Near-Monolayer Platinum Shell on Core–Shell Nanocatalysts for High-Performance Direct Methanol Fuel Cell

We investigate the Rucore-Ptshell nanoparticles (NPs) with near-monolayer thick shell atoms as the electrocatalysts at anode in the direct methanol fuel cell (DMFC). The results of X-ray diffraction indicate that its crystal structure experienced a compressive strain in Pt shell region. The shell thickness of Rucore-Ptshell NPs was determined to be 1.5 atomic layers by small-angle X-ray scattering by using a core–shell scattering model, and the surface atomic morphology was illustrated via high-resolution transmission electron microscopy (HRTEM). Compared with the Pt NPs, the power density of DMFC with Rucore-Ptshell NPs was improved by ∼450% (from 17.1 to 92.8 mW cm–2 mg–1), and the open-circuit voltage was improved by 0.18 V (from 0.49 to 0.67 V). Our results fulfill the development of cost-effective DMFC with outstanding performance.

[1]  Tsan-Yao Chen,et al.  Crystal growth of platinum–ruthenium bimetallic nanocrystallites and their methanol electrooxidation activity , 2013 .

[2]  T. Wen,et al.  Ruthenium core-activated platinum monolayer shell high redox activity cathodic electrocatalysts for dye-sensitized solar cells , 2013 .

[3]  Chi-Chang Hu,et al.  Core-dependent growth of platinum shell nanocrystals and their electrochemical characteristics for fuel cells , 2013 .

[4]  T. Wen,et al.  Core Dominated Surface Activity of Core–Shell Nanocatalysts on Methanol Electrooxidation , 2012 .

[5]  Zhong Lin Wang,et al.  Misfit dislocations in multimetallic core-shelled nanoparticles , 2012 .

[6]  Ping Liu,et al.  Core-protected platinum monolayer shell high-stability electrocatalysts for fuel-cell cathodes. , 2010, Angewandte Chemie.

[7]  Jyhfu Lee,et al.  Effects of Pt shell thicknesses on the atomic structure of Ru-Pt core-shell nanoparticles for methanol electrooxidation applications. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

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

[9]  K. Kaneko,et al.  Effect of Catalyst Size on Hydrogen Storage Capacity of Pt-Impregnated Active Carbon via Spillover , 2010 .

[10]  Tsan-Yao Chen,et al.  Improved Catalytic Performance of Pt Supported on Multi-Wall Carbon Nanotubes as Cathode for Direct Methanol Fuel Cell Applications Prepared by Dual-stepped Surface Thiolation Processes , 2009 .

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

[12]  B. Eichhorn,et al.  Rh-Pt bimetallic catalysts: synthesis, characterization, and catalysis of core-shell, alloy, and monometallic nanoparticles. , 2008, Journal of the American Chemical Society.

[13]  Manos Mavrikakis,et al.  Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen. , 2008, Nature materials.

[14]  B. Hwang,et al.  Size and Alloying Extent Dependent Physiochemical Properties of Pt-Ag/C Nanoparticles Synthesized by the Ethylene Glycol Method , 2008 .

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

[16]  C. Wan,et al.  A mechanism study on the synthesis of Cu/Pd nanoparticles with citric complexing agent , 2007 .

[17]  J. Nørskov,et al.  Ligand effects in heterogeneous catalysis and electrochemistry , 2007 .

[18]  C. Yeh,et al.  Fractal aggregates of the Pt nanoparticles synthesized by the polyol process and poly(N-vinyl-2-pyrrolidone) reduction , 2007 .

[19]  C. Roth,et al.  Determination of O[H] and CO coverage and adsorption sites on PtRu electrodes in an operating PEM fuel cell. , 2005, Journal of the American Chemical Society.

[20]  Bing-Joe Hwang,et al.  Structural models and atomic distribution of bimetallic nanoparticles as investigated by X-ray absorption spectroscopy. , 2005, Journal of the American Chemical Society.

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

[22]  J. Wagner.  Small‐angle scattering from spherical core–shell particles: an analytical scattering function for particles with Schulz–Flory size distribution , 2004 .

[23]  A. Gross,et al.  Surface strain versus substrate interaction in heteroepitaxial metal layers: Pt on Ru(0001). , 2003, Physical review letters.

[24]  Younan Xia,et al.  Large‐Scale Synthesis of Uniform Silver Nanowires Through a Soft, Self‐Seeding, Polyol Process , 2002 .

[25]  Chi-Chang Hu,et al.  Voltammetric investigation of platinum oxides II. Effect of hydration on their reduction behavior , 2000 .

[26]  Chi-Chang Hu,et al.  Voltammetric investigation of platinum oxides. I. Effects of ageing on their formation/reduction behavior as well as catalytic activities for methanol oxidation , 1999 .

[27]  S. Mukerjee,et al.  Effect of particle size on the electrocatalysis by carbon-supported Pt electrocatalysts: an in situ XAS investigation , 1998 .

[28]  Clausen,et al.  Design of a surface alloy catalyst for steam reforming , 1998, Science.

[29]  D. Sayers,et al.  Hydrogen Chemisorption on Silica-Supported Pt Clusters: In Situ X-ray Absorption Spectroscopy , 1997 .

[30]  Edward A. Fletcher,et al.  Metals, nitrides, and carbides via solar carbothermal reduction of metal oxides , 1995 .

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

[32]  R. Durand,et al.  Particle size effect for oxygen reduction and methanol oxidation on Pt/C inside a proton exchange membrane , 1994 .

[33]  R. Ottewill,et al.  A neutron scattering study of the structure of a bimodal colloidal crystal , 1992 .

[34]  J. Teixeira,et al.  Small‐angle scattering by fractal systems , 1988 .

[35]  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 .

[36]  M. Watanabe,et al.  Electrocatalysis by ad-atoms: Part III. Enhancement of the oxidation of carbon monoxide on platinum by ruthenium ad-atoms , 1975 .

[37]  T. R. Ralph,et al.  Catalysis for low temperature fuel cells. Part I: The cathode challenges , 2002 .