Nucleation of silver upon the reduction by hydrogen in aqueous polyphosphate-containing solutions: Formation of clusters and nanoparticles

In the reduction of Ag⁺ ions by hydrogen in aqueous polyphosphate-containing solutions, the formation of metal nanoparticles is preceded by the emergence of clusters comprising a few silver atoms and ions. In the process of cluster aggregation, their nuclearity increases and quasi-metallic particles followed by metal nanoparticles are formed. The efficiency of nanoparticle formation rises with the increasing concentration of polymer stabilizer. The mechanism of the formation of hydrosol is discussed.     

Formation of long-lived clusters and silver nucleation in the γ-irradiation of aqueous silver perchlorate solutions containing polyphosphate

It was found that long-lived positively charged and neutral silver clusters were formed by the radiation-chemical reduction of Ag⁺ ions in aqueous solutions containing sodium polyphosphate. The nuclearity of the clusters increased with absorbed dose; then, quasi-metal particles were formed. The process culminated in the formation of silver nanoparticles.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 2, 2005, pp. 83–87.Original Russian Text Copyright © 2005 by Ershov, Abkhalimov, Sukhov.This revised version was published online in April 2005 with a corrected cover date.     

Preparation of silver nanoparticles in aqueous solutions in the presence of carbonate ions as stabilizers

Silver nanoparticles are prepared by reducing Ag⁺ ions with sodium borohydride in aqueous solutions containing carbonate ions (5 × 10⁻⁵−1 × 10⁻² mol l⁻¹). It is established that carbonate ions represent an efficient stabilizer that provides nanoparticles with electrostatic protection via the formation of an electrical double layer. The maximum stability of a silver dispersion is observed at a carbonate ion concentration of 1 × 10⁻³ mol l⁻¹. The average size of silver nanoparticles is 10.0 ± 2.5 nm. The formation kinetics of silver nanoparticles is described by an equation for a first-order reaction with a rate constant of 2.3 × 10⁻³ s⁻¹ (±20%).     

Polyethylenimine complexes with silver ions in aqueous solutions as precursors for synthesis of monodisperse silver iodide particles

The conditions of formation and composition of polyethylenimine complexes with silver ions in aqueous solutions are found. The complex is formed according to the model of a uniform distribution of ions throughout the macromolecule, and the composition of the complex may vary depending on pH of the medium. The size parameters are determined and the volume fractions of polyethylenimine macromolecular coils in solution are calculated. The synthesis of silver iodide particles is carried out under conditions where the silver ions are bound in the complex with polyethylenimine macromolecules and are distributed homogeneously over the volume of solution. The use of the polyethyleneimine complex with silver ions as a precursor of silver iodide allows the preparation of particles 1.2 nm in diameter with a narrow size distribution.     

Raman spectra of formate and acetate ions adsorbed on silver particles in aqueous solutions

Raman spectra from the surfaces of black silver particles formed by reduction of silver ions in aqueous solutions have been interpreted as arising from adsorbed formate and adsorbed acetate ions.     

The influence of Ag+ ions on transformations of silver clusters in polyacrylate aqueous solutions

It is shown that transformations of unstable clusters, intermediates of the borohydride reduction of silver cations, in weakly alkaline polyacrylate aqueous solutions are governed by the competition between the processes of their oxidation, coalescence into larger particles, and reduction of silver cations. Moreover, these processes depend on the loading of a polyanion with cations and can be controlled by the addition of Ag⁺ ions.     

Homogeneous nucleation temperatures in aqueous mixed salt solutions

This is the first report on the measurement of homogeneous nucleation temperature, TH, in the presence of aqueous mixed salt systems of varying compositions and ionic strengths. The TH,m (TH value in aqueous mixed salt system) data for these systems have been analyzed in terms of a simple empirical equation. The TH,m values in simple aqueous mixed salts like NaCl-KCl can be approximated by linear summation of the products of ionic strength fraction and the TH values of pure salt solutions at the same ionic strength as that of the mixture. The empirical parameter, q0, indicating ionic interaction is related to the viscosity B-coefficients. The TH,m data, though correlated on the basis of the B-coefficients also depends upon the mixing of two ions of like charges. Further, a linear correlation exists between the q0 parameter and self-diffusion coefficient, D0, of the ionic solute. The q0 parameter is also well correlated with the rotational correlation time, tauch/tauc0 of the ionic species involved in the mixtures. It is possible to compute TH,m for the salt mixtures with no common ions from the knowledge of the TH,m values of the salt mixtures with common ions.     

Colloidal copper and peculiarities of its reaction with silver ions in aqueous solution

Interactions between colloidal copper and silver ions lead to the formation of silver nanoparticles. The reaction proceeds through the intermediate stage of the formation of a copper-silver contact pair. The formation of bimetallic Ag_coreCu_shell nanoparticles is observed in the presence of the “seeding” silver nanoparticles and upon the simultaneous radiochemical reduction of Ag⁺ and Cu²⁺ ions.     

Adsorption preconcentration of pyrene by silver nanoparticles and its determination in aqueous solutions

The reduction of silver nitrate with sodium borohydrate in an aqueous medium in the presence of cetyl trimethylammonium bromide gives a stable sol of silver, which can adsorb nonpolar organic compounds, e.g., polycyclic aromatic hydrocarbons, on the surface of metal nanoparticles. The subsequent luminescent determination demonstrated the effect of sensitized luminescence of silver nanoparticles, which could provide a basis for the determination of traces of polycyclic aromatic compounds in water.     

Synthesis of silver nanoclusters in starch aqueous solutions

The capability of aqueous starch solution for reduction of Ag⁺ ions and stabilization of metallic silver nanoparticles was examined. Kinetic parameters of formation of Ag nanoparticles were determined.     

Electrochemical reduction of actinide ions in aqueous solution

Electrochemical reduction of heavy elements from aqueous solution to amalgams was studied by radiopolarography and radiocoulometry. Mechanism of actinide reduction on a mercury pool is discussed through simulation techniques. Special emphasis is placed on redox reactions and potentials, kinetics of the process and effect of acetate and citrate ions as complexing agents. Three groups of actinides have been found. The first group represents actinium and from uranium to berkelium. Reduction occurs in the experimental conditions via an irreversible 3–0 process. The second group consists of the elements from fermium to nobelium, which are reduced in non-complexing solutions, or with acetate ions, similarly as barium and radium, via a reversible 2–0 reaction. Finally, californium and einsteinium behave as intermediate elements. It is noticeable that such groups are also observed in the actinide series by studying the structure of the trivalent aqua ions. On the basis of the above mentioned investigations of actinides and lanthanides several examples of electrochemical application are presented. Californium has been separated from preceding transuranium and lanthanide elements (except europium) by electrochemical reduction to amalgams in acetic solution. Separation factors from 25–90 are achieved with appropriate cathodic potentials. Similarly, this element could be separated from several heavier actinides with citric media. The electrochemical preparation of mixed uranium-nickel and uranium-tin amalgams from aqueous acetate solutions is investigated. The dependence of redox potentials of mixed amalgams on different atomic ratio UNi and USn in amalgams is measured. The large shift of redox potentials of mixed amalgams to the positive direction is detected when the atomic ratio UNi or USn in amalgams reaches 15. The thermal distillation of mercury from mixed amalgams with different UNi and USn atomic ratios was carried out and the products were identified by chemical analysis and X-ray diffraction. The intermetallics UNi₅ and USn₃ were prepared from mixed amalgams with the atomic ratios UNi=15 and USn=13. The uranium and neptunium amalgams are prepared by electrolysis of aqueous acetate solutions and are processes into metals or nitrides U₂N₃, NpN by thermal distillation of mercury in vacuum or in nitrogen atmosphere.     

Thermochemical transformations of hydrocarbonate ions in aqueous solutions

The influence of heat treatment on the reactivity index k ₁, pH value, and content of hydrocarbonate ions HCO₃⁻ in an aqueous solution was examined. The factors responsible for enhanced reactivity of thermally activated water were discussed.     

Heterogeneous ice nucleation in aqueous solutions: the role of water activity

Heterogeneous ice nucleation experiments have been performed with four different ice nuclei (IN), namely nonadecanol, silica, silver iodide and Arizona test dust. All IN are either immersed in the droplets or located at the droplets surface. The IN were exposed to various aqueous solutions, which consist of (NH4)2SO4, H2SO4, MgCl2, NaCl, LiCl, Ca(NO3)2, K2CO3, CH3COONa, ethylene glycol, glycerol, malonic acid, PEG300 or a NaCl/malonic acid mixture. Freezing was studied using a differential scanning calorimeter and a cold finger cell. The results show that the heterogeneous ice freezing temperatures decrease with increasing solute concentration; however, the magnitude of this effect is solute dependent. In contrast, when the results are analyzed in terms of the solution water activity a very consistent behavior emerges: heterogeneous ice nucleation temperatures for all four IN converge each onto a single line, irrespective of the nature of the solute. We find that a constant offset with respect to the ice melting point curve, Deltaaw,het, can describe the observed freezing temperatures for each IN. Such a behavior is well-known for homogeneous ice nucleation from supercooled liquid droplets and has led to the development of water-activity-based ice nucleation theory. The large variety of investigated solutes together with different general types of ice nuclei studied (monolayers, ionic crystals, covalently bound network-forming compounds, and a mixture of chemically different crystallites) underlines the general applicability of water-activity-based ice nucleation theory also for heterogeneous ice nucleation in the immersion mode. Finally, the ice nucleation efficiencies of the various IN, as well as the atmospheric implication of the developed parametrization are discussed.     

Kinetics of silver nanoparticle growth in aqueous polymer solutions

Silver nanoparticles were prepared in aqueous AgNO₃ solution by using hydroquinone and sodium citrate as reducing agents with neutral polymers poly(vinylpyrrolidone) and poly(vinyl alcohol) as stabilizers. The rate of particle formation was determined with a diode array UV-Vis spectrophotometer. The effects of the polymer concentration on the reaction rate, the size, and the size distribution of the particles formed were studied by transmission electron microscopy. Both the reaction rate and the size of silver nanoparticles decreased with increasing polymer concentration in the range 0.07–0.50 w/v%.     

Precipitation and association of silver laurate in aqueous solutions

The temperature dependency of silver laurate solubility at various concentrations of precipitation components was investigated. Interpretation of the data indicated the formation of silver laurate ion pairs. The equilibrium constants for the precipitation and for ion pairing processes were calculated for the temperature range between 20 and 60 °C. The enthalpy of silver laurate precipitation was obtained by calorimetry. The agreement of the solubility and calorimetric data showed that no change in the structure of silver laurate occurred as the temperature was varied.