Surface-initiated atom transfer radical polymerization from TiO2 nanoparticles

Two kinds of hydrophilic polymers, poly(oxyethylene methacrylate) (POEM) and poly(styrene sulfonic acid) (PSSA), were grafted from TiO₂ nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. Chlorine modified TiO₂ nanoparticles (TiO₂-Cl), the ATRP initiators, were synthesized by the reaction of -OH in TiO₂ with 2-chloropropionyl chloride (CPC). FT-IR, UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS) clearly showed that the polymer chains were successfully grafted from the surface of TiO₂ nanoparticles. The hydrophilically modified TiO₂ nanoparticles have a better dispersion in alcohol than unmodified nanoparticles, as revealed by transmission electron microscopy (TEM). It was also found that the polymer grafting did not significantly alter the crystalline structure of the TiO₂ nanoparticles according to the X-ray diffraction (XRD) patterns. Grafting amounts were 10% of the weight for both TiO₂-POEM and TiO₂-PSSA nanoparticles, as determined by thermogravimetric analysis (TGA).     

The synergistic effect of nitrogen-doped titanium dioxide/mercaptobenzoic acid/silver nanocomplexes for surface-enhanced Raman scattering

We synthesized titanium dioxide (TiO₂) and nitrogen-doped TiO₂ nanoparticles (N-TiO₂ NPs) via a sol-hydrothermal method using ammonium chloride (NH₄Cl) as the nitrogen (N) source. Furthermore, an N-TiO₂/4-mercaptobenzoic acid (4-MBA)/silver (Ag) nanocomplex served as an active substrate for surface-enhanced Raman scattering (SERS) and was prepared by self-assembly. During SERS, the Raman signals of 4-MBA of the N-TiO₂/MBA/Ag nanocomplexes exhibited higher intensity and sensitivity than pure TiO₂/MBA/Ag, with 1% N doping in N-TiO₂, producing the strongest Raman signals. We characterized the N-TiO₂ hybrid materials by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and ultraviolet-visible diffuse reflectance spectra. N doping did not influence the phase of the TiO₂ crystal. The doped N entered into the crystal lattice of the TiO₂, replacing some oxygen (O) to form Ti-O-N or Ti-N-O linkage. The results indicated that an appropriate amount of N doping could enhance the SERS performance of the TiO₂ SERS substrate via N substitution doping. These doping forms were beneficial to the molecular charge transfer (CT), and this resulted in improved SERS performance for N-doped TiO₂ NPs. We attributed this improvement to the formation of N-doping energy levels that were beneficial to the process of TiO₂ to MBA molecule CT. This work not only enriched the nonmetal-doped CT mechanism in SERS but also provided several reference values for practical applications.

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Graphical abstract N-doped TiO₂ nanoparticles were synthesized. Whereafter, N-TiO₂/MBA/Ag nanocomplexes were prepared and served as a SERS-active substrate. An appropriate amount of N doping can enhance the SERS properties of TiO₂ SERS-active substrate by nitrogen substitution doping. The nonmetal doping TiO₂-to-molecule CT mechanism and the synergistic effect in N-TiO₂/MBA/Ag charge transfer systems have been studied.

     

Synthesis of CdSe and CdSe/TiO2 nanoparticles under multibubble sonoluminescence condition

CdSe and CdSe/TiO₂ nanoparticles were synthesized under multibubble sonoluminescence (MBSL) condition. The influences of TiO₂ introduced as the sensitizer on the morphology and crystal transformation were investigated. The morphology, phase and optical properties of the final products have been characterized by X-ray powder diffraction, transmission electron microscope, UV-vis absorption spectroscopy and photoluminescence spectroscopy. The results showed that as-prepared nanoparticles are well-crystallized, and the suppression of crystal pattern transition as well as the control of CdSe crystal growth can be implemented by coupling of TiO₂ semiconductor. Furthermore, the possible growth mechanism for different morphologies and crystal phases of the nanocrystals were also discussed.     

银/二氧化钛核壳纳米颗粒对碲化镉纳米晶的荧光增强研究

利用新合成的复合纳米结构银/二氧化钛核壳纳米颗粒,研究了金属银纳米颗粒对碲化镉纳米晶层荧光的增强情况.结果表明,这种新型复合金属纳米结构能极大地增强发光纳米晶层的荧光强度.银/二氧化钛核壳纳米颗粒是以水合肼、硝酸银和四异丙氧基钛为原材料,利用胶体化学法在水溶液中合成.透射电子显微镜图片表明这种新合成的银/二氧化钛纳米材料基本上呈球形,有较为明显的核壳结构,中间黑色的核是银纳米颗粒,外层颜色较浅部分是二氧化钛壳层.另外,包裹二氧化钛壳层后,银纳米颗粒的表面等离子吸收带从409 nm红移至430 nm,也证实了这种新型核壳纳米材料的形成.将此合成方法得到的银/二氧化钛纳米颗粒和碲化镉纳米晶用旋转涂覆方法进行直接组合后,得到了银纳米颗粒对碲化镉纳米晶荧光的明显增强,并对其增强的物理过程进行了讨论.这种能够增强荧光团发光的新型复合银纳米结构将在发光器件、荧光成像、生物探测等方面具有一定的应用价值.     

In situ Radical Copolymerization in Presence of Surface‐Modified TiO2 Nanoparticles: Influence of a Double Modification on Properties of Unsaturated Polyester (UP) Nanocomposites

In the preparation of nanocomposites, there is competition between the dispersion of nanoparticles and the formation of agglomerates. In this study, radical copolymerization of ethyl acrylate and methyl methacrylate initiated by 2,2‐azobis (isobutyro) nitrile (AIBN) was performed, in the presence of titanium oxide (TiO₂) nanoparticles modified in a new approach; a good dispersion of the nanoparticles in the unsaturated polyester (UP) matrix was obtained. The TiO₂ nanoparticles were exposed to 3‐(methacryloxy) propyl trimethoxy silane as the coupling agent. The presence of coupling agent‐grafted TiO₂ nanoparticles in the copolymerization process resulted in the formation of a polymeric layer on the surface of the TiO₂ nanoparticles (doubly modified‐TiO₂). The grafting of coupling agent molecules and consequently copolymer macromolecular chains onto the surface of TiO₂ nanoparticles was investigated using Fourier transform infrared (FTIR) analysis. It found that the formation of an acrylate layer on the surface of nanoparticles was successful. Then, unsaturated polyester (UP)/TiO₂ nanocomposites were prepared. The morphology was studied using transmission electron microscopy (TEM). Mechanical properties and ultraviolet visible (UV/VIS) spectroscopy of various samples, including the doubly modified‐TiO₂ nanoparticles, with different nanoparticle inclusions and the unmodified‐TiO₂ nanoparticles, were also investigated. The results showed the doubly modified‐TiO₂ nanoparticles, compared to those of unmodified‐TiO₂, had better nanoparticle dispersion causing improvement in the mechanical properties and UV shielding.     

Preparation and photoelectrochemical performance of Ag/graphene/TiO2 composite film

By dipping-lifting in sol-gel solution and reducing process, the graphene/TiO₂ composite film on the glass plate was first prepared. Then, the Ag/graphene/TiO₂ composite film was fabricated by interface reaction with AgNO₃ and N₂H₄·H₂O on the surface of graphene/TiO₂ composite film. The characterization results show that the uniform porous TiO₂ film is made up of the anatase crystal, and the Ag/graphene/TiO₂ composite film is constructed by doping or depositing graphene sheets and Ag nanoparticles on the surface of TiO₂ film. The photoelectrochemical measurement results indicate that the Ag/graphene/TiO₂ composite film has an excellent photoelectrochemical conversion property.     

Synthesis and characterization of poly(N-methylpyrrole)/TiO2 composites on steel

Poly(N-methyl pyrrole) coating was successfully electrodeposited on steel substrates in mixed electrolytes of dodecyl benzene sulphonic acid (DBSA) with oxalic acid in the absence and the presence of TiO₂ nanoparticles (NPs). The morphology and compositions were characterized by Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform Infrared Spectroscopy (FTIR), Energy-Dispersive X-ray spectroscopy (EDX). X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to calculate the size of nanoparticles. Electrode/polymer/electrolyte system was studied by Electrochemical Impedance Spectroscopy (EIS). The FESEM micrographs suggest that the incorporation of TiO₂ nanoparticles affects the morphology of the film significantly and makes the TiO₂ to be loosely piled up with PMPy. The results of EIS showed that synthesized PMPy in the presence of TiO₂ NPs increases and decreases the R_po and C_c of the coating respectively. The increase of the area of synthesized PMPy in the presence of nanoparticles can increase its ability to interact with the ions liberated during the corrosion reaction of steel in NaCl solution.     

Photocatalytic properties of porous C-doped TiO2 and Ag/C-doped TiO2 nanomaterials by eggshell membrane templating

Porous organic carbon-doped titania (C-TiO₂) nanomaterials and their composites with Ag nanoparticles (Ag/C-TiO₂) were synthesized by an eggshell membrane templating method, and their structural and photocatalytic properties were systematically characterized. These nanomaterials, exhibiting a macroscopic morphology of a thin film, are composed of interwoven tubes, and the tube wall consists of nanocrystals. The doped organic carbon was composed of the active carbon and carbonate species, which could form a layer around the surface of TiO₂ nanoparticles, while the silver was incorporated into Ag/C-TiO₂ composites as separated Ag nanoparticles. The degradation of methylene blue under visible light irradiation was employed to evaluate the photocatalytic activity of these as-prepared TiO₂-based materials. Both C-TiO₂ and Ag/C-TiO₂ nanomaterials showed higher photocatalytic activity than pure TiO₂ material–commercial Degussa P25. These results can be accounted for the coupling effect of the incorporation of carbon species and Ag nanoparticles.     

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO₂ sol-gels with various Ag/TiO₂ molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO₂ thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO₂ nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO₂ sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO₂ sol-gel, four types of the TiO₂ thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO₂), TA (bottom layer was pure TiO₂, surface layer was Ag modified), TT (pure TiO₂ thin film) and AA (TiO₂ thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I_ph). LSV confirmed the existence of Ag⁰ state in the TiO₂ thin film. SEM and XRD experiments indicated that the sizes of the TiO₂ nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO₂ thin film.     

In situ spectroelectrochemical surface-enhanced Raman scattering (SERS) investigations on composite Ag/TiO2-nanotubes/Ti substrates

A tubular array of TiO₂-nanotubes on a Ti substrate was used as a support for an Ag sputter-deposited layer intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples of Ag/TiO₂-nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the TiO₂-nanotube/Ti substrates covered with the Ag deposit. In addition, SERS spectra on a bulk electrochemically-roughened Ag reference substrate, were also measured.The SERS activity of the composite samples was strongly dependent on the amount of Ag deposit and, in some cases, was even higher than that for the Ag reference substrate. The SERS intensity vs. electrode potential dependences measured were interpreted in terms of the modified electronic structure of the Ag deposits due to the interaction of the Ag clusters with the TiO₂-nanotube/Ti substrate.     

The irradiation influence on the properties of silver sulfide (Ag2S) colloidal nanoparticles

The aqueous solutions of different stability containing silver sulfide (Ag₂S) nanoparticles are studied. The stable, transparent, and turbid solutions have been subjected to daylight for 7 months, to ultraviolet and laser irradiation, as well as to an electron beam. Solar radiation is found to favor the Ag₂S reduction to Ag and/or the formation of Ag₂S/Ag hybrid nanoparticles in the solution. At a high amount of hybrid nanoparticles, the exciton–plasmon interaction causes asymmetry in the absorption spectra. The exposure of Ag₂S particles precipitated from the solution with the electron beam leads to the reversible growth of Ag threads. The possible exciton–plasmon interplay mechanisms in Ag₂S/Ag hybrid nanoparticles are considered. The physical mechanisms of the changing Ag₂S stoichiometry, the formation of metallic Ag and Ag₂S/Ag hybrid nanoparticles are the generation of hot carriers and the energy transfer (exciton–plasmon interaction) in a metal–semiconductor hybrid nanosystem are elucidated, as well.

     

Preparation and characterization of amine-functionalized SiO2/TiO2 films for formaldehyde degradation

This paper investigated the gaseous formaldehyde degradation by the amine-functionalized SiO₂/TiO₂ photocatalytic films for improving indoor air quality. The films were synthesized via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and 3-aminopropyltrimethoxysilane (APTMS). The physicochemical properties of prepared photocatalysts were characterized with N₂ adsorption/desorption isotherms measurement, X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FT/IR). The effect of amine-functional groups and the ratio of MTMOS/APTMS precursors on the formaldehyde adsorption and photocatalytic degradation were investigated. The results showed that the formaldehyde adsorption and photocatalytic degradation of the APTMS-functionalized SiO₂/TiO₂ film was higher than that of SiO₂/TiO₂ film due to the surface adsorption on amine sites and the relatively high of the specific surface area of the APTMS-functionalized SiO₂/TiO₂ film (15 times higher than SiO₂/TiO₂). The enhancement of the formaldehyde degradation of the film can be attributed to the synergetic effect of adsorption and subsequent photocatalytic decomposition. The repeatability of photocatalytic film was also tested and the degradation efficiency was 91.0% of initial efficiency after seven cycles.     

Surface‐enhanced Raman scattering investigations on silver nanoparticles deposited on alumina and titania nanotubes: influence of the substrate material on surface‐enhanced Raman scattering activity of Ag nanoparticles

Silver nanoparticles deposited on various ‘inert’ porous materials (mainly Al₂O₃ and TiO₂) are often used as substrates for surface‐enhanced Raman scattering (SERS) measurements. In this study, we used the sputter deposition technique to cover tubular arrays of Al₂O₃ and TiO₂ with Ag nanoparticles. Raman spectra of pyridine (as a probe molecule) and of two selected dyes (5‐(4‐dimethylaminobenzylidene)rhodanine and 5‐(4‐(dimethylamino)benzylidene)‐3‐(3‐methoxypropyl)rhodanine) adsorbed on fabricated Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al substrates were measured. We found that the SERS spectra of pyridine adsorbed on Ag nanoparticles deposited on an Al₂O₃‐n/Al substrate are distinctly different from those measured for an Ag/TiO₂‐n/Ti composite. Similar effects were observed for dyes adsorbed on the surface of both composites. The spectral differences between two kinds of composites (Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al) are discussed in terms of (1) the modified electronic structure of the Ag nanoparticles due to their interaction with different substrate materials and (2) the different atomic topology of the metal particles thus deposited on the surfaces of the substrates. Composite samples were also studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Copyright © 2012 John Wiley & Sons, Ltd.     

S180 cell growth on low ion energy plasma treated TiO2 thin films

X-ray photoelectron spectroscopy (XPS) was used to characterise the effects of low energy (<2 eV) argon ion plasma surface modification of TiO₂ thin films deposited by radio frequency (RF) magnetron sputter system. The low energy argon ion plasma surface modification of TiO₂ in a two-stage hybrid system had increased the proportion of surface states of TiO₂ as Ti³⁺. The proportion of carbon atoms as alcohol/ether (COX) was decreased with increase the RF power and carbon atoms as carbonyl (CO) functionality had increased for low RF power treatment. The proportion of C(O)OX functionality at the surface was decreased at low power and further increase in power has showed an increase in its relive proportion at the surface. The growth of S180 cells was observed and it seems that cells are uniformly spreads on tissue culture polystyrene surface and untreated TiO₂ surfaces whereas small-localised cell free area can be seen on plasma treated TiO₂ surfaces which may be due to decrease in C(O)OX, increase in CO and active sites at the surface. A relatively large variation in the surface functionalities with no change in the surface roughness was achieved by different RF plasma treatments of TiO₂ surface whereas no significant change in S180 cell growth with different plasma treatments. This may be because cell growth on TiO₂ was mainly influenced by nano-surface characteristics of oxide films rather than surface chemistry.     

Photoinduced nanocomposites—creation, modification, linear and nonlinear optical properties

UV irradiation of materials consisting of a polymer matrix that possesses precursors of noble metals followed by annealing results in creation of metal nanoparticles within the irradiated domains. Such photoinduced nanocomposites are promising for photonics applications due to the strong alteration of their optical properties compared to initial nonirradiated materials. We report our results on the synthesis and investigation of two kinds of these materials:

1. Photoinduced Au nanocomposites based on PMMA matrices, including bulk materials prepared by means of the polymerization technique;
2. photoinduced Ag nanocomposites with an organic–inorganic hybrid matrix based on TiO₂ gels.

The experimental data on evolution of absorption spectra of these materials due to laser irradiation at different wavelengths are presented. The linear and nonlinear refractive index changes in these materials owing to light-induced nanonstructuring are investigated.     

亚纳米厚的氧化铝包裹层可以显著提高负载型金纳米颗粒催化剂的热稳定性

负载型金纳米颗粒催化剂在许多催化反应中展现出非常好的催化活性,但是金纳米颗粒在高温等反应条件下容易烧结团聚,极大地限制了金催化剂的应用。利用原子层沉积技术在Au/TiO₂催化剂表面分别精确沉积了一层超薄的二氧化钛和氧化铝包裹层,并对比研究了包裹层对金纳米颗粒的热稳定性影响。原位红外漫反射CO吸附和x-射线光电子能谱数据证实了氧化物包裹层的存在。发现亚纳米厚的氧化铝包裹层能够在600 C完全避免金纳米颗粒的团聚;相反,二氧化钛包裹层对金纳米颗粒稳定性的提高没有明显效果。通过CO氧化探针反应的活性测试,发现随着煅烧温度的升高氧化铝包裹的Au/TiO₂ 催化剂的活性逐渐提高,表明高温处理可以促进被包裹金原子的暴露并表现出催化活性。提供了提高金纳米颗粒稳定性的有效方法,为拓展金催化剂在条件苛刻的反应中的应用奠定了技术基础.     

Investigations of Pulse‐Plasma‐Polymer Coating on TiO2 Nanoparticles and Their Dispersion

An amorphous acrylic acid (AA) polymer coating was generated on TiO₂ nanoparticles through pulse radio frequency (RF) plasma polymerization. The AA plasma synthesis mechanism was studied by its optical emission spectrum. The chemical structures of AA–plasma‐polymer were carefully investigated by Fourier transform infrared spectroscopy (FTIR). The dispersion behaviors of AA‐coated and uncoated TiO₂ nanoparticles in glycol solution were characterized by ultraviolet absorbency and particle size distribution measurements. The results showed that the aggregation of TiO₂ nanoparticles in glycol solution was effectively lowered and the dispersion was improved a lot after AA–plasma‐polymer coating. The pulse plasma coating parameters played an important role in the dispersion enhancement of TiO₂ nanoparticles. By properly regulating the pulse discharge parameters, the system could gain the highest radical–monomer reactions rate, the most compatible functional groups on the nanoparticles, and the best dispersion in the background media.     

Highly Active TiO2/Polyelectrolytes Hybrid Multilayered Hollow Nanofibrous Photocatalyst Prepared from Electrouspun Fibers Using Electrostatic Layer-by-Layer Technique

Compared to conventional film photocatalysts, fiber photocatalyst has a greater surface-to-volume ratio and a 3-D open structure that allows its surface active sites to be accessible for reactants more easily and effectively. However, TiO ₂ powder (Degussa P25), by itself, cannot be prepared in the form of fibers, but with the help of a polymer nanofiber, TiO ₂ particles can be immobilized in a fibrous network of polyelectrolyte. Here, hybrid multilayered hollow nanofibers (HMHNFs) composed of TiO ₂ /polyelectrolyte (PE) have been prepared by a combination of a electrospinning method and layer-by-layer (LBL) technology. The results show that both the average diameter and the wall thickness of the HMHNFs can be well controlled by the template, as well as the number of coating layers. The dried morphology of the obtained HMHNFs is dependent on the inner deposited numbers of the polyelectrolyte layers. When compared with other nanostructured TiO ₂ materials, such as commercial TiO ₂ nanoparticles (P25, Degussa) and TiO ₂ films, the hollow TiO ₂ /PE hybrid nanofibers exhibited higher photocatalytic activities.     

Ag/TiO2 sol prepared by a sol–gel method and its photocatalytic activity

Ag/TiO₂ sol with narrow particle size distribution was synthesized using TiCl₄ as the starting material. TiCl₄ was converted to Ti(OH)₄ gel. The Ag/TiO₂ sol was prepared by a process where H₂O₂ was added and then heated at 90–97 °C. After condensation reaction and crystallization, a transparent sol with suspended Ag/TiO₂ was formed. Ag/TiO₂ was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, contact angle analysis, and X-ray photoelectron spectroscopy. The photocatalytic properties of Ag/TiO₂ film were evaluated by degradation of methylene blue in aqueous solution under UV light irradiation. The suspended Ag/TiO₂ particles were rhombus primary particles with the major axis ca. 40 nm and the minor axis ca. 10 nm. Ag nanoparticles were well dispersed on TiO₂ and the particle size was only 1–2 nm. Ag could restrain the recombination of photo-generated electrons and holes effectively. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The thin film had strong hydrophilicity after being illuminated by UV light. Ag/TiO₂ film showed a significant increase in photocatalytic activity compared to the TiO₂ film. The high amount of surface hydroxyls on Ag/TiO₂ film also played an important role in its photocatalytic activity.     

Surface-enhanced Raman scattering (SERS) activity of Ag, Au and Cu nanoclusters on TiO2-nanotubes/Ti substrate

Tubular arrays of TiO₂ nanotubes (ranging in diameter from 40 to 110 nm) on a Ti substrate were used as a support for Ag, Au or Cu deposits obtained by the sputter deposition technique, where the amount of metal varied from 0.01 to 0.2 mg/cm². Those composite supports were intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the metal-covered TiO₂ nanotube/Ti substrates. In addition, SERS spectra on a bulk standard activated Ag, Au and Cu substrates were also measured. The SERS activity of the composite samples was strongly dependent on the amount of metal deposit, e.g. at and above 0.06 mg Ag/cm², the intensity of SERS signal was even higher than that for the Ag reference substrate. The high activity of these composites is mainly a result of their specific morphology. The high SERS sensitivity on the surface morphology of the substrate made it possible to monitor very small temporal changes in the Ag metal clusters. This rearrangement was not detectable with microscopic (SEM) or microanalytical (AES) methods. The SERS activity of Au or Cu clusters was distinctly lower than those of Ag. The spectral differences exhibited by the three kinds of composites as compared to the reference metal samples are discussed.