Metal-insulator transitions in metal clusters: a high-energy spectroscopy study of palladium and silver clusters

Bremsstrahlung isochromat spectroscopy (BIS) along with ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS) has been employed to investigate the electron states of Pd and Ag deposited on amorphous graphite at different coverages. The metal core level binding energies increase with decreasing cluster size while the UPS valence bands show a decrease in the 4d states at E(F) accompanied by a shift in the intensity maximum to higher binding energies. BIS measurements show the emergence of new states closer to E(F) with increase in the cluster size. It is pointed out that the observed spectral shifts cannot be accounted for by final-state effects alone and that initial-state effects have a significant role. It therefore appears that a decrease in cluster size is accompanied by a metal-insulator transition.

Photostimulated luminescence of silver clusters in zeolite-Y

Upon UV-irradiation at 254 nm, the photoluminescence of silver atoms in zeolite-Y decreases, meanwhile an absorption band shows up around 840 nm. By photostimulation at 840 nm, fluorescence of silver atoms is detected, which is called photostimulated luminescence, and the photoluminescence of silver atoms is increased slightly. These phenomena are attributed to the charge-transfer interaction between the zeolite framework and the entrapped silver atoms. (C) 1997 Published by Elsevier Science B.V.

Sensitive detection of cysteine based on fluorescent silver clusters

In this work,we report the application of novel, water-soluble fluorescent Ag clusters in fluorescent sensors for detecting cysteine, an important biological analyte. The fluorescence of poly(methacrylic acid) (PMAA)templated Ag clusters was found to be quenched effectively by cysteine, but not when the other alpha-amino acids were present. By virtue of the specific response, a new, simple, and sensitive fluorescent method for detecting cysteine has been developed based on Ag clusters. The present assay allows for the selective determination of cysteine in the range of 2.5 x 10(-8) to 6.0 x 10(-6) M with a detection limit of 20 nM at a signal-to-noise ratio of 3. Based on the absorption and fluorescence studies, we suggested that cysteine quenched the emission by the thiol-adsorption-accelerated oxidation of the emissive Ag clusters. The present study shows a promising step toward the application of silver clusters, a new class of attractive fluorescence probes.

Fabrication and characterization of SERS-active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4-aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS-based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80-100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 x 10(4) relative to silver colloid, which might have resulted from the presence of 'hot-spots' at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 x 10(7) by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface.

Polyol-mediated synthesis of polyhedral silver clusters

Besides the spheres, polyhedral silver nanoclusters were prepared by the polyol process with 3-aminopropyl triethoxysilane (APTES). In the process, APTES acts as not only the stabilizer but also the template.

Controlled growth of uniform silver clusters on HOPG

We have investigated growth of silver clusters on three different, i.e. normally cleaved, thermally oxidized and Ar+ ion sputtered highly oriented pyrolytic graphite (HOPG), surfaces. Scanning tunneling microscopy (STM) observations reveal that uniformly sized and spaced Ag clusters only form on the sputtered surface. Ar+ sputtering introduces relatively uniform surface defects compared to other methods. These defects are found to serve as preferential sites for Ag cluster nucleation, which leads to the formation of uniform clusters. (c) 2005 Elsevier B.V. All rights reserved.

Single-molecule detection in a liquid by surface-enhanced resonance Raman scattering

Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters in a liquid has been studied. The first observation of single molecule resonance Raman scattering in a liquid in a probed volume of 10 pL was achieved. Anisotropy of SERRS spectra of single R6G molecule and huge SERRS spectra were observed and compared with that of single molecule fixed in the dried films of sols, which revealed the intricate complex interaction between R6G molecules and the environment in a liquid.

Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even "breathing" of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.

Nano-structural investigation of Ag/Al2O3 catalyst for selective removal of O-2 with excess H-2 in the presence of C2H4

Ag/gamma-Al2O3 catalysts have been characterized in-depth during different thermo-chemical treatments by in situ diffuse reflectance UV-visible spectroscopy and quasi in situ Transmission Electron Microscopy. The combination of these techniques indicates that sintering and redispersion of silver is clearly observed from the increases and decreases in the absorption band intensity over the range of 250-600 nm due to the presence of silver clusters and silver nanoparticles. These results allow us to study the effect of the reaction feed on the metal dispersion at different operation conditions and discuss the formation of active sites during the selective catalytic reduction of O-2 with excess H-2 in the presence of unsaturated hydrocarbons. In this case high catalytic activity and selectivity toward the oxygen removal was achieved for this catalyst. (C) 2010 Elsevier B.V. All rights reserved.

Low-Temperature Selective Catalytic Reduction (SCR) of NOx with n-Octane Using Solvent-Free Mechanochemically Prepared Ag/Al2O3 Catalysts

Low-temperature (<200 degrees C) hydrocarbon selective catalytic reduction of NOx has been achieved for the first time in the absence of hydrogen using a solvent-free mechanochemically prepared Ag/Al2O3 catalyst. Catalysts prepared by this ball-milling method show a remarkable increase in activity for the reduction of nitrogen oxides with octane by lowering the light-off temperature by up to 150 degrees C compared with a state-of-the-art 2 wt %Ag/Al2O3 catalyst prepared by wet impregnation. The best catalyst prepared from silver oxide showed 50% NOx conversion at 240 degrees C and 99%, at 302 degrees C. The increased activity is not due to an increased surface area of the support, but may be associated with a change in.the'defeet structure of the alumina surface, leading to the formation of the small silver clusters necessary for the activation of the octane without leading to total combustion. On the other hand, since one possible role of hydrogen is to remove inhibiting species from the silver, we cannot exclude some change in the chemical properties of the silver as a result of the ball-milling treatment.

Benchmarking Density Functional Based Tight-Binding for Silver and Gold Materials: From Small Clusters to Bulk

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Molecular dynamics study of ‘contact epitaxy’ in Ag clusters supported on a copper (001) surface

In this paper, the formation of heteroepitaxial interfacial layers was investigated by molecular dynamics simulation of soft silver particles landing on the (001) surface of single-crystal copper. In our simulations, the clusters Ag13, Ag55, Ag147 and Ag688 were chosen as projectiles. A small cluster will rearrange into an f.c.c. structure when it is supported on the substrate, due to the large value of its surface/volume ratio. Contact epitaxy appeared in large clusters. The characteristic structure of an epitaxial layer in large silver cluster shows the 〈111〉 direction to be the preferential orientation of heteroepitaxial layers on the surface because of the lattice mismatch between the cluster and the substrate. This was confirmed by studying soft landing events in other systems (Au/Cu and Al/Ni).

Exploiting the facile oxidation of evaporated gold films to drive electroless silver deposition for the creation of bimetallic Au/Ag surfaces

Gold is often considered as an inert material but it has been unequivocally demonstrated that it possesses unique electronic, optical, catalytic and electrocatalytic properties when in a nanostructured form.[1] For the latter the electrochemical behaviour of gold in aqueous media has been widely studied on a plethora of gold samples, including bulk polycrystalline and single-crystal electrodes, nanoparticles, evaporated films as well as electrodeposited nanostructures, particles and thin films.[1b, 2] It is now well-established that the electrochemical behaviour of gold is not as simple as an extended double-layer charging region followed by a monolayer oxide-formation/-removal process. In fact the so-called double-layer region of gold is significantly more complicated and has been investigated with a variety of electrochemical and surface science techniques. Burke and others[3] have demonstrated that significant processes due to the oxidation of low lattice stabilised atoms or clusters of atoms occur in this region at thermally and electrochemically treated electrodes which were confirmed later by Bond[4] to be Faradaic in nature via large-amplitude Fourier transformed ac voltammetric experiments. Supporting evidence for the oxidation of gold in the double-layer region was provided by Bard,[5] who used a surface interrogation mode of scanning electrochemical microscopy to quantify the extent of this process that forms incipient oxides on the surface. These were estimated to be as high as 20% of a monolayer. This correlated with contact electrode resistance measurements,[6] capacitance measurements[7] and also electroreflection techniques...

Effect of cerium oxide on the precipitation of silver nanoparticles in femtosecond laser irradiated silicate glass

We investigated the effect of cerium oxide on the precipitation of Ag nanoparticles in silicate glass via a femtosecond laser irradiation and successive annealing. Absorption spectra show that Ce3+ ions may absorb part of the laser energy via multiphoton absorption and release free electrons, resulting in an increase of the concentration of Ag atoms and a decrease of the concentration of hole-trapped color centers, which influence precipitation of the Ag nanoparticles. In addition, we found that the formed Ag-0 may reduce Ce4+ ions to Ce3+ ions during the annealing process, which inhibits the growth of the Ag nanoparticles.

Photostimulated luminescence of AgI clusters in zeolite-Y

AgI clusters in zeolite-Y (AgI/Y) were prepared by Ag+ exchange followed by reaction with NaI in solution. The formation of the clusters was determined by transmission electron microscopy and Auger electron spectroscopy. The clusters were uniform and even in size, 1.0-2.0 nm. The fluorescence spectrum of the clusters consists of two emission bands, which are attributed to AgI and Ag clusters, respectively. Photostimulated luminescence (PSL) is observed by stimulation at 675 or at 840 nm. The PSL spectrum of AgI/Y is consistent with the emission spectrum of Ag clusters and thus the PSL is considered to be caused by the charge transfer or carrier migration from the zeolite framework or from the AgI clusters to the Ag clusters. The appearance of PSL indicates that these materials may find application as a medium for erasable optical memory. (C) 1998 American Institute of Physics. [S0021-8979(98)02407-4].