Plasma chloriding of thin-film silver - A novel process in silver-silver chloride reference electrode fabrication

Silver thin films were modified using a novel plasma modification process for the development of thin-film silver-silver chloride reference electrodes. The surface, physical, and electrochemical properties of these electrodes were investigated by atomic force microscopy, thickness and resistivity measurement techniques, as well as impedance spectroscopy and potentiometry. After plasma treatment, thin-film growth was observed and the electrodes, in general, exhibited low interface impedance and a roughened surface. Evidence of a complex surface reorganization was found. Correlating plasma conditions with film properties suggested that increasing pressure and exposure duration increased species availability, therefore governing the reaction rates, while input power appeared to influence the type of surface chemical reactions. Results also indicated that Ar/Cl-2 mixtures should be employed rather than pure chlorine plasmas. (C) 2002 The Electrochemical Society.

On the nature of the silver phases of Ag/Al2O3 catalysts for reactions involving nitric oxide

The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV-VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV-VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV-VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H-2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O-2). The low activity for N-2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can. therefore, he related to the presence of metallic silver. which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2. (C) 2002 Elsevier Science B.V. All rights reserved.

The cyclic “silver-diphos” motif [Ag2(-diphosphine)2]2+ as a synthon for building up larger structure structures

The dinuclear, cyclic structural motif [Ag-2(diphosphine)(2)](2+), here termed the

Multiple Evidence for Gold(I)center dot center dot center dot Silver(I) Interactions in Solution

[AuAg3(C6F5)(CF3CO2)(3)(CH2PPh3)](n) (2) was prepared by reaction of [Au(C6F5)(CH2PPh3)] (1) and [Ag(CF3CO2)] (1:3). The crystal structures of complexes I and 2 were determined by X-ray diffraction, and the latter shows a polymeric 2D arrangement built by Au - Ag, Ag - Ag, and Ag - O contacts. The metallophilic interactions observed in 2 in the solid state seem to be preserved in concentrated THF solutions, as suggested by EXAFS, pulsed-gradient spin-echo NMR, and photophysical studies, which showed that the structural motif [AuAg3(C6F5)(CF3CO2)(3)(CH2PPh3)] is maintained under such conditions. Time-dependent DFT calculations agree with the experimental photophysical energies and suggest a metal-to-ligand charge-transfer phosphorescence process. Ab initio calculations give an estimated interaction energy of around 60 kJ mol(-1) for each Au - Ag interaction.

Templated electrodeposition of silver nanowires in a nanoporous polycarbonate membrane from a nonaqueous ionic liquid electrolyte

Template electrodeposition has been used to prepare a wide range of nanostructures but has generally been restricted to aqueous electrolytes. We report the deposition of silver nanowires in a commercial nuclear track-etched polycarbonate template from the nonaqueous ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) using silver electrochemically dissolved from the anode. Transmission electron microscopy (TEM) shows that the nanowires have a very high aspect ratio with an average diameter of 80 nm and length of 5 mu m. Ionic liquid electrolytes should greatly extend the range of metals that can be electrodeposited as nanowires using templates.

Sol-gel-entrapped nano silver catalysts-correlation between active silver species and catalytic behavior

Silver colloids prepared by reducing AgNO3 in aqueous solution with sodium citrate were embedded in alumina following two different preparation procedures resulting in samples containing 3 and 5 wt.% silver. Characterization of these materials using TEM. XPS, XAES, CP/MAS NMR, XRD, and adsorption-desorption isotherms of nitrogen showed that embedding the pre-prepared silver colloids into the alumina via the sol-gel procedure preserved the particle size of silver. However, as XAES demonstrates, the catalysts prepared in a sol-gel with a lower amount of water led to embedded colloids with a higher population of Ag+ species. The catalytic behaviors of the resultant catalysts were well correlated with the concentration of these species. Thus, the active silver species of the catalysts containing more Ag+ species selectively converts NO to N-2. However, subsequent thermal aging leads to an enhancement of the conversion of NO parallel to slight alteration of the selectivity with the appearance of low amounts of N2O despite an increase of Ag+ species. Accordingly, an optimal surface Ag-0/Ag+ ratio is probably needed, independently of the size of silver particles. It was found that this optimal ratio strongly depends on the operating conditions during the synthesis route. (C) 2010 Elsevier Inc. All rights reserved.

Surface enhanced Raman evidence for Ag+ complexes of adenine, deoxyadenosine and 5'-dAMP formed in silver colloids

We report the formation of highly scattering silver complexes of adenine, deoxyadenosine and 5'-dAMP under alkaline pH conditions in the colloidal silver solutions which are used for surface-enhanced Raman spectroscopy. These complexes, and other pH-dependent phenomena, help to explain the diversity of previously reported adenine SERS spectra. Using conditions which promote complex formation allows nucleotides to be detected at <1 ppm, even in solutions with high salt concentrations.