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1.
The substrate‐dependent surface‐enhanced Raman scattering (SERS) of 4‐aminobenzenethiol (4‐ABT) adsorbed on Au surfaces has been investigated. 4‐ABT is one of the very unique adsorbate molecules whose SERS spectral patterns are known to be noticeably dependent on the relative contribution of chemical enhancement mechanism vs electromagnetic enhancement mechanism. The SERS spectral patterns of 4‐ABT adsorbed on gold substrates with various surface morphology have thus been analyzed in terms of the symmetry types of the vibrational modes. Almost invisibly weak b2 type vibrational bands were observed in the SERS spectra of the 4‐ABT adsorbed on Au colloidal sol nanoparticles or commercially available Au micro‐powders because of the weak contribution of the chemical enhancement. However, greatly enhanced b2 vibrational bands were observed in the spectra of the 4‐ABT molecules adsorbed on the synthesized Au(Zn) sponge or the electrochemically roughened Au(ORC) foil caused by the strong contribution of the chemical enhancement mechanism. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

2.
The preparation of Au‐on‐Pd heteronanostructure (HNS) using citrate‐stabilized polycrystalline Pd nanoparticles (NPs) as the seeds is described. The resulting Au‐on‐Pd HNS is characterized and it is found that the formation of Au‐on‐Pd HNS depends greatly on a ratio between Pd seeds and AuCl4? ions added and the optimal molar ratio is 10:1. If fewer AuCl4? ions are added (Pd/Au ratio is 100:1), the growth of Au NPs only occurs on part of the Pd seeds’ surface. The addition of more AuCl4? ions (Pd/Au ratio is 5:1) hinders the growth of Au NPs on the Pd seeds’ surface. To demonstrate the catalytic performance, the electrochemistry oxidation of ethanol and the reduction of p‐nitrophenol by NaBH4 are chosen to examine the catalytic activity of Au‐on‐Pd HNS. Pd seeds, Au NPs, and poly(vinyl pyrrolidone) (PVP)‐stabilized PdAu nanoalloy are used as the references for comparison. In the first reaction, the catalytic reactivity of Au‐on‐Pd HNS is better than that of corresponding pure Pd or Au NPs, while the opposite occurs for the latter reaction. The catalytic activity of Au‐on‐Pd HNS is much higher than that of PVP‐stabilized PdAu nanoalloy.  相似文献   

3.
The surface chain geometry of atactic poly (methyl methacrylate) (a‐PMMA) film and nanosphere (NS) was revealed by surface‐enhanced Raman scattering (SERS) spectra. The Ag nanoparticles and nanoplates were prepared by electrochemical deposition and chemical synthesis for SERS substrates. The experimental results suggested that the molecular chain axis of a‐PMMA film adopted a trans‐conformation on bonding to Ag surface ascribed to the short‐range chemical (CHEM) effect according to the SERS selection rules. However, for the well‐coated monolayer of a‐PMMA NSs, the α‐CH3 in polymer chains stood vertically to the Ag surface due to the giant local electromagnetic effect, then the chain conformation presented in the interface between a‐PMMA NSs and Ag metal was adopted the opposite orientation compared with a‐PMMA film. The Raman enhancement of the Ag nanoparticles was more prominent than that of the Ag nanoplates due to the free energies of face‐centered cubic crystal faces in nanoparticles, but the single crystals with (111) plane of Ag nanoplates could improve the stability of SERS signals when the annealed temperature was above Tg of a‐PMMA NSs. The present work can provide some useful information of surface chain geometry and conformation of NSs for designing various materials with well‐defined structure via a‐PMMA NSs template. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

4.
Ag films on tinning glass substrates were fabricated by modified silver-mirror (Tollen’s) reaction with the advantage of low-cost, simple and quick fabrication process. The obtained Ag films were served as sacrificial materials for preparation of Ag/Au nanocomposite films by immersing in a chlorauric acid (HAuCl4) solution at room temperature. After a short time of galvanic replacement reaction, Ag/Au bimetallic nanostructures were synthesized with “concave” structures. The morphology, properties and composition of the Ag and Ag/Au nanocomposite films were analyzed by using scanning electron microscopy (SEM), UV-visible spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDS) and surface enhanced Raman scattering (SERS). SEM images displayed that the large area of Ag film and Ag/Au bimetallic nanostructures experienced structural evolution process during galvanic reaction. The UV-Vis spectra showed the absorbencies characterization of Ag film and Ag/Au nanocomposite films. SERS measurements using methylene blue as an analyte showed that SERS intensities of bimetallic films were enhanced significantly compared with that of pure Ag films. The SERS enhancement ability of Ag/Au bimetallic films was dependent on the immersion time for galvanic replacement reaction.  相似文献   

5.
We have been able to observe the surface‐enhanced Raman scattering (SERS) from 4‐mercaptopyridine (4‐Mpy) molecules adsorbed on ZnO nanocrystals, which display 103 enhancement factors (EFs). An excitation wavelength‐dependent behavior is clearly observed. Another molecule BVPP is also observed to have surface‐enhanced Raman signals. The chemical enhancement is most likely responsible for the observed enhancement, since plasmon resonances are ruled out. The research is important not only for a better understanding of the SERS mechanism, but also for extension of the application of Raman spectroscopy to a variety of adsorption problems on a semiconductor surface. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

6.
The NC stretching frequency in the potential‐dependent surface‐enhanced Raman scattering spectrum of 1,4‐phenylenediisocyanide (1,4‐PDI) is very sensitive to the electrode potential, and much the same peak shift is observed when an Au nanoparticle with mean diameter from 16 to 90 nm attached to 1,4‐PDI‐adsorbed gold nanogap system is exposed solely to organic vapors. This leads us to conclude that the surface potential of Au nanoparticles should change by as much as +0.57 and −0.34 V, respectively, in the presence of CCl4 and NH3 because of their respective electron‐withdrawing and electron‐donating properties, regardless of the size of Au nanoparticles in the gold nanogap system. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

7.
Plasmonic systems based on metal nanoparticles on a metal film with high optical absorption have generated great interests for surface‐enhanced Raman scattering (SERS). In this study, we prepare a broadband‐visible light absorber consisting Au nanotriangles on the surface of a continuous optically opaque gold film separated with a dielectric SiO2 layer, which is a typical metal‐insulator‐metal (MIM) system, and demonstrate it as an efficient SERS substrate. The MIM nanostructure, prepared using nanosphere lithography with a very large area, shows a broadband with absorption exceeding 90% in the wavelength regime of 630–920 nm. We observe an average SERS enhancement factor (EF) as large as 4.9 × 106 with a 22‐fold increase compared to a single layer of Au nanotriangles directly on a quartz substrate. A maximum SERS EF can be achieved by optimizing the thicknesses of the dielectric layer to control the optical absorption. Owing to the simple, productive, and inexpensive fabrication technique, our MIM nanostructure could be a potential candidate for SERS applications. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

8.
The capability of anti‐Stokes/Stokes Raman spectroscopy to evaluate chemical interactions at the interface of a conducting polymer/carbon nanotubes is demonstrated. Electrochemical polymerisation of the monomer 3,4‐ethylenedioxythiophene (EDOT) on a Au support covered with a single‐walled carbon nanotube (SWNT) film immersed in a LiClO4/CH3CN solution was carried out. At the resonant optical excitation, which occurs when the energy of the exciting light coincides with the energy of an electronic transition, poly(3,4‐ethylenedioxythiophene) (PEDOT) deposited electrochemically as a thin film of nanometric thickness on a rough Au support presents an abnormally intense anti‐Stokes Raman spectrum. The additional increase in Raman intensity in the anti‐Stokes branch observed when PEDOT is deposited on SWNTs is interpreted as resulting from the excitation of plasmons in the metallic nanotubes. A covalent functionalisation of SWNTs with PEDOT both in un‐doped and doped states takes place when the electropolymerisation of EDOT, with stopping at +1.6 V versus Ag/Ag+, is performed on a SWNT film deposited on a Au plate. The presence of PEDOT covalently functionalised SWNTs is rationalised by (1) a downshift by a few wavenumbers of the polymer Raman line associated with the symmetric C C stretching mode and (2) an upshift of the radial breathing modes of SWNTs, both variations revealing an interaction between SWNTs and the conjugated polymer. Raman studies performed at different excitation wavelengths indicate that the resonant optical excitation is the key condition to observe the abnormal anti‐Stokes Raman effect. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

9.
Surface‐enhanced Raman scattering of p‐aminothiophenol and p‐nitrothiophenol were obtained on the surface of Cu2O nanoparticles, showing novel spectral changes with morphology‐dependent and time‐dependent characteristics. The measured Raman signals were believed to partly originate from the newly produced surface species p,p′‐dimercaptoazobenzene. The nature of surface chemisorption status during Raman measurement was investigated experimentally and theoretically via combined surface‐enhanced Raman scattering and density functional theory study, indicating that surface catalytic reaction of p‐aminothiophenol and p‐nitrothiophenol could take place on the surface of oxide nanostructures as well as coinage metal material. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

10.
Shell‐isolated nanoparticles (NPs)‐enhanced Raman spectroscopy (SHINERS) can be potentially applied to virtually any substrate type and morphology. How to take a step forward to prepare SHINERS NPs (SHINs) with superior performance is critical for the practical applications of surface‐enhanced Raman scattering (SERS) in the breadth and depth. Here, we present a method to obtain 120 nm diameter gold NPs coated with ultrathin silica shells (1–4 nm). The silica shell can be controlled growth through carefully tuning a series of parameters, such as amount of 3‐aminopropyl triethoxysilane used, pH, reaction time, and reaction temperature. We compare the enhancement factor of the obtained 120 nm Au with a 4 nm silica shell NPs to the 55 nm Au with a 4 nm silica shell NPs, and the activity of a 120 nm SHINs is nearly 24 times that the 55 nm SHIN from a single particle view. We also compare the enhancement factor of 1 nm silica shell Au@SiO2 NPs with the bare Au NPs. The enhancement factor of 1 nm silica shell Au@SiO2 NPs was found to be about twice that of the bare particles. For a deeper understanding of the source of the giant enhanced electrical field of the 1 nm silica shell Au@SiO2 NPs, we study the plasmonic property of single 1 nm silica shell Au@SiO2 NP on a gold film substrate through correlation of the structure of single NP using SEM with its SPR spectroscopy. We find that the multipolar interaction between the single Au@SiO2 NP and gold film substrate is important for the SERS. Our studies on the performance of 120 nm SHINs and the plasmonic property of these particles can significantly expand the applications of SHINERS technique and improve the understanding of physical nature of SHINs. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

11.
In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl4 into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl4 solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.  相似文献   

12.
Surface‐enhanced Raman scattering (SERS) spectroscopy is an analytical method for the detection of low amounts of analytes adsorbed on an appropriate coinage metal (Au, Ag, Cu) surface. Generally, the values of the enhancement factor are the highest on silver, lower on gold and relatively very low on copper. In this study, we have focused on the estimation of the enhancement factors of copper surface/substrates formed by different preparation procedures. The SERS activity of large electrochemically prepared substrates and colloidal systems is compared. The surface morphology of the large substrates was studied using scanning electron microscopy and atomic force microscopy. The size distribution of colloidal nanoparticles was monitored by dynamic light scattering. The values of enhancement factor are in both cases more than 105 for the FT‐SERS spectra, demonstrating the fundamental role of nanostructured copper as a substrate material at the excitation wavelength (1064 nm) used. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

13.
We achieved single‐molecule surface‐enhanced Raman scattering (SM‐SERS) spectra from ultralow concentrations (10−15 M) of fullerene C60 on uniformly assembled Au nanoparticles. It was found that resonant excitation at 785 nm is a powerful tool to probe SM‐SERS in this system. The appearance of additional bands and splitting of some vibrational modes were observed because of the symmetry reduction of the adsorbed molecule and a relaxation in the surface selection rules. Time‐evolved spectral fluctuation and ‘hot spot’ dependence in the SM‐SERS spectra were demonstrated to result from the single‐molecule Raman behavior of the spherical C60 on Au nanoparticles. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

14.
Reactive ion etching was used to fabricate black‐Si over the entire surface area of 4‐inch Si wafers. After 20 min of the plasma treatment, surface reflection well below 2% was achieved over the 300–1000 nm spectral range. The spikes of the black‐Si substrates were coated by gold, resulting in an island film for surface‐enhanced Raman scattering (SERS) sensing. A detection limit of 1 × 10?6 M (at count rate > 102 s?1 . mW?1) was achieved for rhodamine 6G in aqueous solution when drop cast onto a ~ 100‐nm‐thick Au coating. The sensitivity increases for thicker coatings. A mixed mobile‐on‐immobile platform for SERS sensing is introduced by using dog‐bone Au nanoparticles on the Au/black‐Si substrate. The SERS intensity shows a non‐linear dependence on the solid angle (numerical aperture of excitation/collection optics) for a thick gold coating that exhibits a 10 times higher enhancement. This shows promise for augmented sensitivity in SERS applications.  相似文献   

15.
We report surface‐enhanced Raman scattering (SERS) spectra from 4‐mercaptopyridine (4‐Mpy) adsorbed on sub‐monolayers of α‐Fe2O3 nanocrystals (sphere, spindle, cube). The maximum enhancement factor has been estimated to be about 104 compared to that of 4‐Mpy in solution. A possible mechanism has been proposed that the charge transfer between the α‐Fe2O3 nanocrystals and the 4‐Mpy molecules is most likely responsible for the observed enhancement of Raman intensity of adsorbed 4‐Mpy molecules as surface plasmon resonances have not occurred. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

16.
《Surface science》1988,206(3):L921-L926
The coverage of an Au overlayer on an Ag island film has been measured using surface enhanced Raman scattering from chemisorbed SO3. XPS was also employed to determine the chemisorption.  相似文献   

17.
We report the observation of large surface‐enhanced Raman scattering (SERS) (106) for 4‐tert‐butylpyridine molecules adsorbed on a silver electrode surface in an electrochemical cell with electrode potential set at − 0.5 V. A decrease in electrode potential to − 0.3 V was accompanied by a decrease in relative intensities of the vibrational modes. However, there were no changes in vibrational wavenumbers. Comparison of both normal solution Raman and SERS spectra shows very large enhancement of the intensities of a1, a2, and b2 modes at laser excitation of 488 nm. Enhancement of the non‐totally symmetric modes indicates the presence of charge transfer as a contributor to the enhancement. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

18.
Potential dependent adsorption of target molecules on electrode surface has long been analyzed by several analytical techniques at the electrochemical interfaces. Here, the adsorption of thiocyanate (SCN) on gold electrodes [Au (111) and Au (poly)] is investigated by electrochemical shell isolated nanoparticle‐enhanced Raman spectroscopy (EC‐SHINERS) and surface‐enhanced Raman spectroscopy. Based on the experimental observation, C − N stretching mode of N‐bound SCN can be observed around 2080 cm−1 throughout the whole potential range. The band corresponding to νC−N of S‐bound SCN appears as a shoulder at more negative potentials, and as a well‐defined band are more positive potentials. However, the overlapped bands provoke a negative shift in the frequency of S‐bound thiocyanate. Therefore, a change in the calculated Stark slope is observed. Interestingly, SHINERS has been employed to demonstrate the thiocyanate orientation and its effect on Raman spectra. Our results widen the opportunities of SHINERS to unravel the potential‐dependent adsorption behavior of target molecules on single‐crystal electrode surfaces. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

19.
A dual‐emission ratiometric fluorescent sensing film for metal ion detection is designed. This dual‐emission film is successfully prepared from chitosan, graphitic carbon nitride (g‐C3N4), and gold nanoclusters (Au NCs). Here, it is shown that the g‐C3N4 not only serves as the fluorescence emission source, but also enhances the mechanical and thermal stability of the film. Meanwhile, the Au NCs are adsorbed on the surface of chitosan film by the electrostatic interaction. The as‐prepared dual‐emission film can selectively detect Cu2+, leading to the quench of red fluorescence of Au NCs, whereas the blue fluorescence from g‐C3N4 persists. The ratio of the two fluorescence intensities depends on the Cu2+ concentration and the fluorescence color changes from orange red to yellow, cyan, and finally to blue with increasing Cu2+ concentration. Thus, the as‐prepared dual‐emission film can be worked as ratiometric sensing paper for Cu2+ detection. Furthermore, the film shows high sensitivity and selectivity, with low limit of detection (LOD) (10 ppb). It is observed that this novel gold‐cluster‐based dual‐emission ratiometric fluorescent sensing paper is an easy and convenient way for detecting metal ions. It is believed that this research work have created another avenue for the detection of metal ions in the environment.  相似文献   

20.
Electromagnetic coupling between localised plasmons on metal nanoparticles and the strong localised fields on a micro‐structured surface is demonstrated as a means to increase the enhancement factor in surface‐enhanced Raman scattering (SERS) spectroscopy. Au nanoparticles of diameter 20 nm were deposited on a micro‐structured Au surface consisting of a periodic array of square‐based pyramidal pits (Klarite). The spectra of 4‐aminothiophenol (4‐ATP) were compared before and after deposition of Au nanoparticles on the micro‐structured surface. The addition of Au nanoparticles is shown to provide significantly higher signal intensities, with improvements of the order of ∼103 per molecule compared with spectra obtained from the micro‐structured substrate alone. This hybrid approach offers promise for combining nanoparticles with micro‐ and nano‐structured surfaces in order to design SERS substrates with higher sensitivities. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

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