Au@Ag Nanoparticles: Halides Stabilize {100} Facets

Seed-mediated growth is the most efficient methodology to control the size and shape of colloidal metal nanoparticles. In this process, the final nanocrystal shape is defined by the crystalline structure of the initial seed as well as by the presence of ligands and other additives that help to stabilize certain crystallographic facets. We analyze here the growth mechanism in aqueous solution of silver shells on presynthesized gold nanoparticles displaying various well-defined crystalline structures and morphologies. A thorough three-dimensional electron microscopy characterization of the morphology and internal structure of the resulting core–shell nanocrystals indicates that {100} facets are preferred for the outer silver shell, regardless of the morphology and crystallinity of the gold cores. These results are in agreement with theoretical analysis based on the relative surface energies of the exposed facets in the presence of halide ions.

[1]  P. Patra,et al.  Single-Molecule Surface-Enhanced Raman Scattering Sensitivity of Ag-Core Au-Shell Nanoparticles: Revealed by Bi-Analyte Method. , 2013, The journal of physical chemistry letters.

[2]  N. Jana Nanorod shape separation using surfactant assisted self-assembly. , 2003, Chemical communications.

[3]  Yizhak Marcus,et al.  Thermodynamics of solvation of ions. Part 5.—Gibbs free energy of hydration at 298.15 K , 1991 .

[4]  O. Magnussen Ordered anion adlayers on metal electrode surfaces. , 2002, Chemical reviews.

[5]  Huanjun Chen,et al.  Unraveling the Evolution and Nature of the Plasmons in (Au Core)–(Ag Shell) Nanorods , 2012, Advanced materials.

[6]  R. Vaia,et al.  Ag shell morphology on Au nanorod core: role of Ag precursor complex , 2011 .

[7]  L. Qi,et al.  Surfactant-assisted, shape-controlled synthesis of gold nanocrystals. , 2011, Nanoscale.

[8]  Z. Tang,et al.  Synthesis of Au@Ag core-shell nanocubes containing varying shaped cores and their localized surface plasmon resonances. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[9]  L. Liz‐Marzán,et al.  Chemical sharpening of gold nanorods: the rod-to-octahedron transition. , 2007, Angewandte Chemie.

[10]  Weiya Zhou,et al.  Gold nanorod-seeded growth of silver nanostructures: from homogeneous coating to anisotropic coating. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[11]  Hafner,et al.  Ab initio molecular dynamics for liquid metals. , 1995, Physical review. B, Condensed matter.

[12]  Younan Xia,et al.  Au@Ag core-shell nanocubes with finely tuned and well-controlled sizes, shell thicknesses, and optical properties. , 2010, ACS nano.

[13]  L. Liz‐Marzán,et al.  Atomic-scale determination of surface facets in gold nanorods. , 2012, Nature materials.

[14]  R. Vaia,et al.  Growth Mechanism of Gold Nanorods , 2013 .

[15]  M. El-Sayed,et al.  Different Plasmon Sensing Behavior of Silver and Gold Nanorods. , 2013, The journal of physical chemistry letters.

[16]  L. Liz‐Marzán,et al.  N,N‐Dimethylformamide as a Reaction Medium for Metal Nanoparticle Synthesis , 2009, Colloidal Synthesis of Plasmonic Nanometals.

[17]  Catherine J. Murphy,et al.  Seed‐Mediated Growth Approach for Shape‐Controlled Synthesis of Spheroidal and Rod‐like Gold Nanoparticles Using a Surfactant Template , 2001 .

[18]  Mostafa A. El-Sayed,et al.  Preparation and Growth Mechanism of Gold Nanorods (NRs) Using Seed-Mediated Growth Method , 2003 .

[19]  C. Mirkin,et al.  Defining rules for the shape evolution of gold nanoparticles. , 2012, Journal of the American Chemical Society.

[20]  L. Liz‐Marzán,et al.  Modulation of Localized Surface Plasmons and SERS Response in Gold Dumbbells through Silver Coating , 2010 .

[21]  Paul Mulvaney,et al.  Electric‐Field‐Directed Growth of Gold Nanorods in Aqueous Surfactant Solutions , 2004 .

[22]  L. Liz‐Marzán,et al.  The crystalline structure of gold nanorods revisited: evidence for higher-index lateral facets. , 2010, Angewandte Chemie.

[23]  H. Davenport,et al.  The oxidation of ascorbic acid and its reduction in vitro and in vivo , 1937 .

[24]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[25]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[26]  Luis M Liz-Marzán,et al.  Shape control in gold nanoparticle synthesis. , 2008, Chemical Society reviews.

[27]  D. Sinclair,et al.  Direct Atomic Observation in Powdered 4H-Ba0.8Sr0.2Mn0.4Fe0.6O2.7 , 2013 .

[28]  G. D. Barmparis,et al.  Dependence on CO adsorption of the shapes of multifaceted gold nanoparticles: A density functional theory , 2012 .

[29]  W. Cao,et al.  A novel cetyltrimethyl ammonium silver bromide complex and silver bromide nanoparticles obtained by the surfactant counterion. , 2007, Journal of colloid and interface science.

[30]  Jianfang Wang,et al.  Crystalline structure-dependent growth of bimetallic nanostructures. , 2012, Nanoscale.

[31]  Catherine J. Murphy,et al.  Fine-tuning the shape of gold nanorods , 2005 .

[32]  Younan Xia,et al.  Symmetry breaking during seeded growth of nanocrystals. , 2012, Nano letters.

[33]  Benito Rodríguez-González,et al.  Synthesis and Optical Properties of Gold Nanodecahedra with Size Control , 2006 .

[34]  K. Honkala,et al.  A Density Functional Theory study on gold cyanide interactions: The fundamentals of ore cleaning , 2010 .

[35]  Younan Xia,et al.  Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics? , 2009, Angewandte Chemie.

[36]  Philippe Guyot-Sionnest,et al.  Mechanism of silver(I)-assisted growth of gold nanorods and bipyramids. , 2005, The journal of physical chemistry. B.

[37]  Scheffler,et al.  Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111). , 1992, Physical review. B, Condensed matter.

[38]  B. Rodríguez-González,et al.  Multishell bimetallic AuAg nanoparticles: synthesis, structure and optical properties , 2005 .

[39]  C. J. Johnson,et al.  Growth and form of gold nanorods prepared by seed-mediated, surfactant-directed synthesis , 2002 .

[40]  B. Nikoobakht,et al.  種結晶を媒介とした成長法を用いた金ナノロッド(NR)の調製と成長メカニズム , 2003 .

[41]  F. Testard,et al.  Cetyltrimethylammonium bromide silver bromide complex as the capping agent of gold nanorods. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[42]  N. Nakashima,et al.  Uniform and controllable preparation of Au-Ag core-shell nanorods using anisotropic silver shell formation on gold nanorods. , 2010, Nanoscale.

[43]  L. Liz‐Marzán,et al.  Light concentration at the nanometer scale , 2010 .