CO adsorption in PdxCoyXz (X = Au, Mo, Ni) tertiary alloy nanocatalysts for PEM fuel cells—a theoretical analysis

Application of tertiary alloy nanoparticles is becoming more important, however, the local structure of such alloyed particles, which is critical for tailoring their properties, is not yet very clearly understood. In this study, we present detailed theoretical analysis on the atomistic structure and CO adsorption in Pd70Co20X10 (X=Au, Mo, Ni) tertiary composite alloys for their application in fuel cells toward oxygen reduction reaction (ORR). Basic structure and the most stable configurations for all the three composites are determined. Quantum mechanical approaches and classic molecular dynamics methods are applied to model the structure and to determine the lowest energy configurations. Our theoretical results agree well with the experimental results of XRD patterns. Considering those structures as the base, simulations were performed to determine the magnitude of CO poisoning. The results obtained by ab‐initio calculations allow us to estimate the CO‐tolerance that these catalysts might have, along with those obtained for Pd‐Co‐Ni (70:20:10 atom %) tertiary alloy, and compared with commercial Pt (1 1 0) catalyst. From these results, a comparison has been made to show different CO adsorption strengths. This is the first step to fabricate an efficient engineering design that allows us to obtain high‐performance, low‐cost nanostructured catalysts. Copyright © 2010 John Wiley & Sons, Ltd.

[1]  A. López-Ortiz,et al.  Low Pt content on the Pd45Pt5Sn50 cathode catalyst for PEM fuel cells , 2010 .

[2]  Ermete Antolini,et al.  Alkaline direct alcohol fuel cells , 2010 .

[3]  Xin Wang,et al.  Novel palladium-lead (Pd-Pb/C) bimetallic catalysts for electrooxidation of ethanol in alkaline media , 2010 .

[4]  R. Masel,et al.  Performance of the direct formic acid fuel cell with electrochemically modified palladium–antimony anode catalyst , 2010 .

[5]  V. Noto,et al.  Synthesis, characterization and electrochemical performance of tri-metal Pt-free carbon nitride electrocatalysts for the oxygen reduction reaction , 2010 .

[6]  P. Chu,et al.  Preparation and characterization of novel nickel–palladium electrodes supported by silicon microchannel plates for direct methanol fuel cells , 2010 .

[7]  Y. Sung,et al.  Pd-based PdPt(19:1)/C electrocatalyst as an electrode in PEM fuel cell , 2007 .

[8]  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 .

[9]  T. He,et al.  Preparation and characterization of carbon-supported PtVFe electrocatalysts , 2006 .

[10]  A. Pasturel,et al.  Ab initio calculation of the phase stability in Au-Pd and Ag-Pt alloys , 2006 .

[11]  E. Kreidler,et al.  Combinatorial Discovery of Alloy Electrocatalysts for Oxygen Reduction Reaction , 2006 .

[12]  Arumugam Manthiram,et al.  Pd-Co-Mo electrocatalyst for the oxygen reduction reaction in proton exchange membrane fuel cells. , 2005, The journal of physical chemistry. B.

[13]  B. Viswanathan,et al.  Nanocrystalline pyrochlore bonded to proton exchange membrane electrolyte as electrode material for oxygen reduction , 2005 .

[14]  José L. Fernández,et al.  Pd-Ti and Pd-Co-Au electrocatalysts as a replacement for platinum for oxygen reduction in proton exchange membrane fuel cells. , 2005, Journal of the American Chemical Society.

[15]  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 .

[16]  Rodney L. Borup,et al.  Durability of PEFCs at High Humidity Conditions , 2005 .

[17]  A. Manthiram,et al.  Mesoporous Carbon with Larger Pore Diameter as an Electrocatalyst Support for Methanol Oxidation , 2004 .

[18]  K. Sawai,et al.  Heat-Treated Transition Metal Hexacyanometallates as Electrocatalysts for Oxygen Reduction Insensitive to Methanol , 2004 .

[19]  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 .

[20]  K. Ota,et al.  New palladium alloys catalyst for the oxygen reduction reaction in an acid medium , 2004 .

[21]  José L. Fernández,et al.  Oxygen is electroreduced to water on a "wired" enzyme electrode at a lesser overpotential than on platinum. , 2003, Journal of the American Chemical Society.

[22]  A. Vijh,et al.  Non-noble metal-carbonized aerogel composites as electrocatalysts for the oxygen reduction reaction , 2003 .

[23]  A. Wokaun,et al.  Oxygen reduction on high surface area Pt-based alloy catalysts in comparison to well defined smooth bulk alloy electrodes , 2002 .

[24]  Adam Heller,et al.  An oxygen cathode operating in a physiological solution. , 2002, Journal of the American Chemical Society.

[25]  Kwong‐Yu Chan,et al.  Microemulsion synthesis and electrocatalytic properties of platinum–cobalt nanoparticles , 2002 .

[26]  Juhyoun Kwak,et al.  Ordered nanoporous arrays of carbon supporting high dispersions of platinum nanoparticles , 2001, Nature.

[27]  Andrei V. Ruban,et al.  Anode materials for low-temperature fuel cells : A density functional theory study , 2001 .

[28]  H. Gasteiger,et al.  On the CO tolerance of novel colloidal PdAu/carbon electrocatalysts , 2001 .

[29]  B. Tolochko,et al.  Formation of Nanosized Metal Particles of Cobalt, Nickel, and Copper in the Matrix of Layered Double Hydroxide , 2000 .

[30]  V. Plzak,et al.  The PEMFC-integrated CO oxidation — a novel method of simplifying the fuel cell plant , 1999 .

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

[32]  D. Guay,et al.  High energy ball-milled Pt and Pt–Ru catalysts for polymer electrolyte fuel cells and their tolerance to CO , 1999 .

[33]  Hiroshi Igarashi,et al.  Enhancement of the electrocatalytic O2 reduction on Pt–Fe alloys , 1999 .

[34]  H. Gasteiger,et al.  Electrooxidation of CO and H2/CO Mixtures on a Well-Characterized Pt3Sn Electrode Surface , 1995 .

[35]  U. Bardi.  The atomic structure of alloy surfaces and surface alloys , 1994 .

[36]  J. Zen,et al.  Oxygen Reduction on Ruthenium‐Oxide Pyrochlore Produced in a Proton‐Exchange Membrane , 1994 .

[37]  H. Tributsch,et al.  Energy conversion catalysis using semiconducting transition metal cluster compounds , 1986, Nature.

[38]  C. Koval,et al.  Electrode catalysis of the four-electron reduction of oxygen to water by dicobalt face-to-face porphyrins , 1980 .