Beery,et al.  Oxygen Reduction at Pt0.65Cr0.35, Pt0.2Cr0.8 and Roughened Platinum , 1988 .

[74]  Younan Xia,et al.  Polyol synthesis of platinum nanostructures: control of morphology through the manipulation of reduction kinetics. , 2005, Angewandte Chemie.

[75]  N. Marković,et al.  Effect of surface composition on electronic structure, stability, and electrocatalytic properties of Pt-transition metal alloys: Pt-skin versus Pt-skeleton surfaces. , 2006, Journal of the American Chemical Society.

[76]  Matthew Neurock,et al.  Elucidation of the electrochemical activation of water over Pd by first principles. , 2006, Angewandte Chemie.

[77]  Nathan T. Hahn,et al.  Efficient oxygen reduction fuel cell electrocatalysis on voltammetrically dealloyed Pt-Cu-Co nanoparticles. , 2007, Angewandte Chemie.

[78]  Manos Mavrikakis,et al.  Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen. , 2008, Nature materials.

[79]  Younan Xia,et al.  Single-crystal nanowires of platinum can be synthesized by controlling the reaction rate of a polyol process. , 2004, Journal of the American Chemical Society.

[80]  Kyriakos Komvopoulos,et al.  Platinum nanoparticle shape effects on benzene hydrogenation selectivity. , 2007, Nano letters.

[81]  Ermete Antolini,et al.  The methanol oxidation reaction on platinum alloys with the first row transition metals The case of Pt-Co and -Ni alloy electrocatalysts for DMFCs: A short review , 2006 .

[82]  Joseph M. McLellan,et al.  Kinetically controlled synthesis of triangular and hexagonal nanoplates of palladium and their SPR/SERS properties. , 2005, Journal of the American Chemical Society.

[83]  A. Wiȩckowski,et al.  Adsorption of bisulfate anion on a Pt(100) electrode : a comparison with Pt(111) and Pt(poly) , 1993 .

[84]  P. Ross,et al.  The Structure and Activity of Pt‐Co Alloys as Oxygen Reduction Electrocatalysts , 1990 .

[85]  H. Gasteiger,et al.  Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs , 2005 .

[86]  M. Márquez,et al.  Micro/Nano Encapsulation via Electrified Coaxial Liquid Jets , 2002, Science.

[87]  Y. P. Lee,et al.  Electronic structure of Co-Pt alloys: X-ray spectroscopy and density-functional calculations , 2003 .

[88]  Hiroyuki Uchida,et al.  Enhancement of the Electroreduction of Oxygen on Pt Alloys with Fe, Ni, and Co , 1999 .

[89]  Shouheng Sun,et al.  A general approach to the size- and shape-controlled synthesis of platinum nanoparticles and their catalytic reduction of oxygen. , 2008, Angewandte Chemie.

[90]  K. Sasaki,et al.  Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters , 2007, Science.

[91]  H. Yano,et al.  Oxygen reduction activity of carbon-supported Pt-M (M = V, Ni, Cr, Co, and Fe) alloys prepared by nanocapsule method. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[92]  Wenzheng Li,et al.  Supportless Pt and PtPd nanotubes as electrocatalysts for oxygen-reduction reactions. , 2007, Angewandte Chemie.

[93]  E. Shevchenko,et al.  Study of nucleation and growth in the organometallic synthesis of magnetic alloy nanocrystals: the role of nucleation rate in size control of CoPt3 nanocrystals. , 2003, Journal of the American Chemical Society.

[94]  B. Popov,et al.  Durability study of Pt3Ni1 catalysts as cathode in PEM fuel cells , 2004 .

[95]  S. Gottesfeld,et al.  Electrochemical and surface science investigations of PtCr alloy electrodes , 1987 .

[96]  Philip N. Ross,et al.  Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability , 2007, Science.

[97]  Sanjeev Mukerjee,et al.  Enhanced electrocatalysis of oxygen reduction on platinum alloys in proton exchange membrane fuel cells , 1993 .

[98]  P. Strasser,et al.  Electrocatalysis on bimetallic surfaces: modifying catalytic reactivity for oxygen reduction by voltammetric surface dealloying. , 2007, Journal of the American Chemical Society.

[99]  Younan Xia,et al.  Mechanistic study on the replacement reaction between silver nanostructures and chloroauric acid in aqueous medium. , 2004, Journal of the American Chemical Society.

[100]  N. Marković,et al.  A study of electronic structures of Pt3M (M=Ti,V,Cr,Fe,Co,Ni) polycrystalline alloys with valence-band photoemission spectroscopy. , 2005, The Journal of chemical physics.

[101]  Younan Xia,et al.  Direct Fabrication of Composite and Ceramic Hollow Nanofibers by Electrospinning , 2004 .

[102]  Jianglan Shui,et al.  Platinum nanowires produced by electrospinning. , 2009, Nano letters.

[103]  Fred Joseck,et al.  2008 DOE Hydrogen Program Merit Review and Peer Evaluation Meeting , 2008 .

[104]  Sanjeev Mukerjee,et al.  Role of Structural and Electronic Properties of Pt and Pt Alloys on Electrocatalysis of Oxygen Reduction An In Situ XANES and EXAFS Investigation , 1995 .

[105]  J. Clavilier,et al.  Influence of specific adsorption of anions on the electrochemical behaviour of the Pt (100) surface in acid medium: Comparison with Pt (111) , 1989 .

[106]  Shuhui Sun,et al.  Controlled Growth of Pt Nanowires on Carbon Nanospheres and Their Enhanced Performance as Electrocatalysts in PEM Fuel Cells , 2008 .

[107]  H. Gasteiger,et al.  Just a Dream—or Future Reality? , 2009, Science.

[108]  A. Wiȩckowski,et al.  Adsorption of anions on ultrathin metal deposits on single-crystal electrodes: Part 3. Voltammetric and radiochemical study of bisulfate adsorption on Pt(111) and Pt(poly) electrodes containing silver adatoms , 1993 .

[109]  Ping Yu,et al.  PtCo/C cathode catalyst for improved durability in PEMFCs , 2005 .

[110]  S. Ball,et al.  Enhanced Stability of PtCo catalysts for PEMFC , 2006 .

[111]  Younan Xia,et al.  Alloying and Dealloying Processes Involved in the Preparation of Metal Nanoshells through a Galvanic Replacement Reaction , 2003 .

[112]  J. Liu,et al.  One-step synthesis of FePt nanoparticles with tunable size. , 2004, Journal of the American Chemical Society.

[113]  Zhong Lin Wang,et al.  Synthesis of Tetrahexahedral Platinum Nanocrystals with High-Index Facets and High Electro-Oxidation Activity , 2007, Science.

[114]  Lei Zhang,et al.  A review of heat-treatment effects on activity and stability of PEM fuel cell catalysts for oxygen reduction reaction , 2007 .

[115]  Ping Liu,et al.  Nano-scale effects in electrochemistry , 2004 .

[116]  E. Herrero,et al.  On the kinetics of oxygen reduction on platinum stepped surfaces in acidic media , 2004 .

[117]  Younan Xia,et al.  One‐Dimensional Nanostructures: Synthesis, Characterization, and Applications , 2003 .

[118]  Younan Xia,et al.  Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics? , 2009, Angewandte Chemie.

[119]  A. Manthiram,et al.  Effect of Atomic Ordering on the Catalytic Activity of Carbon Supported PtM (M = Fe , Co, Ni, and Cu) Alloys for Oxygen Reduction in PEMFCs , 2005 .