Rapid and Surfactant-Free Synthesis of Bimetallic Pt–Cu Nanoparticles Simply via Ultrasound-Assisted Redox Replacement

The synthesis of bimetallic nanoparticles (NPs) with well-defined morphology and a size of <5 nm remains an ongoing challenge. Here, we developed a facile and efficient approach to the design of bimetallic nanostructures by the galvanic replacement reaction facilitated by high-intensity ultrasound (100 W, 20 kHz) at low temperatures. As a model system, Pt–Cu NPs deposited on nitrogen-doped carbon nanotubes (NCNTs) were synthesized and characterized by spectroscopic and microscopic techniques. Transmission electron microscopy (TEM) inspection shows that the mean diameter of Pt–Cu NPs can be as low as ≈2.8 nm, regardless of the much larger initial Cu particle size, and that a significant increase in particle number density by a factor of 35 had occurred during the replacement process. The concentration of the Pt precursor solution as well as of the size of the seed particles were found to control the size of the bimetallic NPs. Energy dispersive X-ray spectroscopy performed in the scanning TEM mode confirme...

[1]  R. M. Sankaran,et al.  Plasma-assisted dissociation of organometallic vapors for continuous, gas-phase preparation of multimetallic nanoparticles. , 2011, Angewandte Chemie.

[2]  Adria R. Wilson,et al.  Synthesis and catalytic properties of Au-Pd nanoflowers. , 2011, ACS nano.

[3]  Stanislaus S. Wong,et al.  Enhanced electrocatalytic performance of processed, ultrathin, supported Pd-Pt core-shell nanowire catalysts for the oxygen reduction reaction. , 2011, Journal of the American Chemical Society.

[4]  Hong Yang,et al.  Platinum-based electrocatalysts with core-shell nanostructures. , 2011, Angewandte Chemie.

[5]  J. Hong,et al.  Synthesis of AuPt heteronanostructures with enhanced electrocatalytic activity toward oxygen reduction. , 2010, Angewandte Chemie.

[6]  M. Chi,et al.  Synthesis and characterization of multimetallic Pd/Au and Pd/Au/FePt core/shell nanoparticles. , 2010, Angewandte Chemie.

[7]  Hong Yang,et al.  An Electrochemical Approach to PtAg Alloy Nanostructures Rich in Pt at the Surface , 2010 .

[8]  B. Pollet.  The use of ultrasound for the fabrication of fuel cell materials , 2010 .

[9]  Nicholas P. Irish,et al.  Electrochemical and Structural Study of a Chemically Dealloyed PtCu Oxygen Reduction Catalyst. , 2010, The journal of physical chemistry. C, Nanomaterials and interfaces.

[10]  Zhimin Liu,et al.  The solvent-free selective hydrogenation of nitrobenzene to aniline: an unexpected catalytic activity of ultrafine Pt nanoparticles deposited on carbon nanotubes , 2010 .

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

[12]  Wei Xia,et al.  The formation of nitrogen-containing functional groups on carbon nanotube surfaces: a quantitative XPS and TPD study. , 2010, Physical chemistry chemical physics : PCCP.

[13]  A. Manthiram,et al.  Synthesis of Pt@Cu Core−Shell Nanoparticles by Galvanic Displacement of Cu by Pt4+ Ions and Their Application as Electrocatalysts for Oxygen Reduction Reaction in Fuel Cells , 2010 .

[14]  Jianbo Wu,et al.  Synthesis and Oxygen Reduction Electrocatalytic Property of Platinum Hollow and Platinum-on-silver Nanoparticles , 2010 .

[15]  A S Bondarenko,et al.  Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. , 2009, Nature chemistry.

[16]  M. Arenz,et al.  Fuel cells: log on for new catalysts. , 2009, Nature chemistry.

[17]  Jaclyn D. Wiggins-Camacho,et al.  Highly Stable and Active Pt−Cu Oxygen Reduction Electrocatalysts Based on Mesoporous Graphitic Carbon Supports , 2009 .

[18]  B. Pollet.  A novel method for preparing PEMFC electrodes by the ultrasonic and sonoelectrochemical techniques , 2009 .

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

[20]  Caixia Xu,et al.  Nanotubular Mesoporous Bimetallic Nanostructures with Enhanced Electrocatalytic Performance , 2009 .

[21]  C. Jin,et al.  A highly efficient gas-phase route for the oxygen functionalization of carbon nanotubes based on nitric acid vapor , 2009 .

[22]  Feng Tao,et al.  Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles , 2008, Science.

[23]  J. Coleman,et al.  Quantitative Evaluation of Surfactant-stabilized Single-walled Carbon Nanotubes: Dispersion Quality and Its Correlation with Zeta Potential , 2008 .

[24]  P. Strasser,et al.  Dealloyed Pt−Cu Core−Shell Nanoparticle Electrocatalysts for Use in PEM Fuel Cell Cathodes , 2008 .

[25]  A. Zaban,et al.  Direct Measurement of the Recombination Losses via the Transparent Conductive Substrate in Dye Sensitized Solar Cells , 2008 .

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

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

[28]  J. Koberstein,et al.  Quantitative Analysis of Copper Oxide Nanoparticle Composition and Structure by X-ray Photoelectron Spectroscopy , 2006 .

[29]  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.

[30]  Giancarlo Cravotto,et al.  Power ultrasound in organic synthesis: moving cavitational chemistry from academia to innovative and large-scale applications. , 2006, Chemical Society reviews.

[31]  M. Shao,et al.  Platinum monolayer on nonnoble metal-noble metal core-shell nanoparticle electrocatalysts for O2 reduction. , 2005, The journal of physical chemistry. B.

[32]  Junliang Zhang,et al.  Mixed-metal pt monolayer electrocatalysts for enhanced oxygen reduction kinetics. , 2005, Journal of the American Chemical Society.

[33]  G. Jackson,et al.  Pt-Cu core-shell and alloy nanoparticles for heterogeneous NO(x) reduction: anomalous stability and reactivity of a core-shell nanostructure. , 2005, Angewandte Chemie.

[34]  Yong Wang,et al.  Fabrication of Ruthenium–Carbon Nanotube Nanocomposites in Supercritical Water , 2005 .

[35]  Junliang Zhang,et al.  Controlling the catalytic activity of platinum-monolayer electrocatalysts for oxygen reduction with different substrates. , 2005, Angewandte Chemie.

[36]  Eitan Grossman,et al.  Synthesis of nanoparticles with femtosecond laser pulses , 2004 .

[37]  Yu‐Guo Guo,et al.  Pt hollow nanospheres: facile synthesis and enhanced electrocatalysts. , 2004, Angewandte Chemie.

[38]  Younan Xia,et al.  Template-Engaged Replacement Reaction: A One-Step Approach to the Large-Scale Synthesis of Metal Nanostructures with Hollow Interiors , 2002 .

[39]  L. Mädler,et al.  Flame Synthesis of Nanoparticles , 2001 .

[40]  Andrei V. Ruban,et al.  Surface segregation energies in transition-metal alloys , 1999 .

[41]  A. Borodziński,et al.  Relation between Crystallite Size and Dispersion on Supported Metal Catalysts , 1997 .

[42]  K. Hodgson,et al.  Electronic structure of the perturbed blue copper site in nitrite reductase: spectroscopic properties, bonding and implications for the entatic/rack state. , 1996 .

[43]  A. Gedanken,et al.  The application of ultrasound radiation to the synthesis of nanocrystalline metal oxide in a non-aqueous solvent. , 2010, Ultrasonics sonochemistry.

[44]  K. Suslick,et al.  Sonochemical synthesis of amorphous iron , 1991, Nature.

[45]  L. Vegard,et al.  Die Konstitution der Mischkristalle und die Raumfüllung der Atome , 1921 .