A facile method for the synthesis of large‐size Ag nanoparticles as efficient SERS substrates

Silver nanoparticles (Ag NPs) enjoy a reputation as an ultrasensitive substrate for surface-enhanced Raman spectroscopy (SERS). However, large-scale synthesis of Ag NPs in a controlled manner is a challenging task for a long period of time. Here, we reported a simple seed-mediated method to synthesize Ag NPs with controllable sizes from 50 to 300 nm, which were characterized by scanning electron microscopy (SEM) and UV–Vis spectroscopy. SERS spectra of Rhodamine 6G (R6G) from the as-prepared Ag NPs substrates indicate that the enhancement capability of Ag NPs varies with different excitation wavelengths. The Ag NPs with average sizes of ~150, ~175, and ~225 nm show the highest SERS activities for 532, 633, and 785-nm excitation, respectively. Significantly, 150-nm Ag NPs exhibit an enhancement factor exceeding 108 for pyridine (Py) molecules in electrochemical SERS (EC-SERS) measurements. Furthermore, finite-difference time-domain (FDTD) calculation is employed to explain the size-dependent SERS activity. Finally, the potential of the as-prepared SERS substrates is demonstrated with the detection of malachite green. Copyright © 2016 John Wiley & Sons, Ltd.

[1]  M. Temgire,et al.  Optical and structural studies of silver nanoparticles , 2004 .

[2]  R. Dasari,et al.  Single Molecule Detection Using Surface-Enhanced Raman Scattering (SERS) , 1997 .

[3]  Catherine J. Murphy,et al.  Wet chemical synthesis of silver nanorods and nanowiresof controllable aspect ratio , 2001 .

[4]  Jian-Feng Li,et al.  Synthesis, characterization, and 3D-FDTD simulation of Ag@SiO2 nanoparticles for shell-isolated nanoparticle-enhanced Raman spectroscopy. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[5]  Younan Xia,et al.  Shape-Controlled Synthesis of Gold and Silver Nanoparticles , 2002, Science.

[6]  Zhong-Qun Tian,et al.  Quantitative SHINERS analysis of temporal changes in the passive layer at a gold electrode surface in a thiosulfate solution. , 2015, Analytical chemistry.

[7]  Rajender S Varma,et al.  Microwave-assisted green synthesis of silver nanostructures. , 2011, Accounts of chemical research.

[8]  D. Carroll,et al.  Silver Nanoplates : Size Control in Two Dimensions and Formation Mechanisms , 2004 .

[9]  N. Pellegri,et al.  Effect of amine groups in the synthesis of Ag nanoparticles using aminosilanes , 2005 .

[10]  Zhilin Yang,et al.  Optimization of SERS activities of gold nanoparticles and gold-core-palladium-shell nanoparticles by controlling size and shell thickness , 2008 .

[11]  P. Hildebrandt,et al.  Surface-enhanced resonance Raman spectroscopy of Rhodamine 6G adsorbed on colloidal silver , 1984 .

[12]  Bingsheng Yin,et al.  Electrochemical Synthesis of Silver Nanoparticles under Protection of Poly(N-vinylpyrrolidone) , 2003 .

[13]  Yan Lu,et al.  In Situ Formation of Ag Nanoparticles in Spherical Polyacrylic Acid Brushes by UV Irradiation , 2007 .

[14]  M. J. Weaver,et al.  Surface-enhanced Raman scattering on uniform transition-metal films:  toward a versatile adsorbate vibrational strategy for solid-nonvacuum interfaces? , 1998, Analytical chemistry.

[15]  N. Pieczonka,et al.  Single molecule analysis by surfaced-enhanced Raman scattering. , 2008, Chemical Society reviews.

[16]  M. Faraday.  X. The Bakerian Lecture. —Experimental relations of gold (and other metals) to light , 1857, Philosophical Transactions of the Royal Society of London.

[17]  R. Zenobi,et al.  Nanoscale chemical analysis by tip-enhanced Raman spectroscopy , 2000 .

[18]  J. Solla-Gullón,et al.  Nanoparticles-on-electrode approach forin situ surface-enhanced Raman spectroscopy studies with platinum-group metals: examples and prospects , 2005 .

[19]  M. El-Sayed,et al.  Chemistry and properties of nanocrystals of different shapes. , 2005, Chemical reviews.

[20]  G. Frens.  Controlled Nucleation for the Regulation of the Particle Size in Monodisperse Gold Suspensions , 1973 .

[21]  Nannan Mao,et al.  Graphene: a platform for surface-enhanced Raman spectroscopy. , 2013, Small.

[22]  A. Gewirth,et al.  Shell‐isolated nanoparticle enhanced Raman spectroscopy (SHINERS) investigation of benzotriazole film formation on Cu(100), Cu(111), and Cu(poly) , 2012 .

[23]  M. Natan,et al.  Self-Assembled Metal Colloid Monolayers: An Approach to SERS Substrates , 1995, Science.

[24]  Duncan Graham,et al.  The next generation of advanced spectroscopy: surface enhanced Raman scattering from metal nanoparticles. , 2010, Angewandte Chemie.

[25]  Chad A. Mirkin,et al.  Designing, fabricating, and imaging Raman hot spots , 2006, Proceedings of the National Academy of Sciences.

[26]  Neus G Bastús,et al.  Kinetically controlled seeded growth synthesis of citrate-stabilized gold nanoparticles of up to 200 nm: size focusing versus Ostwald ripening. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[27]  Zhong-Qun Tian,et al.  Surface-enhanced Raman spectroscopy: substrate-related issues , 2009, Analytical and bioanalytical chemistry.

[28]  Steven R. Emory,et al.  Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering , 1997, Science.

[29]  C. Haynes,et al.  Nanosphere Lithography: A Versatile Nanofabrication Tool for Studies of Size-Dependent Nanoparticle Optics , 2001 .

[30]  Bai Yang,et al.  Mercaptoacetic Acid-Capped Silver Nanoparticles Colloid: Formation, Morphology, and SERS Activity , 2003 .

[31]  C. Mirkin,et al.  Controlling anisotropic nanoparticle growth through plasmon excitation , 2003, Nature.

[32]  Absar Ahmad,et al.  Synthesis of Gold Nanotriangles and Silver Nanoparticles Using Aloevera Plant Extract , 2006, Biotechnology progress.

[33]  Tapan K. Sau,et al.  Size Controlled Synthesis of Gold Nanoparticles using Photochemically Prepared Seed Particles , 2001 .

[34]  M. Moskovits.  Surface-enhanced spectroscopy , 1985 .

[35]  J. Baumberg,et al.  Tuning plasmons on nano-structured substrates for NIR-SERS. , 2007, Physical chemistry chemical physics : PCCP.

[36]  Hongxing Xu,et al.  Spectroscopy of Single Hemoglobin Molecules by Surface Enhanced Raman Scattering , 1999 .

[37]  Claire M. Cobley,et al.  Shape-Controlled Synthesis of Silver Nanoparticles for Plasmonic and Sensing Applications , 2009 .

[38]  O. Lev,et al.  Direct Synthesis and Characterization of Gold and Other Noble Metal Nanodispersions in Sol−Gel-Derived Organically Modified Silicates , 1999 .

[39]  Bing Zhao,et al.  Seed-mediated growth of large, monodisperse core-shell gold-silver nanoparticles with Ag-like optical properties. , 2002, Chemical communications.

[40]  Weihong Tan,et al.  Alkyne-Functionalized Superstable Graphitic Silver Nanoparticles for Raman Imaging , 2014, Journal of the American Chemical Society.

[41]  David R. Smith,et al.  Probing the mechanisms of large Purcell enhancement in plasmonic nanoantennas , 2014, Nature Photonics.

[42]  Facundo Ruiz,et al.  Synthesis and antibacterial activity of silver nanoparticles with different sizes , 2008 .

[43]  Zhong-Qun Tian,et al.  Synthesis of AgcoreAushell bimetallic nanoparticles for immunoassay based on surface-enhanced Raman spectroscopy. , 2006, The journal of physical chemistry. B.

[44]  Yukihiro Ozaki,et al.  Simple Method for Preparing Controllably Aggregated Silver Particle Films Used as Surface-Enhanced Raman Scattering Active Substrates , 2002 .

[45]  Paul Mulvaney,et al.  Synthesis of Nanosized Gold−Silica Core−Shell Particles , 1996 .

[46]  A. Blaaderen,et al.  Synthesis and Characterization of Large Colloidal Silver Particles , 2003 .