Roles of surface steps on Pt nanoparticles in electro-oxidation of carbon monoxide and methanol.

Design of highly active nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. Increasing steps on single-crystal Pt surfaces is shown to enhance the activity of CO and methanol electro-oxidation up to several orders of magnitude. However, little is known about the surface atomic structure of nanoparticles with sizes of practical relevance, which limits the application of fundamental understanding in the reaction mechanisms established on single-crystal surfaces to the development of active, nanoscale catalysts. In this study, we reveal the surface atomic structure of Pt nanoparticles supported on multiwall carbon nanotubes, from which the amount of high-index surface facets on Pt nanoparticles is quantified. Correlating the surface steps on Pt nanoparticles with the electrochemical activity and stability clearly shows the significant role of surface steps in enhancing intrinsic activity for CO and methanol electro-oxidation. Here, we show that increasing surface steps on Pt nanoparticles of approximately 2 nm can lead to enhanced intrinsic activity up to approximately 200% (current normalized to Pt surface area) for electro-oxidation of methanol.

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

[2]  Liang Chen,et al.  Hydrothermal synthesis of size-dependent Pt in Pt/MWCNTs nanocomposites for methanol electro-oxidation , 2008 .

[3]  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 .

[4]  M. Koper,et al.  Mechanisms of Carbon Monoxide and Methanol Oxidation at Single-crystal Electrodes , 2007 .

[5]  Thomas F. Jaramillo,et al.  Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts , 2007, Science.

[6]  A. Kirkland,et al.  Aberration-corrected imaging of active sites on industrial catalyst nanoparticles. , 2007, Angewandte Chemie.

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

[8]  Yang Shao-Horn,et al.  Formation Mechanism of Pt Single-Crystal Nanoparticles in Proton Exchange Membrane Fuel Cells , 2007 .

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

[10]  U. Stimming,et al.  CO monolayer oxidation on Pt nanoparticles: Further insights into the particle size effects , 2007 .

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

[12]  T. Uruga,et al.  Fine size control of platinum on carbon nanotubes: from single atoms to clusters. , 2006, Angewandte Chemie.

[13]  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.

[14]  M. Arenz,et al.  CO surface electrochemistry on Pt-nanoparticles: A selective review , 2005 .

[15]  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.

[16]  P. Ross,et al.  The effect of the particle size on the kinetics of CO electrooxidation on high surface area Pt catalysts. , 2005, Journal of the American Chemical Society.

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

[18]  M. Eikerling,et al.  Size effects on reactivity of Pt nanoparticles in CO monolayer oxidation: the role of surface mobility. , 2004, Faraday discussions.

[19]  M. Koper,et al.  Methanol Oxidation on Stepped Pt[n(111) × (110)] Electrodes: A Chronoamperometric Study , 2003 .

[20]  Andrzej Wieckowski,et al.  Catalysis and Electrocatalysis at Nanoparticle Surfaces , 2003 .

[21]  J. Feliu,et al.  Role of Crystalline Defects in Electrocatalysis: Mechanism and Kinetics of CO Adlayer Oxidation on Stepped Platinum Electrodes , 2002 .

[22]  T. Iwasita Electrocatalysis of methanol oxidation , 2002 .

[23]  M. J. Weaver,et al.  Electrocatalytic Pathways on Carbon-Supported Platinum Nanoparticles: Comparison of Particle-Size-Dependent Rates of Methanol, Formic Acid, and Formaldehyde Electrooxidation , 2002 .

[24]  M. V. Ganduglia-Pirovano,et al.  Oxygen induced Rh 3d_5/2 surface core-level shifts on Rh(111) , 2001 .

[25]  P. Hu,et al.  A density functional theory study of CO and atomic oxygen chemisorption on Pt(111) , 2000 .

[26]  J. Frenken,et al.  Are Vicinal Metal Surfaces Stable , 1999 .

[27]  Bjørk Hammer,et al.  Structure sensitivity in adsorption: CO interaction with stepped and reconstructed Pt surfaces , 1997 .

[28]  C. Korzeniewski,et al.  Infrared Spectroscopic Detection of CO Formed at Step and Terrace Sites on a Corrugated Electrode Surface Plane during Methanol Oxidation , 1995 .

[29]  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 .

[30]  W. Visscher,et al.  Particle size effect of carbon-supported platinum catalysts for the electrooxidation of methanol , 1995 .

[31]  H. Skriver,et al.  Surface energy and work function of elemental metals. , 1992, Physical review. B, Condensed matter.

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

[33]  Fu,et al.  Photoemission from mass-selected monodispersed Pt clusters. , 1990, Physical review letters.

[34]  R. Parsons,et al.  The oxidation of small organic molecules: A survey of recent fuel cell related research , 1988 .

[35]  J. Ehrhardt,et al.  On the interaction of O2 with Pt(111) and Pt(557) surfaces: core-level shift study using conventional and synchrotron radiation sources , 1988 .

[36]  Foiles,et al.  Embedded-atom-method functions for the fcc metals Cu, Ag, Au, Ni, Pd, Pt, and their alloys. , 1986, Physical review. B, Condensed matter.

[37]  I. Lindau,et al.  Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103 , 1985 .

[38]  D. Sayers,et al.  Quantitative technique for the determination of the number of unoccupied d-electron states in a platinum catalyst using the L2,3 x-ray absorption edge spectra , 1984 .

[39]  V. Korchak,et al.  The adsorption of oxygen on a stepped platinum single crystal surface , 1978 .

[40]  S. Gilman,et al.  The Mechanism of Electrochemical Oxidation of Carbon Monoxide and Methanol on Platinum. II. The “Reactant-Pair” Mechanism for Electrochemical Oxidation of Carbon Monoxide and Methanol1 , 1964 .