Polyaniline-silver composites prepared by the oxidation of aniline with mixed oxidants, silver nitrate and ammonium peroxydisulfate: The control of silver content

Aniline was oxidized with mixtures of two oxidants, ammonium peroxydisulfate and silver nitrate, to give polyaniline-silver composites with variable content of silver in the composites. The presence of peroxydisulfate has a marked accelerating effect on the oxidation of aniline with silver nitrate. Oxidations in 1 M methanesulfonic acid produced composites in high yield. The molecular structure of the polyaniline was confirmed by UV-visible and FTIR spectra, and the polymeric character was established by gel-permeation chromatography. The content of silver varied between 0 and 70 wt.%. The silver nanoparticles were smaller than 100 nm. The conductivity of the composites was of the order of units S cm⁻¹. Only at high silver nitrate contents in the reaction mixture, the conductivity of products exceeded 100 S cm⁻¹. The conductivity of the composites sometimes increased after deprotonation of the polyaniline salt to a non-conducting base. Such conductivity behaviour is discussed in terms of the percolation model.     

Novel high dielectric constant nanocomposites of polyaniline dispersed with γ‐Fe2O3 nanoparticles

Novel nanocomposites of polyaniline dispersed with γ‐Fe₂O₃ nanoparticles were prepared by the in situ polymerization of aniline in the presence of ammonium peroxysulfate as an oxidizing agent. Dielectric constants of the derived composites varied with the composition of γ‐Fe₂O₃ present in the matrix. A maximum dielectric constant of ～5500 was achieved when 10 mass % γ‐Fe₂O₃ nanoparticles were present. Nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared, scanning electron microscopy, and thermal analytical techniques. Conductivity increased marginally by increasing the amount of γ‐Fe₂O₃ in the matrix. Dielectric constants increased 100–150 times compared to plain polyaniline matrix and were 20–40 times higher than that of γ‐Fe₂O₃ nanoparticles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1868–1874, 2005     

Polyaniline–silver composites prepared by the oxidation of aniline with silver nitrate in acetic acid solutions

The reaction between two non‐conducting chemicals, aniline and silver nitrate, yields a composite of two conducting components, polyaniline and metallic silver. Such conducting polymer composites combine the electrical properties of metals and the materials properties of polymers. In the present study, aniline was oxidized with silver nitrate in solutions of acetic acid; in this context, aniline oligomers are often a major component of the oxidation products. An insoluble precipitate of silver acetate is also present in the samples. The optimization of reaction conditions with respect to aniline and acetic acid concentrations leads to a conductivity of the composite as high as 8000 S cm^?1 at ca 70 wt% (ca 21 vol%) of silver. A sufficient concentration of acetic acid, as well as a time extending to several weeks, has to be provided for the successful polymerization of aniline. Polyaniline is present as nanotubes or nanobrushes composed of thin nanowires. The average size of the silver nanoparticles is 30–50 nm; silver nanowires are also observed. Copyright © 2009 Society of Chemical Industry     

A novel shape-controlled synthesis of dispersed silver nanoparticles by combined bioaffinity adsorption and TiO2 photocatalysis

Shape-controlled silver nanoparticles (Ag NPs) were prepared in a well-dispersed mode on the active imprinting sites of chitosan-TiO₂ adsorbent (CTA) by means of bioaffinity adsorption and TiO₂ photocatalysis. Nontoxic hydrogen peroxide (H₂O₂) was used as a suitable etching reagent in our production of shape-controlled Ag NPs, since it could regulate the TiO₂ photocatalysis and accelerate the generation of O₂. With the same amount of H₂O₂ addition, silver nanocubes, nanospheres and truncated triangular nanoplates were individually obtained on the surface of CTA under UV irradiation by facilely adjusting the initial Ag⁺ concentration. The FE-SEM, XRD and UV-visible characterizations confirmed single crystal Ag NPs with different shapes loaded on CTA. The mechanism for the formation of shape-controlled Ag NPs was discussed based on a photocatalytic reaction system. As an example of applications of the Ag NPs, we tested the biocidal properties, and silver nanocubes exhibited the highest antibacterial activity. Our research provided a simple synthesis for shape-regulated Ag NPs steadily loaded on CTA. It might moreover be a guide in preparing metal nanocrystals monodispersely immobilized on chemical substrates.     

The oxidation of aniline with silver nitrate to polyaniline-silver composites

Silver nitrate oxidizes aniline in the solutions of nitric acid to conducting nanofibrillar polyaniline. Nanofibres of 10-20 nm thickness are assembled to brushes. Nanotubes, having cavities of various diameters, and nanorods have also been present in the oxidation products, as well as other morphologies. Metallic silver is obtained as nanoparticles of ∼50 nm size accompanying macroscopic silver flakes. The reaction in 0.4 M nitric acid is slow and takes several weeks to reach 10-15% yield. It is faster in 1 M nitric acid; a high yield, 89% of theory, has been found after two weeks oxidation of 0.8 M aniline. The emeraldine structure of polyaniline has been confirmed by FTIR and UV-vis spectra. The resulting polyaniline-silver composites contain 50-80 wt.% of silver, close to the theoretical expectation of 68.9 wt.% of silver. The highest conductivity was 2250 S cm⁻¹. The yield of a composite is lower when the reaction is carried out in dark, the effect of daylight being less pronounced at higher concentrations of reactants.     

Ionic Liquid-assisted Synthesis of Polyaniline/Gold Nanocomposite and Its Biocatalytic Application

In this report, a novel chemical synthesis of polyaniline/gold nanocomposite is explored using ionic liquid (IL) 1-Butyl-3-methylimidazolium hexafluorophosphate. The direct chemical synthesis of polyaniline/gold nanocomposite was initiated via the spontaneous oxidation of aniline by AuCl₄ ⁻ in IL. A nearly uniform dispersion of polyaniline/Au particles with a diameter of 450 ± 80 nm was produced by this method, which indicates that this method is more suitable for controlling particle dimensions. It was also found that the electrical conductivity of the polyaniline/gold nanocomposite was more than 100 times higher than that of the pure polyaniline nanoparticles. The polyaniline/gold nanocomposite displays superior function in the biocatalytic activation of microperoxidase-11 because of the high surface area of the assembly and the enhanced charge transport properties of the composite material. We also report the possible application of polyaniline/gold nanocomposite as a H₂O₂ biosensor.     

Microwave Absorption Studies on Superparamagnetic Conducting Nanocomposites as Signal Coating Materials

In this paper, preparation and characterization of superparamagnetic nanoparticles and their polymer composites prepared by varing doping level of conducting polymer and their microwave absorption studies at radar system in 8–12 GHz frequency range have been discussed. These composites are conducting polymers have been widely used because of their lower density as well their good environmental stability as in the case of polyaniline (PAN). In the present work, in situ polymerization of aniline was carried out in the presence of 30 mole% Fe₃O₄ nanoparticles to synthesize polyaniline/Fe₃O₄(PAN/Fe₃O₄) composites in epoxy resin matrix. The composites, thus synthesized have been characterized by infrared (IR) spectroscopy and X-ray diffraction. The morphology of these composites was studied by scanning electron microscopy. The measurement of % absorption was carried out in X and K band microwave region.     

Facile synthesis,antibacterial mechanisms and cytocompatibility of Ag–MnFe2O4 magnetic nanoparticles

Magnetic MnFe₂O₄ nanoparticles containing 0, 1 and 3 at.% silver, respectively were synthesized by one-pot sol-gel method for antibacterial applications in biomedical fields. Material characterizations indicate that MnFe₂O₄ begins crystallization at 134 °C and oxidation at 450 °C, the grain size and agglomeration degree increase with the silver content and silver exists as metallic state for the particles. The saturation magnetization decreases with the sintering temperature and slightly increases with the silver content, with the maximum of 50.0 emu/g obtained. Antibacterial tests by plate counting and PI-Hoechst 33342 staining suggest that the antibacterial activity of Ag–MnFe₂O₄ nanoparticles is silver content-dependent. Silver ions concentration measurement, β-galactosidase activity assay and transmission electron microscopic observation show that the antibacterial activity is dominated by the actions of the released silver ions, rather than the membrane cell impairment or reactive oxygen species-induced oxidative stress mechanism. MC3T3-E1 cell test demonstrates the best cytocompatibility of the nanoparticles with 3 at.% silver, which is likely related to the reduced cell endocytosis of the aggregated particles. The combination of magnetism, antibacterial activity and biocompatibility would make Ag–MnFe₂O₄ nanoparticles a potential multi-functional material in various biomedical applications.     

A comparative study of the effect of addition of CeO x and Li2O on γ-Al2O3 supported copper, silver and gold catalysts in the preferential oxidation of CO

In the study described in this paper we deposited gold, silver and copper on γ-Al₂O₃ as nanoparticles (<4 nm) and investigated the behavior of these nanoparticles in the preferential oxidation of CO in presence of H₂. In addition, the effect of addition of CeO _x and/or Li₂O was investigated. All the three metals show preferential oxidation of CO at low temperatures. The oxides added to Au/γ-Al₂O₃, Ag/γ-Al₂O₃ and Cu/γ-Al₂O₃ improve the catalytic performance of the gold, silver and copper. Interesting and synergistic effects were observed when both the CeO _x and Li₂O were added. Possible mechanisms are proposed.     

Preparation and characterization of polyaniline powder synthesized on microstructured aluminium

Aluminium surfaces were microstructured in 0.1 M HNO₃ by potentiodynamic anodic activation to potentials generating pitting. This surface was then used as an electrode to prepare polyaniline powder. The number of pits is responsible for the amount of powder produced. Emeraldine salt powder was successfully prepared from 0.4 M aniline in 0.5 M H₂SO₄ solution. Other acid solutions for deposition are not convenient because powders are electrochemically inactive (e.g., in 1 M HNO₃) or the electrode is covered by a film (e.g., in 0.5 M H₂C₂O₄).     

Reversed micelle Synthesis of Ag/polyaniline nanocomposites via an in situ ultraviolet photo‐redox mechanism

Silver/polyaniline nanocomposites were synthesized in reversed micellar solution, and the reaction was performed via in situ reduction of silver nitrate in aniline by photolysis. The nanocomposites were characterized by ultraviolet‐visible spectroscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, thermo‐gravimetric analysis, differential scanning calorimetric analysis, and electrochemical methods. The results showed that the Ag/polyaniline nanocomposites are composed of nano‐sized particles of 15–30 nm that contain Ag domains of 10–15 nm. The electrical conductivity of an Ag/polyaniline pellet is 95.89 S cm⁻¹, whereas a polyaniline pellet is found to be 3.1 × 10⁻² S cm⁻¹. Ag/polyaniline composites also have a higher degradation temperature and specific capacitance, when compared with pure polyaniline. Potentiodynamic polarization showed the anodic shifting of the zero current potential and a lower exchange current density for the Ag/polyaniline composite. Compared with polyaniline, the Ag/polyaniline nanocomposite is a promising candidate for coatings with improved anticorrosion performance. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

Metal-assisted etching of p-type silicon under anodic polarization in HF solution with and without H2O2

Pore formation under anodic polarization of a lightly doped p-type Si wafer previously loaded with Pt, Pd and Ag nanoparticles was investigated in HF solution with and without H₂O₂. In HF solution without H₂O₂, a microporous layer was formed in p-Si loaded with Pt or Pd. However, Ag metal nanoparticles yielded pores due to their intrusion in the Si wafer. The addition of H₂O₂ to the etching solution leads to different pore morphologies depending on the metals. Particles of Ag were found at the bottom of most pores. In the presence of Pt nanoparticles, cone-shaped macropores were produced, and the pore depth and diameter increased with increasing H₂O₂ content. Current density influenced the pore morphology. For a sample loaded with Pt or Ag, an increase in applied current density widened the pore diameter. The mechanism of the metal-assisted pore formation was discussed by considering a competitive process between the formation of a microporous layer under polarization and metal-assisted chemical oxidation of the microporous layer by a dissolved oxidizing agent.     

Synthesis and characterization of polyaniline derivative and silver nanoparticle composites

BACKGROUND: There has been a recent surge of interest in the synthesis and applications of electroactive polymers with incorporated metal nanoparticles. These hybrid systems are expected to display synergistic properties between the conjugated polymers and the metal nanoparticles, making them potential candidates for applications in sensors and electronic devices. RESULTS: Composites of polyaniline derivatives—polyaniline, poly(2,5‐dimethoxyaniline) and poly(aniline‐2,5‐dimethoxyaniline)—and silver nanoparticles were prepared through simultaneous polymerization of aniline derivative and reduction of AgNO₃ in the presence of poly(styrene sulfonic acid) (PSS). We used AgNO₃ as one of the initial components (1) to form the silver nanoparticles and (2) as an oxidizing agent for initiation of the polymerization reaction. UV‐visible spectra of the synthesized nanocomposites reveal the synchronized formation of silver nanoparticles and polymer matrix. The morphology of the silver nanoparticles and degree of their dispersion in the nanocomposites were characterized by transmission electron microscopy. Thermogravimetric analysis and differential scanning calorimetry results indicate an enhancement of the thermal stability of the nanocomposites compared to the pure polymers. The electrical conductivity of the nanocomposites is in the range 10^?4 to 10^?2 S cm^?1. CONCLUSION: A single‐step process for the synthesis of silver nanoparticle–polyaniline derivative nanocomposites doped with PSS has been demonstrated. The approach in which silver nanoparticles are formed simultaneously during the polymerization process results in a good dispersion of the nanoparticles in the conductive polymer matrix. Copyright © 2008 Society of Chemical Industry     

Conducting IPN Based on Polyaniline and Crosslinked Cellulose

Polyaniline/crosslinked cellulose conductive interpenetrating polymer networks (IPNs) were prepared by oxidative polymerization of aniline within the self-synthesized cellulose network using ammonium persulphate as oxidant. The conductivity of the IPN increases and then decreases with decrease in the aniline/(NH₄)₂S₂O₈ ratio, with increase in the HCl/aniline ratio, with increase in aniline content, as well as with increase in reaction time. In addition, the conductivity of the films strongly depends on the amount of tetraethyl orthosilicate crosslinker. In comparison with polyaniline/cellulose acetate composites, the conductivity increases by an order of one to two magnitudes in spite of the lower polyaniline content in this work. © of SCI.     

Chemical anchoring of silica nanoparticles onto polyaniline chains via electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of SiO2

Chemical anchoring of silica nanoparticles onto polyaniline (PANI) chains was conducted through electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of silica nanoparticles. The grafting of N-substituted aniline on surfaces of silica nanoparticles were realized through hydrolysis of triethoxysilylmethyl N-substituted aniline (ND42) and the following condensation reaction with silanol groups on surfaces of SiO₂. Organic-inorganic interactions between PANI and SiO₂ involved in electro-co-polymerization process pushed the polymer chains apart and so facilitated the 1D growth of the polymer. Hence, the obtained hybrid film PANI/ND42-SiO₂ displayed nano-fibrous morphologies (ca. 50 nm in diameter). Consequently, PANI/ND42-SiO₂ exhibited an average specific capacitance of 380 F g⁻¹, ca. 40% higher than that of PANI/SiO₂ (276 F g⁻¹). The hybrid film also showed improved cyclic stability.     

Synthesis of high conductivity Polyaniline/Ag/graphite nanosheet composites via ultrasonic technique

A new process for the synthesis of high conductivity polyaniline/Ag/graphite nanosheet (PANI/Ag/NanoG) composites was developed. Graphite nanosheet was prepared by treating the expanded graphite in aqueous alcohol solution using sonication, and a uniform silver film about 470 nm thick was obtained on graphite nanosheet surface via an improved electroless plating method. Then PANI/Ag/NanoG composites were fabricated via in situ polymerization of aniline monomer in the presence of silver coated graphite nanosheet through using ultrasonic technique. The sliver particles and composites were evidenced by scanning and transmission electron microscopy examinations, the results showed that the silver coated graphite nanosheet particles played an important role in forming conducting bridge in polyaniline matrix. According to the electrically test, the conductivity of the PANI/Ag/NanoG composites was dramatically increased compared with pure PANI. From the thermogravimetric analysis, the PANI/Ag/NanoG composites exhibited a beneficial effect on the thermal stability of pure PANI.     

Selective catalytic oxidation of aniline to azoxybenzene over titanium silicate molecular sieves

The oxidation of aniline using aqueous H₂O₂ and titanium silicates, TS-1 and TS-2 as catalysts was carried out in a batch reactor in the temperature range 333–353 K. TS-1 catalyzes aniline selectively to azoxybenzene and is superior to TS-2. The influence of different solvents, concentration of H₂O₂ and the catalyst in the reaction mixture on the conversion and product distribution has been studied. Acetonitrile is a suitable solvent in this reaction, while acetone is not. For the TS-1 catalyzed oxidation reaction,t-butyl hydroperoxide is not a suitable oxidant. At optimum conditions, a H₂O₂ efficiency of about 100% for aniline conversion is obtained with a selectivity of 97% to azoxybenzene in the product.     

In situ preparation of monodispersed Ag/polyaniline/Fe3O4 nanoparticles via heterogeneous nucleation

Acrylic acid and styrene were polymerized onto monodispersed Fe₃O₄ nanoparticles using a grafting copolymerization method. Aniline molecules were then bonded onto the Fe₃O₄ nanoparticles by electrostatic self-assembly and further polymerized to obtain uniform polyaniline/Fe₃O₄ (PANI/Fe₃O₄) nanoparticles (approximately 35 nm). Finally, monodispersed Ag/PANI/Fe₃O₄ nanoparticles were prepared by an in situ reduction reaction between emeraldine PANI and silver nitrate. Fourier transform infrared and UV-visible spectrometers and a transmission electron microscope were used to characterize both the chemical structure and the morphology of the resulting nanoparticles.     

Enhanced photocatalytic properties of a novel GO-Ag-C6H5Ag3O7 nanocomposite

A novel graphene oxide-Ag-C₆H₅Ag₃O₇ nanocomposite was prepared by a facile precipitation reaction with the aid of photo-reduction. The rich surface functional groups of graphene oxide (GO) interacted with silver cations, provided the nucleation sites and induced the formation of C₆H₅Ag₃O₇ nanoparticles on the GO surface uniformly. The nanocomposite displayed an enhanced photocatalytic activity compared with pure C₆H₅Ag₃O₇ and GO under simulated sunlight, due to the reduced recombination of plasmon-induced electron–hole pairs on the Ag nanoparticles by the GO. This study likely provides one possibility of exploiting stable Ag/silver (I) complex photocatalysts in dealing with environmental contaminants.     

A novel hydrogen peroxide sensor based on Ag nanoparticles decorated polyaniline/graphene composites

A novel electrochemical sensor based on Ag nanoparticles (AgNPs) decorated polyaniline/graphene composites (PANI/G) is developed, which can be used for sensitive determination of H₂O₂. For the construction of the H₂O₂ sensor, polyaniline (PANI) is first electrodeposited on the surface of graphene (G) to form PANI/G, and then horseradish peroxidase (HRP) loaded on AgNPs (HRP/AgNPs) is immobilized on to the PANI/G. H₂O₂ can be catalyzed by HRP to generate current response which can be significantly enhanced by AgNPs, and thus the PANI/G based sensor can be utilized for the detection of H₂O₂. Under the optimized conditions, the proposed H₂O₂ sensor exhibits wide linear response to H₂O₂ concentration ranging from 0.25 to 2.25 mM with a detection limit of 0.03 mM (signal‐to‐noise ratio of 3), and it also shows high selectivity and reproducibility. The method is simple and cost‐effective, and can be a promising candidate as the sensitive sensing platform for H₂O₂. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42409.