One-Step, Facile and Ultrafast Synthesis of Phase- and Size-Controlled Pt-Bi Intermetallic Nanocatalysts through Continuous-Flow Microfluidics.

Ordered intermetallic nanomaterials are of considerable interest for fuel cell applications because of their unique electronic and structural properties. The synthesis of intermetallic compounds generally requires the use of high temperatures and multiple-step processes. The development of techniques for rapid phase- and size-controlled synthesis remains a formidable challenge. The intermetallic compound Pt1Bi2 is a promising candidate catalyst for direct methanol fuel cells because of its high catalytic activity and excellent methanol tolerance. In this work, we explored a one-step, facile and ultrafast phase- and size-controlled process for synthesizing ordered Pt-Bi intermetallic nanoparticles (NPs) within seconds in microfluidic reactors. Single-phase Pt1Bi1 and Pt1Bi2 intermetallic NPs were prepared by tuning the reaction temperature, and size control was achieved by modifying the solvents and the length of the reaction channel. The as-prepared Pt-Bi intermetallic NPs exhibited excellent methanol tolerance capacity and high electrocatalytic activity. Other intermetallic nanomaterials, such as Pt3Fe intermetallic nanowires with a diameter of 8.6 nm and Pt1Sn1 intermetallic nanowires with a diameter of 6.3 nm, were also successfully synthesized using this method, thus demonstrating its feasibility and generality.

[1]  Xiaole Chen,et al.  Converting nanocrystalline metals into alloys and intermetallic compounds for applications in catalysis , 2008 .

[2]  Mark A. Rodriguez,et al.  Rare-earth transition-metal intermetallic compounds produced via self-propagating, high-temperature synthesis , 2010 .

[3]  Andrew J. deMello,et al.  On-line analysis of CdSe nanoparticle formation in a continuous flow chip-based microreactor , 2004 .

[4]  Saif A. Khan,et al.  Droplet-based microfluidic synthesis of anisotropic metal nanocrystals. , 2009, Small.

[5]  K. Jensen,et al.  Synthesis of micro and nanostructures in microfluidic systems. , 2010, Chemical Society reviews.

[6]  Yanglong Hou,et al.  Synthesis and electrocatalytic properties of PtBi nanoplatelets and PdBi nanowires. , 2014, Nanoscale.

[7]  Younan Xia,et al.  Scaling up the Production of Colloidal Nanocrystals: Should We Increase or Decrease the Reaction Volume? , 2014, Advanced materials.

[8]  K. Jensen,et al.  A Continuous‐Flow Microcapillary Reactor for the Preparation of a Size Series of CdSe Nanocrystals , 2003 .

[9]  Katla Sai Krishna,et al.  Lab-on-a-chip synthesis of inorganic nanomaterials and quantum dots for biomedical applications. , 2013, Advanced drug delivery reviews.

[10]  Dong Sung Choi,et al.  Monodisperse pattern nanoalloying for synergistic intermetallic catalysis. , 2013, Nano letters.

[11]  Josef Hormes,et al.  Microfluidic synthesis of nanomaterials. , 2008, Small.

[12]  Paul F. Mutolo,et al.  Synthesis, Characterization, and Electrocatalytic Activity of PtBi and PtPb Nanoparticles Prepared by Borohydride Reduction in Methanol , 2006 .

[13]  C. Kumar,et al.  Microfluidic Synthesis of Cobalt Nanoparticles , 2006 .

[14]  C. Sönnichsen,et al.  Microfluidic continuous flow synthesis of rod-shaped gold and silver nanocrystals. , 2006, Physical Chemistry, Chemical Physics - PCCP.

[15]  H. Abruña,et al.  Surface Treatment Effects on the Electrocatalytic Activity and Characterization of Intermetallic Phases , 2004 .

[16]  M. E. Williams,et al.  Controlling transport and chemical functionality of magnetic nanoparticles. , 2008, Accounts of chemical research.

[17]  Richard A. Mathies,et al.  Size-Controlled Growth of CdSe Nanocrystals in Microfluidic Reactors , 2003 .

[18]  Jiujun Zhang,et al.  Synthesis of Ordered Intermetallic PtBi2 Nanoparticles for Methanol-Tolerant Catalyst in Oxygen Electroreduction , 2006 .

[19]  Moon J. Kim,et al.  Continuous and scalable production of well-controlled noble-metal nanocrystals in milliliter-sized droplet reactors. , 2014, Nano letters.

[20]  D. Muller,et al.  Structurally ordered intermetallic platinum-cobalt core-shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. , 2013, Nature materials.

[21]  H. Abruña,et al.  Pt skin on AuCu intermetallic substrate: a strategy to maximize Pt utilization for fuel cells. , 2014, Journal of the American Chemical Society.

[22]  A. deMello,et al.  The past, present and potential for microfluidic reactor technology in chemical synthesis. , 2013, Nature chemistry.

[23]  H. Abruña,et al.  Electrocatalytic activity of ordered intermetallic phases for fuel cell applications. , 2004, Journal of the American Chemical Society.

[24]  F. Disalvo,et al.  Ordered Intermetallic Pt–Sn Nanoparticles: Exploring Ordering Behavior across the Bulk Phase Diagram , 2014 .

[25]  V. Cabuil,et al.  Multistep continuous-flow microsynthesis of magnetic and fluorescent gamma-Fe2O3@SiO2 core/shell nanoparticles. , 2009, Angewandte Chemie.

[26]  A. Sra,et al.  Synthesis of atomically ordered AuCu and AuCu(3) nanocrystals from bimetallic nanoparticle precursors. , 2004, Journal of the American Chemical Society.

[27]  Valérie Cabuil,et al.  Microfluidics in inorganic chemistry. , 2010, Angewandte Chemie.

[28]  Wolfgang Fritzsche,et al.  Au/Ag/Au double shell nanoparticles with narrow size distribution obtained by continuous micro segmented flow synthesis , 2011 .

[29]  Paul F. Mutolo,et al.  Synthesis, Characterization, and Electrocatalytic Activity of PtBi Nanoparticles Prepared by the Polyol Process , 2005 .

[30]  K. Kimura,et al.  Thermoelectric Properties of Binary Semiconducting Intermetallic Compounds Al2Ru and Ga2Ru Synthesized by Spark Plasma Sintering Process , 2010 .

[31]  Xiulei Ji,et al.  Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. , 2010, Nature chemistry.

[32]  Younan Xia,et al.  Synthesis of colloidal metal nanocrystals in droplet reactors: the pros and cons of interfacial adsorption. , 2014, Nano letters.

[33]  Andrew D Griffiths,et al.  Droplet-based microreactors for the synthesis of magnetic iron oxide nanoparticles. , 2008, Angewandte Chemie.

[34]  R. E. Schaak,et al.  Shape-controlled conversion of beta-Sn nanocrystals into intermetallic M-Sn (M=Fe, Co, Ni, Pd) nanocrystals. , 2007, Journal of the American Chemical Society.

[35]  Andrew J deMello,et al.  Microfluidic routes to the controlled production of nanoparticles. , 2002, Chemical communications.

[36]  Wantai Yang,et al.  Fine Crystal Structure Transition of Cobalt Nanoparticles Formed in a Microfluidic Reactor , 2008 .

[37]  H. Abruña,et al.  Electrocatalytic oxidation of formic acid at an ordered intermetallic PtBi surface. , 2003, Chemphyschem : a European journal of chemical physics and physical chemistry.

[38]  Paola Laurino,et al.  Synthesis of carbohydrate-functionalized quantum dots in microreactors. , 2010, Angewandte Chemie.

[39]  H. Abruña,et al.  Adsorption of CO on PtBi2 and PtBi surfaces , 2005 .

[40]  Yingchao Yu,et al.  Synthesis of structurally ordered Pt3Ti and Pt3V nanoparticles as methanol oxidation catalysts. , 2014, Journal of the American Chemical Society.

[41]  Shikuan Yang,et al.  Shape-Controlled Synthesis of Hybrid Nanomaterials via Three-Dimensional Hydrodynamic Focusing , 2014, ACS nano.

[42]  A. deMello Control and detection of chemical reactions in microfluidic systems , 2006, Nature.