Bimetallic multifunctional core@shell plasmonic nanoparticles for localized surface plasmon resonance based sensing and electrocatalysis.

Smart bimetallic core@shell nanoparticles were fabricated based on gold nanoparticles (AuNPs) decorated with pH-sensitive polymer shell. Concretely, AuNPs having poly(4-vinylpyridine) (P4VP) on the surface were first fabricated through surface-initiated atom transfer radical polymerization (SI-ATRP). Then, they were mixed with selected metal precursor solutions followed by reduction using reducing agent. The metal NPs thus introduced were uniformly distributed in P4VP polymer shells. In order to explore the diversity and viable function of the resultant nanostructures, we controlled the size of AuNP, pH, selectivity of metal precursors, etc. We investigated the structural alteration during the sequential synthetic process. The bimetallic nanostructures of AuNP@P4VP nanocomposites containing another type of metal NP at the P4VP periphery exhibit a controlled sensing property in terms of the change in the refractive index of surrounding media and a typical electrocatalytic activity for methanol oxidation reaction.

[1]  Yena Kim,et al.  Synthesis and Electrocatalytic Activity of Au−Pd Alloy Nanodendrites for Ethanol Oxidation , 2010 .

[2]  S. Jiang,et al.  Controlled deposition of Pt on Au nanorods and their catalytic activity towards formic acid oxidation , 2008 .

[3]  H. Möhwald,et al.  Two-Stage pH Response of Poly(4-vinylpyridine) Grafted Gold Nanoparticles , 2008 .

[4]  S. Maier,et al.  Plasmonics: Localization and guiding of electromagnetic energy in metal/dielectric structures , 2005 .

[5]  Bo-Qing Xu,et al.  Enhancement of Pt utilization in electrocatalysts by using gold nanoparticles. , 2006, Angewandte Chemie.

[6]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[7]  E. Wang,et al.  Three-Dimensional Pt-on-Au Bimetallic Dendritic Nanoparticle: One-Step, High-Yield Synthesis and Its Bifunctional Plasmonic and Catalytic Properties , 2010 .

[8]  M. Tsuji,et al.  Synthesis of Au core Au/Ag alloy shell nanoparticles using branched Au nanoparticles as seeds , 2011 .

[9]  Yoshinobu Nakamura,et al.  Synthesis of pH-responsive nanocomposite microgels with size-controlled gold nanoparticles from ion-doped, lightly cross-linked poly(vinylpyridine). , 2010, Langmuir : the ACS journal of surfaces and colloids.

[10]  Chen Guo,et al.  Effect of pH on the single-step synthesis of gold nanoparticles using PEO-PPO-PEO triblock copolymers in aqueous media. , 2011, Journal of colloid and interface science.

[11]  M. Sastry,et al.  Keggin ion-mediated synthesis of aqueous phase-pure Au@Pd and Au@Pt core–shell nanoparticles , 2004 .

[12]  Sebastian Schlücker,et al.  Synthesis of bifunctional Au/Pt/Au Core/shell nanoraspberries for in situ SERS monitoring of platinum-catalyzed reactions. , 2011, Journal of the American Chemical Society.

[13]  Junbai Li,et al.  Smart core/shell nanocomposites: intelligent polymers modified gold nanoparticles. , 2009, Advances in colloid and interface science.

[14]  Younan Xia,et al.  Gold and silver nanoparticles: a class of chromophores with colors tunable in the range from 400 to 750 nm. , 2003, The Analyst.

[15]  E. Hutter,et al.  Exploitation of Localized Surface Plasmon Resonance , 2004 .

[16]  H. Duan,et al.  Plasmonic vesicles of amphiphilic gold nanocrystals: self-assembly and external-stimuli-triggered destruction. , 2011, Journal of the American Chemical Society.

[17]  Dong Ha Kim,et al.  Grafting poly(4-vinylpyridine) onto gold nanorods toward functional plasmonic core–shell nanostructures , 2011 .

[18]  C. Murphy,et al.  Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications. , 2005, The journal of physical chemistry. B.

[19]  Ian D. Rees,et al.  Using Atom Transfer Radical Polymerization To Amplify Monolayers of Initiators Patterned by Microcontact Printing into Polymer Brushes for Pattern Transfer , 2000 .

[20]  Y. Shon,et al.  Synthesis and catalytic properties of alkanethiolate-capped Pd nanoparticles generated from sodium S-dodecylthiosulfate , 2011 .

[21]  Y. Yamauchi,et al.  Block copolymer mediated synthesis of dendritic platinum nanoparticles. , 2009, Journal of the American Chemical Society.

[22]  Younan Xia,et al.  Shape-Controlled Synthesis and Surface Plasmonic Properties of Metallic Nanostructures , 2005 .

[23]  R. Niessner,et al.  Synthesis of core-shell surface-enhanced Raman tags for bioimaging. , 2010, Analytical chemistry.