Synthesis and oxygen reduction activity of shape-controlled Pt(3)Ni nanopolyhedra.

Platinum-based alloys have been extensively shown to be effective catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Most of these catalysts are nanoparticles without shape control. Recently, extended Pt(3)Ni(111) surfaces prepared in ultrahigh vacuum were demonstrated to possess enhanced ORR catalytic activity as compared to the state-of-the-art carbon supported Pt (Pt/C) nanoparticle catalysts. How and whether this promising surface can be transformed into practical nanoscale electrocatalysts used in PEMFCs remain a challenge. We report a new wet-chemical approach of preparing monodisperse Pt(3)Ni nanoctahedra and nanocubes terminated with {111} and {100} facets, respectively. We further show that the ORR activity on the Pt(3)Ni nanoctahedra is approximately 5-fold higher than that of nanocubes with a similar size. Comparison of ORR activity between carbon-supported Pt(3)Ni nanoctahedra and commercial Pt/C reveals that the Pt(3)Ni nanoctahedra are highly active electrocatalysts. This synthetic strategy may be extended to the preparation of other shape-controlled fuel cell electrocatalysts.

[1]  Hubert A. Gasteiger,et al.  Handbook of Fuel Cells , 2010 .

[2]  Jiye Fang,et al.  A general strategy for preparation of Pt 3d-transition metal (Co, Fe, Ni) nanocubes. , 2009, Journal of the American Chemical Society.

[3]  S. Campbell,et al.  Ex Situ and In Situ Stability of Platinum Supported on Niobium-Doped Titania for PEMFCs , 2009 .

[4]  Alexey Serov,et al.  Review of non-platinum anode catalysts for DMFC and PEMFC application , 2009 .

[5]  G.J.M. Janssen,et al.  Proton-exchange-membrane fuel cells durability evaluated by load-on/off cycling , 2009 .

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

[7]  Kai Sun,et al.  Solution-based evolution and enhanced methanol oxidation activity of monodisperse platinum-copper nanocubes. , 2009, Angewandte Chemie.

[8]  Hong Yang,et al.  Synthesis and oxygen reduction electrocatalytic property of Pt-on-Pd bimetallic heteronanostructures. , 2009, Journal of the American Chemical Society.

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

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

[11]  Howard Wang,et al.  Simple cubic super crystals containing PbTe nanocubes and their core-shell building blocks. , 2008, Journal of the American Chemical Society.

[12]  G. Somorjai,et al.  Molecular surface chemistry by metal single crystals and nanoparticles from vacuum to high pressure. , 2008, Chemical Society reviews.

[13]  N. Marković,et al.  Segregation and stability at Pt3Ni(111) surfaces and Pt75Ni25 nanoparticles , 2008 .

[14]  D. Goodman,et al.  Catalytically active gold on ordered titania supports. , 2008, Chemical Society reviews.

[15]  J. Solla-Gullón,et al.  Shape-dependent electrocatalysis: methanol and formic acid electrooxidation on preferentially oriented Pt nanoparticles. , 2008, Physical chemistry chemical physics : PCCP.

[16]  Jiye Fang,et al.  Super crystal structures of octahedral c-In2O3 nanocrystals. , 2008, Journal of the American Chemical Society.

[17]  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.

[18]  K. Sun,et al.  Shape-Control of ZnTe Nanocrystal Growth in Organic Solution , 2008 .

[19]  P. Rodríguez,et al.  Surface characterization of platinum electrodes. , 2008, Physical chemistry chemical physics : PCCP.

[20]  M. Arenz,et al.  Measurement of oxygen reduction activities via the rotating disc electrode method : from Pt model surfaces to carbon-supported high surface area catalysts. , 2008 .

[21]  R. Maric Spray-based and CVD Processes for Synthesis of Fuel Cell Catalysts and Thin Catalyst Layers , 2008 .

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

[23]  Younan Xia,et al.  Shape‐Controlled Synthesis of Metal Nanostructures: The Case of Palladium , 2007 .

[24]  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.

[25]  Shouheng Sun,et al.  Synthesis of monodisperse Pt nanocubes and their enhanced catalysis for oxygen reduction. , 2007, Journal of the American Chemical Society.

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

[27]  R. Tilley,et al.  Preparation, self-assembly, and mechanistic study of highly monodispersed nanocubes. , 2007, Journal of the American Chemical Society.

[28]  Michael F. Toney,et al.  Structure-activity-stability relationships of Pt-Co alloy electrocatalysts in gas-diffusion electrode layers , 2007 .

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

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

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

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

[33]  N. Marković,et al.  THE STUDY OF SURFACE SEGREGATION, STRUCTURE, AND VALENCE BAND DENSITY OF STATES OF Pt3Ni(100), (110), AND (111) CRYSTALS , 2006 .

[34]  T. He,et al.  Synthesis and characterization of carbon supported PtW catalysts from carbonyl complexes for oxygen electroreduction , 2006 .

[35]  Hongyou Fan,et al.  Synthesis of FePt nanocubes and their oriented self-assembly. , 2006, Journal of the American Chemical Society.

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

[37]  J. Solla-Gullón,et al.  CO monolayer oxidation on semi-spherical and preferentially oriented (100) and (111) platinum nanoparticles , 2006 .

[38]  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.

[39]  E. Higuchi,et al.  Effect of loading level in platinum-dispersed carbon black electrocatalysts on oxygen reduction activity evaluated by rotating disk electrode , 2005 .

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

[41]  Jinke Tang,et al.  Study of quasi-monodisperse In2O3 nanocrystals: synthesis and optical determination. , 2005, Journal of the American Chemical Society.

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

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

[44]  Weigang Lu,et al.  Perfect orientation ordered in-situ one-dimensional self-assembly of Mn-doped PbSe nanocrystals. , 2004, Journal of the American Chemical Society.

[45]  M. Winter,et al.  What are batteries, fuel cells, and supercapacitors? , 2004, Chemical reviews.

[46]  Jiye Fang,et al.  Shape evolution and self assembly of monodisperse PbTe nanocrystals. , 2004, Journal of the American Chemical Society.

[47]  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.

[48]  J. G. Chen,et al.  Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals. , 2004, The Journal of chemical physics.

[49]  P. Yang,et al.  Solution-phase synthesis of single-crystalline iron phosphide nanorods/nanowires. , 2004, Journal of the American Chemical Society.

[50]  J. Lee,et al.  Preparation of PtNi nanoparticles for the electrocatalytic oxidation of methanolElectronic supplementary information (ESI) available: TEM images of Pt nanoparticle seeds prepared from the methanol reduction of Pt salts. See http://www.rsc.org/suppdata/jm/b3/b307040a/ , 2003 .

[51]  Philip N. Ross,et al.  Surface segregation effects in electrocatalysis: Kinetics of oxygen reduction reaction on polycrystalline Pt3Ni alloy surfaces , 2002 .

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

[53]  Jinwoo Cheon,et al.  Single-crystalline star-shaped nanocrystals and their evolution: programming the geometry of nano-building blocks. , 2002, Journal of the American Chemical Society.

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

[55]  M. Dresselhaus,et al.  Alternative energy technologies , 2001, Nature.

[56]  M. Grätzel Photoelectrochemical cells : Materials for clean energy , 2001 .

[57]  Christopher B. Murray,et al.  Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies , 2000 .

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

[59]  B. Gates,et al.  MgO-Supported Platinum–Tungsten Catalysts Prepared from Organometallic Precursors: Platinum Clusters Isolated on Dispersed Tungsten , 1996 .

[60]  Hubert A. Gasteiger,et al.  Oxygen reduction of platinum low-index single-crystal surfaces in alkaline solution: Rotating ring disk{sub Pt(hkl)} studies , 1996 .

[61]  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 .

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

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