Effect of the rate of diffusion of ions on the periodic precipitation of silver chromate

The effect of the rate of diffusion on the formation ofLiesegang rings of silver chromate in gelatin and agar agar medium has been studied. The rate of diffusion of silver ions in the agar agar gel is much slower than that in gelatin gel during the formation of rings of silver chromate. If the rate of diffusion of silver ions in agar agar gel is increased, even then rings do not form. The only change brought about by the rate of diffusion is for the distance between the successive rings.

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Zusammenfassung Der Einflu\ der Diffusionsgeschwindigkeit auf die Bildung vonLiesegang-Ringen aus Silberchromat in Gelatine und Agar-Agar wurde untersucht. Die Diffusionsgeschwindigkeit der Silberionen in den Agar-Agar-Gelen ist viel niedriger als in den Gelatinegelen während der Bildung der Ringe von Silberchromat. Wenn die Diffusionsgeschwindigkeit der Silberionen in Agar-Agar-Gelen gesteigert wird, bilden sich schlie\lich überhaupt keine Ringe. Der einzige Einflu\, den die Diffusionsgeschwindigkeit hervorruft, ist also änderung des Abstandes aufeinanderfolgender Ringe.

     

Room temperature synthesis of silver nanowires from tabular silver bromide crystals in the presence of gelatin

Long silver nanowires were synthesized at room temperature by a simple and fast process derived from the development of photographic films. A film consisting of an emulsion of tabular silver bromide grains in gelatin was treated with a photographic developer (4-(methylamino)phenol sulfate (metol), citric acid) in the presence of additional aqueous silver nitrate. The silver nanowires have lengths of more than 50 μm, some even more than 100 μm, and average diameters of about 80 nm. Approximately, 70% of the metallic silver formed in the reduction consists of silver nanowires. Selected area electron diffraction (SAED) results indicate that the silver nanowires grow along the [111] direction. It was found that the presence of gelatin, tabular silver bromide crystals and silver ions in solution are essential for the formation of the silver nanowires. The nanowires appear to originate from the edges of the silver bromide crystals. They were characterized by transmission electron microscopy (TEM), SAED, scanning electron microscopy (SEM), and powder X-ray diffraction (XRD).     

Role of anions for the reduction behavior of silver ions in polymer/silver salt complex membranes

The reduction of silver ions to silver nanoparticles is an essential issue in polymer/silver salt complex membranes for facilitated olefin transport, because it has a critical influence on the long-term stability of membrane performance. In this study, the role of anions for the formation of silver nanoparticles in polymer/silver salt complexes was investigated. This role was assessed for the complexes of poly(N-vinyl pyrrolidone) (PVP) with three silver salts including AgBF₄, AgCF₃SO₃, and AgNO₃. Especially, UV irradiation to the membranes was used to clearly investigate the reduction behavior of silver ions. Separation performance test, UV–vis spectroscopy and transmission electron microscopy (TEM) clearly show that the reduction rate of silver ions strongly depends on the counteranions of salt, and has the following order: AgBF₄ > AgCF₃SO₃ > AgNO₃. This behavior of the formation of silver nanoparticles in polymer/silver salt complex membranes is explained in terms of the interaction strength of silver ions with the carbonyl oxygens of polymer, and that of silver ions with counteranions. It is concluded that when the former interaction is strong and the latter one is weak, the reduction rate of silver ions to silver nanoparticles is fast, and vice versa. These interactions were characterized using FT-IR, FT-Raman spectroscopy, and theoretical ab initio calculation.     

Preparation of Pt<Subscript>core</Subscript>Ag<Subscript>shell</Subscript> nanoparticles: Catalytic reduction of Ag<Superscript>+</Superscript> ions by hydrogen

It is shown that the saturation of an aqueous solution containing silver ions with hydrogen in the presence of 9.5-nm platinum nanoparticles leads to the reduction of silver and the formation of Pt_coreAg_shell bimetal nanoparticles. An increase in the concentration of silver ions gives rise to a number of elementary silver layers that cover the platinum core. It is established that the concentration of silver ions does not substantially affect the rate of the formation of a silver shell on the surface of platinum nanoparticles.     

Molecular mechanism of the photochemical generation of gold nanoparticles in ethylene glycol: support for the disproportionation mechanism

It is found that replacement of the chloride ions in tetrachloroauric acid with bulky bromide ions inhibits the formation of gold nanoparticles in the photochemical reduction in ethylene glycol. However, the addition of silver ions to either the bromide or the chloride auric acid solution is found to enhance the rate of gold nanoparticle formation. These results are found to be accounted for by the previously proposed mechanism (Eustis, S.; Hsu, H.-Y.; El-Sayed, M. A. J. Phys. Chem. B 2005, 109, 4811) which involves disproportionation of the chloroauric complexes to generate free gold atoms and chloride ions. The steric effects of the bulky bromide ions inhibit the formation of the Au-Au bond needed in the electron transfer process of the disproportionation reaction. The addition of Ag+ ions results in the formation of insoluble silver halide, which shifts the disproportionation reaction toward the formation of gold atoms and thus the formation of gold nanoparticles.     

On the Chemical Processes Accompanying Silver Reduction from Solutions of Its Salts in Organic Media

Silver reduction from its nitrate has been studied in the media of DGEBA-based and aliphatic epoxy resins. It has been found that, under the experimental conditions that were employed, silver ions can be reduced without chemical interaction with the medium only due to photochemical processes. The reduction rate is determined by the rate of dissolution of the initial silver salt in an organic medium and the possibility of the formation of solvates by the system components. Refractometry has been proposed for use in monitoring the kinetics of silver nitrate dissolution in epoxy resins and the formation of silver nanoparticles. Stable dispersions of silver nanoparticles in epoxy resins have been obtained.     

Reduction and aggregation of silver ions in <Emphasis Type="Italic">tert</Emphasis>-butanol

Silver ions undergo reduction reactions induced by radiolytically produced products of tert-butanol, a commonly used solvent and scavenger for hydroxyl radicals. Radiolytic reduction of silver ions and the subsequent formation of their clusters are compared with the corresponding processes in aqueous solution. The surface plasmon UV-Vis absorption band of silver nanocrystallites obtained by bombardment of tert-butanol solutions of silver salts with electron pulses showed an absorption maximum at 400 nm. Formation of different sizes of silver nanoparticles was found to be dependent on the dose rate. The nanocrystallites were found to have an average size of 20 nm.     

Fundamental studies on the intermediate layer of a bipolar membrane V. Effect of silver halide and its dope in gelatin on water dissociation at the interface of a bipolar membrane

The effect of silver ions on the water dissociation of bipolar membranes was first investigated in this paper. To do this, the bipolar membranes were prepared by immersing the anion exchange layers in an AgNO3 solution and then coating a solution of sulfonated polyphenylene oxide (SPPO) on the anion exchange layers. XPS and AES observations indicated that silver at the intermediate layer was in the form of AgCl. The experimental results proved that AgCl has an excellent catalytic function for water dissociation in terms of I-V curves, and the quantity of AgCl played an important role in the behavior of a bipolar membrane. The bipolar membranes with gelatin and the gelatin doped with silver as a catalytic layer were also prepared in the same way, and their I-V behavior and the water dissociation pilot tests were also investigated. The experimental results showed that in the case of gelatin alone, the voltage drop increased slightly at high gelatin concentrations, due mainly to the steric effect and electrostatic interaction, but decreased at low gelatin concentrations due to the hydrophilicity. However, when gelatin was doped with AgCl, the bipolar membranes have an appreciable improvement in both stability and catalytic function, in comparison with those prepared from silver or gelatin.     

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.     

Synthesis,characterization, and application of monodisperse gelatin-stabilized silver nanospheres in reduction of aromatic nitro compounds

Monodisperse colloidal silver nanospheres were synthesized by the reaction of silver nitrate, hydroxylammonium hydrosulphate (NH₂OH)₂ · H₂SO₄ and sodium hydroxide in the presence of gelatin as stabilizer. Colloidal nanospheres were characterized by UV-vis absorption spectroscopy, transmission electron microscopy, X-ray diffraction and dynamic light scattering. X-ray diffraction data confirmed that the silver nanospheres were crystalline with face-centered-cubic structure. Transmission electron microscopy analysis revealed the formation of homogeneously distributed silver nanoparticles of spherical morphology and size of the nanoparticles was in the range of 0.7–5.2 nm. Silver nanospheres were stable for more than two months when stored at ambient temperature. Size and size distribution were studied by varying pH, reaction temperature, silver ion concentration in feed solution, concentration of reducing agent and concentration of the stabilizing agent. Catalytic activity of silver nanospheres was tested for the reduction reaction of nitro compounds in sodium borohydride solution. Monodisperse silver nanospheres showed excellent catalytic activity towards the reduction of aromatic nitro compounds. The reduction rate of aromatic nitro compounds had been observed to follow the sequence 4-nitrophenol > 2-nitrophenol > 3-nitrophenol.     

Complexation of phthalate oxygens in poly(ethylene phthalate) with silver ions and its effect on the formation of silver nanoparticles

The interaction of a phthalate group in poly(ethylene phthalate) (PEP) with silver ion has been elaborated in detail to understand the reduction behavior of silver ions to silver nanoparticles. Previously, the polymer electrolytes consisting of silver ions dissolved in PEP have shown highly stable separation performance for propylene/propane mixtures primarily due to the retardation of the reduction reaction of silver ions to silver nanoparticles, which is possible by means of the chelating bonds between phthalate groups and silver ions. Thus, in this study, the interaction was systematically investigated by both the theoretical ab initio calculation and the experimental Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. The results show that the interaction of silver ion with phthalate group in PEP is approximately two times stronger than that with other functional groups such as amide, ketone, and ester in various polymers, in which the latter ones show the rapid reduction reaction and consequently lose their olefin carrier activity with time. Therefore, it is concluded that the reduction reaction of silver ions to silver nanoparticles is retarded remarkably in PEP/silver salts systems primarily because of the strong interaction between the phthalate group in PEP and silver ion, and consequently the formation of silver nanoparticles would be effectively prohibited, as confirmed by transmission electron microscopy and ultraviolet–visible spectroscopy. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3344–3350, 2004     

Effect of the polymer matrix on the formation of silver nanoparticles in polymer–silver salt complex membranes

When polymer–silver salt complex membranes were exposed to UV irradiation, the separation performances of both the permeance and selectivity for propylene–propane decreased, which was primarily attributed to the reduction of the silver ions in the membranes to silver nanoparticles. Here, the effect of the polymer matrix on the formation of silver nanoparticles in the polymer–silver salt complex membranes was investigated. This effect was assessed for the complexes of two kinds of silver salts (AgBF₄ and AgCF₃SO₃) with several polymeric ligands containing three different carbonyl groups, including poly(vinyl pyrrolidone) (PVP) with an amide group, poly(vinyl methyl ketone) (PVMK) with a ketone group, and poly(methyl methacrylate) (PMMA) with an ester group. UV–vis spectra and transmission electron microscopy (TEM) images clearly indicated that the reduction rate of the silver ions has the following order in the various polymer matrices: PVP > PVMK > PMMA, whereas the size and the distribution of the nanoparticles exhibited the reverse order. The tendency to form silver nanoparticles was explained in terms of the differences between the comparative strengths of the interactions of the silver ions with the different carbonyl oxygens in the matrices, as well as that of the silver ions with counteranions, which was characterized by X‐ray photoelectron spectroscopy (XPS) and FT‐Raman spectroscopy. It was concluded that when the concentration of free silver ions was low due to weak polymer–silver ion and strong silver ion–anion interactions, as found with PMMA, the reduction rate of silver ions to silver nanoparticles was slow. Therefore, the PMMA–silver complex membranes were less sensitive to decreases in separation performance upon UV irradiation than compared to the PVP membranes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1168–1178, 2006     

Role of phenol derivatives in the formation of silver nanoparticles

We demonstrate that dihydroxy benzenes are excellent reducing agents and may be used to reduce silver ions to synthesize stable silver nanoparticles in air-saturated aqueous solutions. The formation of Ag nanoparticles in deaerated aqueous solution at high pH values suggests that the reduction of silver ions occurs due to oxidation of dihydroxy benzenes and probably on the surface of Ag2O. Pulse radiolysis studies show that the semi-quinone radical does not participate in the reduction of silver ions at short time scales. Nevertheless, results show that primary intermediates undergo slower transformation in the presence of dihydroxy benzenes than in their absence. This slow transformation eventually leads to the formation of silver nanoparticles. The Ag nanoparticles were characterized by UV-vis absorption spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). XRD and TEM techniques showed the presence of Ag nanoparticles with an average size of 30 nm.     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法,以气/液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜.考察了镀液pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响.实验发现,酸性镀液的气/液界面上形成的单分子膜不能诱导沉积银,而在中性和碱性镀液的气/液界面上可以诱导银膜的生长.当单分子膜处于液态或固态时,气/液界面有银膜形成;液态单分子膜上的银膜生长速度较快,且银膜的结构一致.随着电极电位的升高,银膜沉积的速度加快,呈环状向外生长的圆形银膜逐渐变得不规则.将不同实验条件下的银膜转移出来,采用扫描电镜(SEM)、透射电镜(TEM)对银膜的结构与形貌进行了表征.研究表明,银首先在单分子膜上异相成核,由八面体构型逐渐发展成星型,最终在气/液界面形成具有松枝状微观结构的光亮银膜.     

Antibacterial activity of silver bionanocomposites synthesized by chemical reduction route

ABSTRACT: BACKGROUND: The aim of this study is to investigate the functions of polymers and size of nanoparticles on the antibacterial activity of silver bionanocomposites (Ag BNCs). In this research, silver nanoparticles (Ag NPs) were incorporated into biodegradable polymers that are chitosan, gelatin and both polymers via chemical reduction method in solvent in order to produce Ag BNCs. Silver nitrate and sodium borohydride were employed as a metal precursor and reducing agent respectively. On the other hand, chitosan and gelatin were added as a polymeric matrix and stabilizer. The antibacterial activity of different sizes of silver nanoparticles was investigated against Gram-positive and Gram-negative bacteria by the disk diffusion method using Mueller-Hinton Agar. RESULTS: The properties of Ag BNCs were studied as a function of the polymer weight ratio in relation to the use of chitosan and gelatin. The morphology of the Ag BNCs films and the distribution of the Ag NPs were also characterized. The diameters of the Ag NPs were measured and their size is less than 20 nm. The antibacterial trait of silver/chitosan/gelatin bionanocomposites was investigated. The silver ions released from the Ag BNCs and their antibacterial activities were scrutinized. The antibacterial activities of the Ag BNC films were examined against Gram-negative bacteria (E. coli and P. aeruginosa) and Gram-positive (S. aureus and M. luteus) by diffusion method using Muller-Hinton agar. CONCLUSIONS: The antibacterial activity of Ag NPs with size less than 20 nm was demonstrated and showed positive results against Gram-negative and Gram-positive bacteria. The Ag NPs stabilized well in the polymers matrix.     

Reduction of silver(II) oxide by the solvent in acid media

The reaction of silver(II) oxide with water to yield silver(I) ions and oxygen is an important side-reaction in procedures which use silver(II) oxide as the oxidant. This reaction has been examined in solutions which were 0.01-1M in respect to sulphuric or perchloric acid. The rate of reduction varied directly with the amount of solid added and was a complex function of the concentrations of hydrogen ions, silver(I) ions and anions present. The kinetic results have been used to postulate a mechanism for the reaction.     

Condition of lead iodide in the medium of lyophilic sols

The condition of lead chromate in gelatin and agar agar medium has been studied. In presence of agar agar medium the colloid formed is stabilised by lead ions and coagulated by the excess of chromate ions. Lead chromate forms a very stable colloid in the presence of gelatin sol which could not be precipitated by excess of lead ions or chromate ions. Due to the formation of a very stable colloid in gelatin medium, well defined rings of lead chromate are not obtained in gelatin gel.     

Synthesis and physicochemical properties of silver nanoparticles stabilized by acid gelatin

Silver nanoparticles were synthesized by the reduction of silver nitrate with sodium borohydride at widely varied concentrations of the starting reagents. A physicochemical study of the synthesized nanosystems was carried out. The stabilizing ability of acid gelatin in the systems under study was considered. The stability diagram in the coordinates initial concentration of silver nitrate-concentration of gelatin was constructed.     

Linear silver clusters in aqueous solution (clusterites): radiation-induced chemical synthesis and properties

The formation and properties of the products of the radiation-induced chemical reduction of silver ions in aqueous solutions containing sodium polyacrylate were investigated. The absorption spectra of these species exhibit a band at 290 mn and a band in the visible region. The latter shifts from 470 nm to -800 nm with time or after the addition of silver ions. The species obtained (clusterites) arc linear silver clusters bound to the carboxyl groups of the ion exchanger. The red shift of the visible band is due to the increase in their size. The mechanism of the formation and the structure of the clusterites are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1429–1435, June, 1996.     

Preparation of Phenolic Resin/Silver Nanocomposites via in-situ Reduction

Polymer/metal nanocomposites have attracted considerable interest because of their potential application in catalysts, electronics, electromagnetics and nonlinear optics1-3. They have been prepared by blending polymer with nanometer metal particles4, reducing polymer-metal ion complexes with reducing agents5, and reducing metal ions in the polymer matrix by high-energy radial irradiation3. In this paper, we report a new approach to phenolic resin/silver nanocomposites, which have potential a…