In Situ Surface‐Enhanced Raman Spectroscopy Study of Plasmon‐Driven Catalytic Reactions of 4‐Nitrothiophenol under a Controlled Atmosphere

We demonstrate the plasmon‐driven catalytic reactions of 4‐nitrothiophenol (4NTP) on a single Ag microsphere by an in situ surface‐enhanced Raman spectroscopy (SERS) technique. The highly SERS‐active hierarchical Ag structures served as an ideal platform to study plasmon‐driven catalytic reactions. This single‐particle surface‐enhanced Raman spectroscopy (SP‐SERS) technique coupled with inbuilt apparatus allow us to study the impact of reaction atmospheres and laser power on the rate of dimerization and reduction of 4NTP. Contrary to that found in previous studies, 4NTP could be transformed into 4‐aminothiophenol under H2O or H2 atmosphere. The broadening and splitting of the ν(CC) band during the reaction results from the frequency shift of the ν(CC) band that arises from different products. Our results suggest that the SP‐SERS technique is ideally suited to study plasmon‐driven catalytic reactions because of the possibility to monitor the reaction under controlled atmospheres in real time.

[1]  Naoki Matsuda,et al.  Charge transfer resonance Raman process in surface-enhanced Raman scattering from p-aminothiophenol adsorbed on silver: Herzberg-Teller contribution , 1994 .

[2]  G. Schatz,et al.  Pyridine-Ag20 cluster: a model system for studying surface-enhanced Raman scattering. , 2006, Journal of the American Chemical Society.

[3]  M. Fiałkowski,et al.  Plastic and Moldable Metals by Self-Assembly of Sticky Nanoparticle Aggregates , 2007, Science.

[4]  L. Brus.  Noble metal nanocrystals: plasmon electron transfer photochemistry and single-molecule Raman spectroscopy. , 2008, Accounts of chemical research.

[5]  J. Keum,et al.  Confined Crystallization of Polyethylene Oxide in Nanolayer Assemblies , 2009, Science.

[6]  Hongxing Xu,et al.  Highly Surface‐roughened “Flower‐like” Silver Nanoparticles for Extremely Sensitive Substrates of Surface‐enhanced Raman Scattering , 2009 .

[7]  Hongxing Xu,et al.  Direct visual evidence for the chemical mechanism of surface-enhanced resonance Raman scattering via charge transfer , 2009 .

[8]  De‐Yin Wu,et al.  Surface Catalytic Coupling Reaction of p-Mercaptoaniline Linking to Silver Nanostructures Responsible for Abnormal SERS Enhancement: A DFT Study , 2009 .

[9]  Zhong-Qun Tian,et al.  When the signal is not from the original molecule to be detected: chemical transformation of para-aminothiophenol on Ag during the SERS measurement. , 2010, Journal of the American Chemical Society.

[10]  Z. Kim,et al.  Charge transfer enhancement in the SERS of a single molecule. , 2010, Nano letters.

[11]  Hongxing Xu,et al.  Ascertaining p,p'-dimercaptoazobenzene produced from p-aminothiophenol by selective catalytic coupling reaction on silver nanoparticles. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[12]  Simion Astilean,et al.  Disentangling SERS signals from two molecular species: A new evidence for the production of p,p′-dimercaptoazobenzene by catalytic coupling reaction of p-aminothiophenol on metallic nanostructures , 2010 .

[13]  Hongxing Xu,et al.  Substrate-, wavelength-, and time-dependent plasmon-assisted surface catalysis reaction of 4-nitrobenzenethiol dimerizing to p,p'-dimercaptoazobenzene on Au, Ag, and Cu films. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[14]  Hong Wei,et al.  Acid-directed synthesis of SERS-active hierarchical assemblies of silver nanostructures , 2011 .

[15]  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.

[16]  Suljo Linic,et al.  Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures. , 2011, Nature chemistry.

[17]  Yingzhou Huang,et al.  The pH-Controlled Plasmon-Assisted Surface Photocatalysis Reaction of 4-Aminothiophenol to p,p′-Dimercaptoazobenzene on Au, Ag, and Cu Colloids , 2011 .

[18]  De‐Yin Wu,et al.  Photon-driven charge transfer and photocatalysis of p-aminothiophenol in metal nanogaps: a DFT study of SERS. , 2011, Chemical communications.

[19]  Hairong Zheng,et al.  In-situ plasmon-driven chemical reactions revealed by high vacuum tip-enhanced Raman spectroscopy , 2012, Scientific Reports.

[20]  Hongxing Xu,et al.  A novel application of plasmonics: plasmon-driven surface-catalyzed reactions. , 2012, Small.

[21]  A. C. Blair,et al.  Discovering Nanoscience , 2012, Science.

[22]  H. Xin,et al.  Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures. , 2012, Nature materials.

[23]  Volker Deckert,et al.  Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. , 2012, Nature nanotechnology.

[24]  Zhong-Qun Tian,et al.  Surface-enhanced Raman spectroscopic study of p-aminothiophenol. , 2012, Physical chemistry chemical physics : PCCP.

[25]  P. Ajayan,et al.  Plasmon-induced doping of graphene. , 2012, ACS nano.

[26]  Richard W. Taylor,et al.  In Situ SERS Monitoring of Photochemistry within a Nanojunction Reactor , 2013, Nano letters.

[27]  K. Schanze,et al.  Mechanistic understanding of surface plasmon assisted catalysis on a single particle: cyclic redox of 4-aminothiophenol , 2013, Scientific Reports.

[28]  K. S. Shin,et al.  Photoreduction of 4,4'-dimercaptoazobenzene on ag revealed by Raman scattering spectroscopy. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[29]  P. Netti,et al.  Tuning gold nanoparticles interfaces by specific peptide interaction for surface enhanced Raman spectroscopy (SERS) and separation applications. , 2013, ACS applied materials & interfaces.

[30]  Hongxing Xu,et al.  Activated vibrational modes and Fermi resonance in tip-enhanced Raman spectroscopy. , 2011, Physical review. E, Statistical, nonlinear, and soft matter physics.

[31]  Hongxing Xu,et al.  Plasmonic scissors for molecular design. , 2013, Chemistry.

[32]  Florian Libisch,et al.  Hot electrons do the impossible: plasmon-induced dissociation of H2 on Au. , 2013, Nano letters.

[33]  Hsing-lin Wang,et al.  Laser wavelength- and power-dependent plasmon-driven chemical reactions monitored using single particle surface enhanced Raman spectroscopy. , 2013, Chemical communications.

[34]  Hsing-lin Wang,et al.  Amino Acid-Assisted Synthesis of Hierarchical Silver Microspheres for Single Particle Surface-Enhanced Raman Spectroscopy , 2013 .

[35]  M. Dresselhaus,et al.  Electronic properties of nano-structured bismuth-antimony materials , 2014 .

[36]  Chaojiang Niu,et al.  VO2 nanowires assembled into hollow microspheres for high-rate and long-life lithium batteries. , 2014, Nano letters.

[37]  K. S. Shin,et al.  Fe3+ to Fe2+ Conversion by Plasmonically Generated Hot Electrons from Ag Nanoparticles: Surface-Enhanced Raman Scattering Evidence , 2014 .

[38]  Plasmon-driven sequential chemical reactions in an aqueous environment , 2014, Scientific reports.

[39]  Luis M Liz-Marzán,et al.  Monodisperse gold nanotriangles: size control, large-scale self-assembly, and performance in surface-enhanced Raman scattering. , 2014, ACS nano.

[40]  J. Pasán,et al.  Oxamato-based coordination polymers: recent advances in multifunctional magnetic materials. , 2014, Chemical communications.

[41]  Jing-fu Liu,et al.  Submonolayer-Pt-Coated Ultrathin Au Nanowires and Their Self-Organized Nanoporous Film: SERS and Catalysis Active Substrates for Operando SERS Monitoring of Catalytic Reactions. , 2014, The journal of physical chemistry letters.

[42]  R. Sardar,et al.  Isolation of Bright Blue Light-Emitting CdSe Nanocrystals with 6.5 kDa Core in Gram Scale: High Photoluminescence Efficiency Controlled by Surface Ligand Chemistry , 2014 .

[43]  Indika U. Arachchige,et al.  Oxidation-induced self-assembly of Ag nanoshells into transparent and opaque Ag hydrogels and aerogels. , 2014, Journal of the American Chemical Society.

[44]  Kun Zhang,et al.  Layer-by-layer self-assembly of TiO2 hierarchical nanosheets with exposed {001} facets as an effective bifunctional layer for dye-sensitized solar cells. , 2014, ACS applied materials & interfaces.