Bifunctional Ag@Pd-Ag Nanocubes for Highly Sensitive Monitoring of Catalytic Reactions by Surface-Enhanced Raman Spectroscopy.

We report a route to the facile synthesis of Ag@Pd-Ag nanocubes by cotitrating Na2PdCl4 and AgNO3 into an aqueous suspension of Ag nanocubes at room temperature in the presence of ascorbic acid and poly(vinylpyrrolidone). With an increase in the total titration volume, we observed the codeposition of Pd and Ag atoms onto the edges, corners, and side faces of the Ag nanocubes in a site-by-site fashion. By maneuvering the Pd/Ag ratio, we could optimize the SERS and catalytic activities of the Ag@Pd-Ag nanocubes for in situ SERS monitoring of the Pd-catalyzed reduction of 4-nitrothiophenol by NaBH4.

[1]  D. Qin,et al.  Transformation of Ag nanocubes into Ag-Au hollow nanostructures with enriched Ag contents to improve SERS activity and chemical stability. , 2014, ACS applied materials & interfaces.

[2]  Shouheng Sun,et al.  Nanocatalyst superior to Pt for oxygen reduction reactions: the case of core/shell Ag(Au)/CuPd nanoparticles. , 2014, Journal of the American Chemical Society.

[3]  S. Rigby A Model for the Surface Diffusion of Molecules on a Heterogeneous Surface , 2003 .

[4]  R. Dasari,et al.  Ultrasensitive chemical analysis by Raman spectroscopy. , 1999, Chemical reviews.

[5]  Yadong Li,et al.  Sophisticated construction of Au islands on Pt-Ni: an ideal trimetallic nanoframe catalyst. , 2014, Journal of the American Chemical Society.

[6]  Dongping Zhan,et al.  Adsorption/desorption of hydrogen on Pt nanoelectrodes: evidence of surface diffusion and spillover. , 2009, Journal of the American Chemical Society.

[7]  L. Liz‐Marzán,et al.  Catalysis by metallic nanoparticles in aqueous solution: model reactions. , 2012, Chemical Society reviews.

[8]  Younan Xia,et al.  Shape-controlled metal nanocrystals for catalytic applications , 2014 .

[9]  Yugang Sun,et al.  Mesoporous Colloidal Superparticles of Platinum‐Group Nanocrystals with Surfactant‐Free Surfaces and Enhanced Heterogeneous Catalysis , 2015 .

[10]  Xianmao Lu,et al.  Tailoring galvanic replacement reaction for the preparation of Pt/Ag bimetallic hollow nanostructures with controlled number of voids. , 2012, ACS nano.

[11]  Younan Xia,et al.  The SERS activity of a supported Ag nanocube strongly depends on its orientation relative to laser polarization. , 2007, Nano letters.

[12]  Joseph M. McLellan,et al.  Surface-enhanced Raman scattering of 4-mercaptopyridine on thin films of nanoscale Pd cubes, boxes, and cages , 2006 .

[13]  Shengli Zou,et al.  Removal of molecular adsorbates on gold nanoparticles using sodium borohydride in water. , 2013, Nano letters.

[14]  T. Pal,et al.  Nitroarene reduction: a trusted model reaction to test nanoparticle catalysts. , 2015, Chemical communications.

[15]  P. Nordlander,et al.  Tunable plasmonic nanoparticles with catalytically active high-index facets. , 2014, Nano letters.

[16]  Liangbao Yang,et al.  Highly sensitive in situ monitoring of catalytic reactions by surface enhancement Raman spectroscopy on multifunctional Fe₃O₄/C/Au NPs. , 2014, Nanoscale.

[17]  M. El-Sayed,et al.  Metallic double shell hollow nanocages: the challenges of their synthetic techniques. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[18]  Younan Xia,et al.  Quantitative analysis of the role played by poly(vinylpyrrolidone) in seed-mediated growth of Ag nanocrystals. , 2012, Journal of the American Chemical Society.

[19]  Peidong Yang,et al.  Shaping binary metal nanocrystals through epitaxial seeded growth. , 2007, Nature materials.

[20]  Claire M. Cobley,et al.  Controlling the synthesis and assembly of silver nanostructures for plasmonic applications. , 2011, Chemical reviews.

[21]  A. Patra,et al.  Core-size-dependent catalytic properties of bimetallic Au/Ag core-shell nanoparticles. , 2014, ACS applied materials & interfaces.

[22]  M. J. Weaver,et al.  Nature of surface bonding on voltammetrically oxidized noble metals in aqueous media as probed by real-time surface-enhanced Raman spectroscopy , 1993 .

[23]  Naomi J Halas,et al.  Observing metal-catalyzed chemical reactions in situ using surface-enhanced Raman spectroscopy on Pd-Au nanoshells. , 2008, Journal of the American Chemical Society.

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

[25]  Hong Yang,et al.  Platinum-based oxygen reduction electrocatalysts. , 2013, Accounts of chemical research.

[26]  S. Skrabalak,et al.  Octopods versus concave nanocrystals: control of morphology by manipulating the kinetics of seeded growth via co-reduction. , 2011, Nano letters.

[27]  Hui Wang,et al.  Structural Evolution of Ag–Pd Bimetallic Nanoparticles through Controlled Galvanic Replacement: Effects of Mild Reducing Agents , 2015 .

[28]  D. Qin,et al.  Galvanic replacement-free deposition of Au on Ag for core-shell nanocubes with enhanced chemical stability and SERS activity. , 2014, Journal of the American Chemical Society.

[29]  Younan Xia,et al.  25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties , 2013, Advanced materials.

[30]  Hui Zhang,et al.  Facile synthesis of Pd-Pt alloy nanocages and their enhanced performance for preferential oxidation of CO in excess hydrogen. , 2011, ACS nano.

[31]  Younan Xia,et al.  Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd. , 2012, Chemical Society reviews.

[32]  Janina Kneipp,et al.  Characterizing the kinetics of nanoparticle-catalyzed reactions by surface-enhanced Raman scattering. , 2012, Angewandte Chemie.

[33]  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.

[34]  Moon J. Kim,et al.  On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystals , 2013, Proceedings of the National Academy of Sciences.

[35]  Yu Han,et al.  Site-specific growth of Au-Pd alloy horns on Au nanorods: a platform for highly sensitive monitoring of catalytic reactions by surface enhancement Raman spectroscopy. , 2013, Journal of the American Chemical Society.

[36]  Jian-Feng Li,et al.  Expanding generality of surface-enhanced Raman spectroscopy with borrowing SERS activity strategy. , 2007, Chemical communications.

[37]  L. Gladden,et al.  Surface diffusion in porous catalysts. , 2010, Physical chemistry chemical physics : PCCP.

[38]  Guobao Xu,et al.  Synthesis of convex hexoctahedral palladium@gold core-shell nanocrystals with {431} high-index facets with remarkable electrochemiluminescence activities. , 2014, ACS nano.

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

[40]  L. Liz‐Marzán,et al.  Size tunable Au@Ag core-shell nanoparticles: synthesis and surface-enhanced Raman scattering properties. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[41]  Younan Xia,et al.  Seed-mediated synthesis of Ag nanocubes with controllable edge lengths in the range of 30-200 nm and comparison of their optical properties. , 2010, Journal of the American Chemical Society.

[42]  C. Mirkin,et al.  Templated techniques for the synthesis and assembly of plasmonic nanostructures. , 2011, Chemical reviews.

[43]  Christine H. Moran,et al.  Generation of hot spots with silver nanocubes for single-molecule detection by surface-enhanced Raman scattering. , 2011, Angewandte Chemie.