Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse PtxNi1‐x Nanoparticles

Monodisperse and homogeneous Pt{sub x}Ni{sub 1-x} alloy nanoparticles of various compositions are synthesized via an organic solution approach in order to reveal the correlation between surface chemistry and their electrocatalytic properties. Atomic-level microscopic analysis of the compositional profile and modeling of nanoparticle structure are combined to follow the dependence of Ni dissolution on the initial alloy composition and formation of the Pt-skeleton nanostructures. The developed approach and acquired knowledge about surface structure-property correlation can be further generalized and applied towards the design of advanced functional nanomaterials.

[1]  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.

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

[3]  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 .

[4]  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 .

[5]  M. Arenz,et al.  Adsorbate-induced surface segregation for core-shell nanocatalysts. , 2009, Angewandte Chemie.

[6]  P. Strasser,et al.  Voltammetric surface dealloying of Pt bimetallic nanoparticles: an experimental and DFT computational analysis. , 2008, Physical chemistry chemical physics : PCCP.

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

[8]  C. Domb,et al.  Cluster Size in Random Mixtures and Percolation Processes , 1961 .

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

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

[11]  Hubert A. Gasteiger,et al.  Platinum-Alloy Cathode Catalyst Degradation in Proton Exchange Membrane Fuel Cells: Nanometer-Scale Compositional and Morphological Changes , 2010 .

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

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

[14]  Sachin Kumar,et al.  Monodisperse and highly active PtNi nanoparticles for O2 reduction , 2009 .

[15]  Mostafa A. El-Sayed,et al.  Alloy Formation of Gold−Silver Nanoparticles and the Dependence of the Plasmon Absorption on Their Composition , 1999 .

[16]  H. Yin,et al.  One-Pot Synthesis of Oleylamine Coated AuAg Alloy NPs and Their Catalysis for CO Oxidation , 2009 .

[17]  S. Campbell,et al.  Oxygen Reduction by Sol-Derived Pt ∕ Co -Based Alloys for PEM Fuel Cells , 2005 .

[18]  J. Newman.  Resistance for Flow of Current to a Disk , 1966 .

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

[20]  J. Dahn,et al.  Dissolution of Transition Metals in Combinatorially Sputtered Pt1 − x − y M x M y ′ ( M , M ′ = Co , Ni , Mn , Fe ) PEMFC Electrocatalysts , 2006 .

[21]  Nathan T. Hahn,et al.  Effects of Composition and Annealing Conditions on Catalytic Activities of Dealloyed Pt–Cu Nanoparticle Electrocatalysts for PEMFC , 2008 .

[22]  P. Ross,et al.  Surface science studies of model fuel cell electrocatalysts , 2002 .

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

[24]  V. Radmilović,et al.  Oxygen Reduction on Carbon-Supported Pt−Ni and Pt−Co Alloy Catalysts , 2002 .

[25]  Peter Strasser,et al.  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 , 2011 .

[26]  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.

[27]  Y. Kang,et al.  Chemical Synthesis and Silica Encapsulation of NiPt Nanoparticles , 2007 .

[28]  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.

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

[30]  J. Dahn,et al.  Oxygen Reduction Activity of Magnetron-Sputtered Pt1 − x Co x ( 0 ⩽ x ⩽ 0.5 ) Films , 2007 .

[31]  M. Mavrikakis,et al.  Alloy catalysts designed from first principles , 2004, Nature materials.

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

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

[34]  Jihoon Cho,et al.  Particle size and alloying effects of Pt-based alloy catalysts for fuel cell applications , 2000 .

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

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

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

[38]  A. Kornowski,et al.  Colloidal synthesis of NixPt1-x nanoparticles with tuneable composition and size. , 2007, Small.