Size specifically high activity of Ru nanoparticles for hydrogen oxidation reaction in alkaline electrolyte.

The hydrogen oxidation reaction (HOR) in alkaline electrolyte was conducted on carbon-supported Ru nanoparticles (Ru/C) of which size was controlled in the range from approximately 2 to 7 nm. The HOR activity of Ru/C normalized by the metal surface area showed volcano shaped dependence on the particle size with a maximum activity at approximately 3 nm. The HOR activity of approximately 3 nm Ru/C was higher than commercially available Pt nanoparticles (ca. 2 nm) supported on carbon. The structural analysis of Ru/C using Cs-corrected scanning transmission electron microscopy with atomic resolution revealed the unique structural change of Ru/C different from Pt/C: Ru nanoparticle structure changed from amorphous-like structure below 3 nm to metal nanocrystallite with roughened surface at approximately 3 nm and then to that with well-defined facets above 3 nm, although Pt/C kept well-defined facets even at approximately 2 nm. It is proposed that the generation of unique structure observed on approximately 3 nm Ru nanoparticles, that is, long bridged coordinatively unsaturated Ru metal surface atoms on its nanocrystallite, is a key to achieve high HOR activity.

[1]  Aicheng Chen,et al.  Platinum-based nanostructured materials: synthesis, properties, and applications. , 2010, Chemical reviews.

[2]  Balasubramanian Viswanathan,et al.  Monodispersed Platinum Nanoparticle Supported Carbon Electrodes for Hydrogen Oxidation and Oxygen Reduction in Proton Exchange Membrane Fuel Cells , 2010 .

[3]  Hubert A. Gasteiger,et al.  Hydrogen electrochemistry on platinum low-index single-crystal surfaces in alkaline solution , 1996 .

[4]  Katsutoshi Sato,et al.  Discovery of face-centered-cubic ruthenium nanoparticles: facile size-controlled synthesis using the chemical reduction method. , 2013, Journal of the American Chemical Society.

[5]  Yu Dai,et al.  A rotating disk electrode study of the particle size effects of Pt for the hydrogen oxidation reaction. , 2012, Physical chemistry chemical physics : PCCP.

[6]  Jim P. Zheng,et al.  Ruthenium Oxide‐Carbon Composite Electrodes for Electrochemical Capacitors , 1999 .

[7]  Lin Zhuang,et al.  Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts , 2008, Proceedings of the National Academy of Sciences.

[8]  Qinghong Zhang,et al.  Ruthenium nanoparticles supported on carbon nanotubes as efficient catalysts for selective conversion of synthesis gas to diesel fuel. , 2009, Angewandte Chemie.

[9]  H. Gasteiger,et al.  H2 and CO Electrooxidation on Well-Characterized Pt, Ru, and Pt-Ru. 1. Rotating Disk Electrode Studies of the Pure Gases Including Temperature Effects , 1995 .

[10]  Hongwei Zhang,et al.  Recent development of polymer electrolyte membranes for fuel cells. , 2012, Chemical reviews.

[11]  Koji Yamada,et al.  A platinum-free zero-carbon-emission easy fuelling direct hydrazine fuel cell for vehicles. , 2007, Angewandte Chemie.

[12]  Alexis T. Bell,et al.  Effects of dispersion on the activity and selectivity of alumina-supported ruthenium catalysts for carbon monoxide hydrogenation , 1982 .

[13]  H. Gasteiger,et al.  H2 and CO Electrooxidation on Well-Characterized Pt, Ru, and Pt-Ru. 2. Rotating Disk Electrode Studies of CO/H2 Mixtures at 62 .degree.C , 1995 .

[14]  Younan Xia,et al.  Structural dependence of oxygen reduction reaction on palladium nanocrystals. , 2011, Chemical communications.

[15]  Minhua Shao,et al.  Electrocatalysis on platinum nanoparticles: particle size effect on oxygen reduction reaction activity. , 2011, Nano letters.

[16]  R. Slade,et al.  Prospects for Alkaline Anion‐Exchange Membranes in Low Temperature Fuel Cells , 2005 .

[17]  K. Uosaki,et al.  Evidence of nonelectrochemical shift reaction on a CO-tolerant high-entropy state Pt-Ru anode catalyst for reliable and efficient residential fuel cell systems. , 2012, Journal of the American Chemical Society.

[18]  R. Nichols,et al.  Substrate Structural Effects on the Synthesis and Electrochemical Properties of Platinum Nanoparticles on Highly Oriented Pyrolytic Graphite , 2010 .

[19]  H. Inoue,et al.  Electrocatalysis of H2 oxidation on Ru(0001) and Ru(10−10) single crystal surfaces , 2003 .

[20]  T. Abe,et al.  CO2 methanation property of Ru nanoparticle-loaded TiO2 prepared by a polygonal barrel-sputtering method , 2009 .

[21]  P. Gallezot,et al.  Catalytic wet air oxidation of acetic acid on carbon-supported ruthenium catalysts , 1997 .

[22]  Ya‐Wen Zhang,et al.  Ru nanocrystals with shape-dependent surface-enhanced Raman spectra and catalytic properties: controlled synthesis and DFT calculations. , 2012, Journal of the American Chemical Society.

[23]  T. Kojima,et al.  Effect of Support Materials on the Selective Methanation of CO over Ru Catalysts , 2010 .

[24]  G. Somorjai,et al.  Size effect of ruthenium nanoparticles in catalytic carbon monoxide oxidation. , 2010, Nano letters.

[25]  K. Shimizu,et al.  Oxidant-free dehydrogenation of alcohols heterogeneously catalyzed by cooperation of silver clusters and acid-base sites on alumina. , 2009, Chemistry.

[26]  G. Hutchings,et al.  Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation , 2008, Science.

[27]  Lijun Wu,et al.  Oxygen reduction on well-defined core-shell nanocatalysts: particle size, facet, and Pt shell thickness effects. , 2009, Journal of the American Chemical Society.

[28]  B. Conway,et al.  The state of electrodeposited hydrogen at ruthenium electrodes , 1977 .

[29]  J. Ohyama,et al.  High performance of Ru nanoparticles supported on carbon for anode electrocatalyst of alkaline anion exchange membrane fuel cell , 2013 .

[30]  Robert J. Davis,et al.  Ammonia Synthesis Catalyzed by Ruthenium Supported on Basic Zeolites , 1996 .

[31]  Masatake Haruta,et al.  Size- and support-dependency in the catalysis of gold , 1997 .

[32]  G. Somorjai,et al.  Intrinsic relation between catalytic activity of CO oxidation on Ru nanoparticles and Ru oxides uncovered with ambient pressure XPS. , 2012, Nano letters.

[33]  Philip N. Ross,et al.  TEMPERATURE-DEPENDENT HYDROGEN ELECTROCHEMISTRY ON PLATINUM LOW-INDEX SINGLE-CRYSTAL SURFACES IN ACID SOLUTIONS , 1997 .

[34]  H. Abruña,et al.  Activating Pd by morphology tailoring for oxygen reduction. , 2009, Journal of the American Chemical Society.

[35]  Yong Wang,et al.  Selective CO methanation catalysts for fuel processing applications , 2007 .

[36]  N. Marković,et al.  Temperature dependent surface electrochemistry on Pt single crystals in alkaline electrolytes: Part 2. The hydrogen evolution/oxidation reaction , 2002 .

[37]  Yuta Yamamoto,et al.  Selective hydrogenation of 2-hydroxymethyl-5-furfural to 2,5-bis(hydroxymethyl)furan over gold sub-nano clusters , 2013 .

[38]  H. Gasteiger,et al.  Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes , 2010 .