Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces.

Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

[1]  U. Bergmann,et al.  In situ X-ray probing reveals fingerprints of surface platinum oxide. , 2011, Physical Chemistry, Chemical Physics - PCCP.

[2]  Karren L. More,et al.  Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse PtxNi1‐x Nanoparticles , 2011 .

[3]  Dusan Strmcnik,et al.  On the importance of correcting for the uncompensated Ohmic resistance in model experiments of the Oxygen Reduction Reaction , 2010 .

[4]  N. Marković,et al.  Monodisperse Pt(3)Co nanoparticles as electrocatalyst: the effects of particle size and pretreatment on electrocatalytic reduction of oxygen. , 2010, Physical chemistry chemical physics : PCCP.

[5]  Michael F Toney,et al.  Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts. , 2010, Nature chemistry.

[6]  Grant Bunker,et al.  Introduction to XAFS: A Practical Guide to X-ray Absorption Fine Structure Spectroscopy , 2010 .

[7]  Jun Zhang,et al.  Synthesis and oxygen reduction activity of shape-controlled Pt(3)Ni nanopolyhedra. , 2010, Nano letters.

[8]  N. Marković,et al.  Monodisperse Pt3Co Nanoparticles as a Catalyst for the Oxygen Reduction Reaction: Size-Dependent Activity , 2009 .

[9]  M. Matsumoto,et al.  In situ and real-time monitoring of oxide growth in a few monolayers at surfaces of platinum nanoparticles in aqueous media. , 2009, Journal of the American Chemical Society.

[10]  A. Wokaun,et al.  Heat-Treated PtCo₃ Nanoparticles as Oxygen Reduction Catalysts , 2009 .

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

[12]  Y. Shao-horn,et al.  Origin of Oxygen Reduction Reaction Activity on “Pt3Co” Nanoparticles: Atomically Resolved Chemical Compositions and Structures , 2009 .

[13]  A. Kornowski,et al.  Nucleation and Growth Mechanism of NixPt1–x Nanoparticles , 2008 .

[14]  J. Greeley,et al.  Unique activity of platinum adislands in the CO electrooxidation reaction. , 2008, Journal of the American Chemical Society.

[15]  Gerbrand Ceder,et al.  Effect of particle size and surface structure on adsorption of O and OH on platinum nanoparticles: A first-principles study , 2008 .

[16]  M. Armand,et al.  Building better batteries , 2008, Nature.

[17]  P. Strasser,et al.  Dealloyed Pt−Cu Core−Shell Nanoparticle Electrocatalysts for Use in PEM Fuel Cell Cathodes , 2008 .

[18]  Mahlon Wilson,et al.  Scientific aspects of polymer electrolyte fuel cell durability and degradation. , 2007, Chemical reviews.

[19]  Chemical Synthesis and Silica Encapsulation of NiPt Nanoparticles , 2007 .

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

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

[22]  Andreas Menzel,et al.  Stability and Dissolution of Platinum Surfaces in Perchloric Acid , 2006 .

[23]  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.

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

[25]  P N Ross,et al.  The impact of geometric and surface electronic properties of pt-catalysts on the particle size effect in electrocatalysis. , 2005, The journal of physical chemistry. B.

[26]  M Newville,et al.  ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. , 2005, Journal of synchrotron radiation.

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

[28]  A. Russell,et al.  X-ray absorption spectroscopy of low temperature fuel cell catalysts. , 2004, Chemical reviews.

[29]  J. Hanson,et al.  Experimental and theoretical studies on the reaction of H(2) with NiO: role of O vacancies and mechanism for oxide reduction. , 2002, Journal of the American Chemical Society.

[30]  M Newville,et al.  IFEFFIT: interactive XAFS analysis and FEFF fitting. , 2001, Journal of synchrotron radiation.

[31]  U. Ruett,et al.  BESSRC-CAT bending magnet beamline at the Advanced Photon Source. , 2000 .

[32]  M. Brust,et al.  Spontaneous ordering of bimodal ensembles of nanoscopic gold clusters , 1998, Nature.

[33]  K. M. Abraham,et al.  A Polymer Electrolyte‐Based Rechargeable Lithium/Oxygen Battery , 1996 .

[34]  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 .

[35]  J. Rehr,et al.  Near-edge x-ray-absorption fine structure of Pb: A comparison of theory and experiment. , 1993, Physical review. B, Condensed matter.

[36]  K. Kinoshita,et al.  Particle Size Effects for Oxygen Reduction on Highly Dispersed Platinum in Acid Electrolytes , 1990 .

[37]  R. V. Hardeveld,et al.  The statistics of surface atoms and surface sites on metal crystals , 1969 .