Non-isothermal decomposition of silver maleate dihydrate and anhydrous silver fumarate

The non-isothermal decompositions of silver maleate dihydrate (C₄H₂O₄Ag₂2H₂O) and anhydrous silver fumarate (C₄H₂O₄Ag₂) were studied up to 500°C, in a dynamic atmosphere of air, by means of TG and DTA measurements. Both compounds showed some sublimation (at 120°C for silver maleate and at 180°C for silver fumarate) prior to the onset of decomposition (at 170°C for silver maleate and at 280°C for silver fumarate). The gaseous decomposition products of both compounds were found, using IR spectroscopy, to be dominated by maleic anhydride and CO₂. Minor proportions of ethylene, ethyl alcohol, acetone, methane and isobutene were also identified. Metallic silver was the final solid product, as identified by X-ray diffractometry. NMR analysis was used to monitor the isomerization of the maleate radical into the more stable fumarate above 230°C. Kinetic parameters (E _a and lnA) were calculated from the effect of heating rate, (2, 5, 10, and 20 deg min^?1) on the DTA measurements. A mechanism is suggested for the decomposition pathways of these compounds, on basis of the results obtained and, also, on similarities with analogous systems.     

Standard potentials of the silver—silver tungstate,silver—silver phosphate,and silver—silver arsenate electrodes in water—dioxane and water—urea mixtures and related thermodynamic functions

The standard potentials of the silver—silver tungstate, silver—silver phosphate and silver—silver arsenate electrodes in four different compositions of water—dioxane and water—urea mixtures at seven different temperatures from 5 to 35°C have been determined from EMF measurements of cells of the type Ag(s), AgCl(s), NaCl(c)//Na_xZ(c/x), Ag_xZ(s), Ag(s), where x is 2 or 3, and Z is WO₄, PO₄ or AsO₄. These values have been used to evaluate the transfer thermodynamic quantities accompanying the transfer of 1 g ion of WO^2?₄. PO^3?₄ or AsO^3?₄ ion from the standard state in water to the standard state in water—dioxane or water—urea mixtures.     

Paramagnetic behaviour of silver nanoparticles generated by decomposition of silver oxalate

Silver oxalate Ag₂C₂O₄, was already proposed for soldering applications, due to the formation when it is decomposed by a heat treatment, of highly sinterable silver nanoparticles. When slowly decomposed at low temperature (125 °C), the oxalate leads however to silver nanoparticles isolated from each other. As soon as these nanoparticles are formed, the magnetic susceptibility at room temperature increases from −3.14 10⁻⁷ emu.Oe⁻¹.g⁻¹ (silver oxalate) up to −1.92 10⁻⁷ emu.Oe⁻¹.g⁻¹ (metallic silver). At the end of the oxalate decomposition, the conventional diamagnetic behaviour of bulk silver, is observed from room temperature to 80 K. A diamagnetic-paramagnetic transition is however revealed below 80 K leading at 2 K, to silver nanoparticles with a positive magnetic susceptibility. This original behaviour, compared to the one of bulk silver, can be ascribed to the nanometric size of the metallic particles.     

Gravimetric determination of silver as silver chromate

Summary Gravimetric estimation of silver, based upon its quantitative precipitation as normal silver chromate, Ag₂CrO₄, is described.     

Determination of silver carbonate in silver oxide(Ag2O) by infrared spectroscopy

Silver carbonate in silver oxide (Ag(2)O) is determined quantitatively by infrared spectroscopy. The deviation of the results from a mean line is +/-0.2% of Ag(2)CO(3) for samples containing only normal silver carbonate, and +/-0.4% of Ag(2)CO(3) for samples containing both normal and basic silver carbonate.     

Solvent-adaptable silver nanoparticles

A simple and efficient way of obtaining silver nanoparticles that are dispersible both in organic and in aqueous solvents using a single capping agent is described. The silver nanoparticles are initially prepared in water in the presence of aerosol OT [sodium bis(2-ethylhexyl)-sulfosuccinate, AOT]. Thereafter, transfer of the AOT-capped silver nanoparticles to an organic phase is induced by the addition of a small amount of orthophosphoric acid during shaking of the biphasic mixture. The AOT-stabilized silver nanoparticles could be separated out from the organic phase in the form of a powder. The hydrophobic nanoparticles thus prepared are stable and are readily resuspended in a variety of other polar (including water) and nonpolar solvents without further surface treatment. The amphiphatic nature of the silver surface is brought about by a small orientational change in the AOT monolayer on the silver surface in response to the polarity of the solvent.     

Synthesis of silver nanoprisms in formamide

Polygonal (mainly triangular) silver nanoprisms were prepared by reducing silver perchlorate in formamide in the presence of polyethylene glycol (PEG) at room temperature. The reduction of silver ions by formamide leads to the deposition of arrays of triangular shaped silver nanoparticles on the glass walls of the container, accompanied by evolution of CO2 gas. In the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and PEG (1:1), both nanospheres and nanoprisms are formed.     

Synthesis of silver (II) oxide by oxidation of silver or silver oxide by means of ozone

The oxidation by ozone of a suspension of silver or silver oxide in an aqueous solution of sodium hydroxide is described. It has been shown that the oxidation proceeds in two steps:Ag^O₃→Ag₂O^O₃→AgO.The experimental results are in good agreement with a mechanism of dissolution and precipitation. The silver (II) oxide obtained has remarkable properties of stability in alkaline solution and of reducibility to metallic silver. These special properties are probably due to the large size of the particles.     

The response of halide ion-selective electrodes to redox systems : A comparison between silver/silver halide electrodes and silver sulphide- based halide ion-selective electrodes

Silver/silver chloride and bromide electrodes, prepared by anodizing ordinary silver electrodes, and the corresponding ion-selective electrodes based on silver sulphide, were tested for their susceptibility towards redox systems. It proved that the latter type of electrode responded significantly to strong oxidants. In contrast, the silver/silver halide types were highly resistant to redox interference provided that the silver halide layer was free from open pores. This could be achieved by generation of sufficiently thick layers and by selection of suitable current densities during electrodeposition (<20 mA cm^-2). The interrelation between the conditions of silver chloride film generation and redox resistance of the resulting electrodes is described in detail.     

Behaviour of silver—silver malonate and silver—silver succinate electrodes in aqueous media

The silver—silver oxalate electrode has been employed by many workers^1–3 in aqueous media as the second order reference electrode, but no work seems to have been done so far on the study of the behaviour of silver—silver malonate and silver—silver succinate electrodes. The present work deals with the study of these electrodes in ionic equilibria of malonate and succinate ions in aqueous media. These electrodes, in conjunction with a saturated calomel electrode, have been employed in the poten- tiometric determination of malonate and succinate ions in aqueous media. In additon, the effect of the added salts, such as, potassium nitrate and sucrose on the behaviour of these electrodes has also been examined in this media.     

A self-generating third-order electrode: Part II. Analytical applications of the silver—silver sulphide electrode

Analytical applications of the silver—silver sulphide electrode are illustrated by potentiometric determinations of Cd(II) and Pb(II) ions. The stability of the electrode potential in the presence of oxidizing agents is demonstrated by various titrations with silver(I) solutions. The influence of pH on the electrode potential in pure acidic solutions is noted. The electrode used was prepared by electrolytic deposition of silver sulphide on a silver rod; after 2 years, it remained reliable, and was unaffected by light under normal laboratory conditions.     

Dissolution-accompanied aggregation kinetics of silver nanoparticles

Bare silver nanoparticles with diameters of 82 ± 1.3 nm were synthesized by the reduction of the Ag(NH(3))(2)(+) complex with D-maltose, and their morphology, crystalline structure, UV-vis spectrum, and electrophoretic mobilities were determined. Dynamic light scattering was employed to assess early stage aggregation kinetics by measuring the change in the average hydrodynamic diameter of the nanoparticles with time over a range of electrolyte types (NaCl, NaNO(3), and CaCl(2)) and concentrations. From this the critical coagulation concentration values were identified as 30, 40, and 2 mM for NaNO(3), NaCl, and CaCl(2), respectively. Although the silver nanoparticles were observed to dissolve in all three electrolyte solutions, the aggregation results were still consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The dissolution of the silver nanoparticles, which were coated with a layer of Ag(2)O, was highly dependent on the electrolyte type and concentration. In systems with Cl(-) a secondary precipitate, likely AgCl, also formed and produced a coating layer that incorporated the silver nanoparticles. Aggregation of the silver nanoparticles was also examined in the presence of Nordic aquatic fulvic acid and was little changed compared to that evaluated under identical fulvic acid-free conditions. These results provide a fundamental basis for further studies evaluating the environmental fate of silver nanoparticles in natural aquatic systems.     

Fabrication of flower-like silver structures through anisotropic growth

Using a simple chemical reaction, a new nanostructure of silver, which we call a "flower-like silver structure", is produced. The flower-like silver structure consists of a silver core and many rod-like tips protruding out in three dimensions. Besides common face-centered-cubic (FCC) phase of silver, there exists hexagonal-close-packed (HCP) phase in these tips. The appearance of HCP silver is the result of rapid growth of silver nuclei when using CH(2)O or C(2)H(4)O as the reducing agent. The formation of the rod-like tips is caused by the anisotropic growth determined by the HCP phase and the directing role of formic acid, which is the oxidation product of CH(2)O. It is also found that the concentration of reactants, the kind of reducing agents and the sequence of adding reactants can influence the morphology and phase constitution of the final products.     

Biosynthesis of silver nanocrystals by Bacillus licheniformis

The use of microorganisms for the synthesis of nanoparticles is in the limelight of modern nanotechnology. Using the bacterium Bacillus licheniformis, the biosynthesis of silver nanoparticles was investigated. These silver nanoparticles were characterized by means of UV-vis spectroscopy, scanning electron microscopy (SEM), electron diffraction spectroscopy (EDX) and X-ray diffraction (XRD). The nanoparticles exhibited maximum absorbance at 440 nm in UV-vis spectroscopy. The XRD spectrum of silver nanoparticles exhibited 2theta values corresponding to the silver nanocrystal. SEM micrographs revealed the formation of well-dispersed silver nanoparticles of 50 nm, and the presence of silver was confirmed by EDX analysis.     

Recovery of silver from silver chloride residues

A new chemical process for recovering silver metal from waste silver chloride residues is described. The silver chloride is digested in an oxidizing mixture before complexation with ammonia. High-purity free silver metal is precipitated from solution by the addition of ascorbic acid as the reducing agent.     

Hydrothermal-induced assembly of colloidal silver spheres into various nanoparticles on the basis of HTAB-modified silver mirror reaction

Small colloidal silver spheres (diameter < 10 nm) were found to assemble into various silver nanoparticles including cubes, triangles, wires, and rods in water in the presence of HTAB (n-hexadecyltrimethylammonium bromide) at 120 degrees C, while the colloids were generated in situ on the basis of a HTAB-modified silver mirror reaction during the synthesis process. Adjustment of the synthesis parameters, in particular the concentrations of HTAB and [Ag(NH3)2]+, led to an obvious shape evolution of silver nanoparticles, thus resulting in the shape-selective formation of the silver nanoparticles. The monodisperse nanocubes with a well-defined crystallographical structure (a single crystal bounded by six {200} facets) have a strong tendency to assemble into two-dimensional arrays on substrates. The nanowires with uniform diameter usually existed in the form of two-dimensional alignments. The findings suggested that hydrothermal-induced assembly of small silver colloidal particles should be a convenient and effective approach to the preparation of various silver nanoparticles.     

A novel shape-selective fabrication of nanostructured silver

A novel protection-reduction technique is developed for the preparation of silver nanoparticles, nanorods and wheatear-like supramolecular nanostructures at room temperature using silver potassium cyanide [KAg(CN)2] as a silver source, vitamin C (Vc) as a reducing agent and polyvinylpyrrolidone (PVP) as a protecting agent. The concentration of KAg(CN)2, the mole ratios of PVP/Vc and KAg(CN)2/Vc have significant effects on the formation and growth of these novel nanostructures. This method may be extended to prepare novel nanostructures of other metals.     

Photo-induced chemical reduction of silver bromide to silver nanoparticles

This paper discusses the experimental results of the production of nanocolloidal silver using photoreduction method. Ultrafine crystalline gelatine-stabilised aqueous suspensions of silver bromide were used as a substrate for the synthesis of silver nanoparticles (Ag NPs). The influences of the reductant to substrate molar ratio, the medium’s pH, the type of the source of actinic radiation and the time of exposure to the efficient production of the Ag NPs were studied. A typical reaction was suggested, which involves the photo-induced reduction of silver bromide nanocrystals in the presence of ascorbic acid under specified physicochemical conditions. The properties of resultant silver particles were examined using UV-Vis spectroscopy and Dynamic Light Scattering (DLS). In addition, Transmission Electron Microscopy (TEM) was used for imaging the silver nanoparticle suspensions.      

Dye-labeled silver nanoshell-bright particle

Silica beads with average diameters of 40-600 nm were prepared, and Ru(bpy)3(2+) complexes were incorporated into the beads. These beads were coated by silver layer by layer to generate porous but continuous metal nanoshells. The thicknesses of these metal shells were 5-50 nm. The emission band from the dyes in the silica cores was more narrow and the intensity was enhanced with growth of silver shell thickness due to coupling of the emission light from Ru(bpy)3(2+) in the cores with the metal plasmon from the silver shells. The enhancement of emission intensity was also dependent on the size of the silica core, showing that the enhancement efficiency decreased with an increase in the size of the silica beads. Lifetime measurements support the coupling mechanism between the dye and metal shell. This study can be used to develop novel dye-labeled metal particles with bright and narrow emission bands.     

Facile size-regulated synthesis of silver nanoparticles by controlled thermolysis of silver alkylcarboxylates in the presence of alkylamines with different chain lengths

Controlled thermolysis of silver alkylcarboxylates with primary alkylamines was investigated as a facile synthetic method of silver nanoparticles. A series of silver alkylcarboxylates, C(7)H(15)COOAg, C(13)H(27)COOAg, and C(17)H(35)COOAg, have been prepared and the thermolysis of those silver alkylcarboxylates in the presence of various alkylamines, C(8)H(17)NH(2), C(12)H(25)NH(2), and C(18)H(37)NH(2), with no use of solvent was conducted at 120 or 180 degrees C for 5 h, providing spherical silver nanoparticles stabilized by alkylcarboxylates and alkylamines. The size and dispersibility of nanoparticles depend on the alkyl chain length of the precursors, alkylcarboxylates and alkylamines.