Metal and Metal Oxide Nanostructures Prepared by Electrical Arc Discharge Method in Liquids

In this review, the importance of electrical arc discharge technique in liquids in synthesis of various nanostructures from carbon based materials to metal and metal oxide nanostructures with their general and specific properties, especially the photocatalytic performance of metal oxide nanostructures is studied. The effect of arc current on size distribution, morphology and physicochemical properties of metal and semiconductor nanostructures was investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray photoelectron spectroscopy (XPS) and UV–Vis spectroscopy. WO₃ Cubic nanostructures with 30 nm mean particle size were formed during the discharge process in water. Discharge between zinc electrodes in water leads to formation of rod like and semi spherical ZnO nanostructures with 15–20 nm diameter range. ZrO₂ nanoparticles were formed using zirconium electrodes in water. Photodegradation of Rhodamine B (Rh. B) shows that the as prepared nanostructures in this method have potential ability for environmental purifications. Also, using silver electrodes in water leads to formation of silver nanoparticles with 8–15 nm average particle size. Moreover, a novel method for synthesis of gold nanoparticles without using gold electrodes is presented. Finally, the future outlook of this technique in synthesis of various nanocrystalline materials is presented.     

Silica–silver core–shell particles for antibacterial textile application

The silica–silver core–shell particles were synthesized by simple one pot chemical method and were employed on the cotton fabric as an antibacterial agent. Extremely small (1–2 nm) silver nanoparticles were attached on silica core particles of average 270 nm size. The optimum density of the nano silver particles was found which was sufficient to show good antibacterial activity as well as the suppression in their surface plasmon resonance responsible for the colour of the core–shell particle for antibacterial textile application. The change in the density and size of the particles in the shell were monitored and confirmed by direct evidence of their transmission electron micrographs and by studying surface plasmon resonance characteristics. The colony counting method of antibacterial activity testing showed excellent results and even the least silver containing core–shell particles showed 100% activity against bacterial concentration of 10⁴ colony counting units (cfu). The bonding between core–shell particles and cotton fabric was examined by X-ray photoelectron spectroscopy. The antibacterial activity test confirmed the firm attachment of core–shell particles to the cotton fabric as a result 10 times washed sample was as good antibacterial as that of unwashed sample. The bacterial growth was inhibited on and beneath the coated fabric, at the same time no zone of inhibition which occurs due to the migration of silver ions into the medium was observed indicating immobilization of silver nanoparticles on silica and core–shell particles on fabric by strong bonding.     

Gamma irradiation route to synthesis of highly re-dispersible natural polymer capped silver nanoparticles

Aqueous dispersions of highly stable, redispersible silver nanoparticles (Ag NPs) were synthesized using gamma radiolysis with gum acacia as a protecting agent. The formation of nanosized silver was confirmed by its characteristic surface plasmon absorption peak at around 405 nm in UV–vis spectra. The size of the silver nanoparticles can be tuned by controlling the radiation dose, ratio of gum acacia to silver ions and also the ionic strength of the medium. Dynamic light scattering (DLS) measurement of the as-synthesized nanoparticles indicated the size less than 3 nm at higher dose of radiation and this also corroborated the size measurement from the width of the corresponding X-ray diffraction (XRD) peak. The face centered cubic (fcc) crystallinity of the nanoparticles was evident from XRD and high resolution transmission electron microscopic (HRTEM) measurements. Fourier transform infra-red (FTIR) spectroscopic data indicate a bonding of Ag NPs with COO^? group of acacia through bridging bidentate linkage.     

Preparation and characterization of stable monodisperse silver nanoparticles via photoreduction

Silver nanoparticles were synthesized by UV irradiation of [Ag(NH₃)₂]⁺ aqueous solution using poly(N-vinyl-2-pyrrolidone) (PVP) as both reducing and stabilizing agents. The formation of silver nanoparticles was confirmed from the appearance of surface plasmon absorption maxima around 420 nm. It was found that the formation rate of silver nanoparticles from Ag₂O was much quicker than that from AgNO₃, and the absorption intensity increased with PVP concentration as well as irradiation time. The maximum absorption wavelength (λ_max) was blue shift with increasing PVP content until 8 times concentration of [Ag(NH₃)₂]⁺ (wt%). The transmission electron microscopy (TEM) showed the resultant particles were 4–6 nm in size, monodisperse and uniform particle size distribution. X-ray diffraction (XRD) demonstrated that the colloidal nanoparticles were the pure silver. In addition, the silver nanoparticles prepared by the method were stable in aqueous solution over a period of 6 months at room temperature (25 °C).     

Growth of ordered silver nanoparticles in silica film mesostructured with a triblock copolymer PEO-PPO-PEO

Elaboration of mesostructured silica films with a triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide, (PEO-PPO-PEO) and controlled growth of silver nanoparticles in the mesostructure are described. The films are characterized using UV-visible optical absorption spectroscopy, TEM, AFM, SEM, X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). Organized arrays of spherical silver nanoparticles with diameter between 5 and 8 nm have been obtained by NaBH₄ reduction. The size and the repartition of silver nanoparticles are controlled by the film mesostructure. The localization of silver nanoparticles exclusively in the upper-side part of the silica-block copolymer film is evidenced by RBS experiment. On the other hand, by using a thermal method, 40 nm long silver sticks can be obtained, by diffusion and coalescence of spherical particles in the silica-block copolymer layer. In this case, migration of silver particles toward the glass substrate-film interface is shown by the RBS experiment.     

Preparation of silver nanoparticles with controlled particle size

Silver colloids show different colors due to light absorption and scattering in the visible region based on plasmon resonance. The resonance wavelength depends on particle size and shape. Here we report chemical reduction methods for preparation of silver nanoparticles exhibiting multicolor in aqueous solutions. Depending on chemical conditions the obtained nanoparticles are different regarding size and morphology.In order to investigate the relationship between size, stability and color of silver colloids we obtained silver nanoparticles in aqueous solutions using different reducing agents. The effect of polyvinyl pyrrolidone (PVP) and polyvinyl alcohol (PVA) on stabilization of obtained silver colloids was investigated. We have also studied the effect of silver precursor and its concentration on the formation of stable silver colloids.UV-VIS spectrum for silver colloids contains a strong plasmon band near 410 nm, which confirms silver ions reduction to Ag° in the aqueous phase. The formation of metal silver was also confirmed by powder X-ray diffraction (XRD) analysis. The diameter size of silver nanoparticles was in the range from 5 nm to 100 nm     

Synthesis,characterization and properties of magnetic colloids supported on chitosan

This work proposes the synthesis, characterization and investigation of the stabilization capabilities of chitosan doped with magnetic nanoparticles. Nanoparticles of Fe, Co, Co(II,III) oxide, Ni and Ni/Ag mixture in 2-propanol were synthesized by chemical liquid deposition and the incorporation on the polymeric matrix was performed by solvated metal atom dispersion. Colloids and nanoparticles supported on chitosan were characterized by ultraviolet, Fourier-transform infrared, thermogravimetric analysis, electron diffraction X-ray and magnetic behaviour; transmission and field electronic scanning electron microscopy. The particle size distribution of colloids ranges from 6 to 50 nm with low particle stability due to flocculation after 120 days. The nanoparticles supported on chitosan had a particle size distribution of approximately between 10 and 80 nm, with low particle distribution; however, these particles do not flocculate because the matrix increases the stabilization of nanoparticles. All compounds present superparamagnetic behaviour at low temperature.     

Methyltriethoxysilane-derived sol-gel coatings doped with silver metal particles

Silica sol-gel films were prepared by dipping, starting from an acid catalyzed solution of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS). Silver metal nanoparticles were produced in the silica layer by introducing in the sol-gel precursor solution AgNO₃ or AgClO₄·H₂O. The silver ions were thermally reduced in air at 800°C, giving an intense yellow coating film. The silver metal particles were observed by transmission electron microscopy and X-ray diffraction. The diameter of the silver particles was found to be about 10 nm. Absorption measurements in the UV-Vis were used to evaluate the volume fraction of silver colloids embedded in the silica layer.     

XPS study of silver and copper nanoparticles demonstrated selective anticancer,proapoptotic, and antibacterial properties

Silver and copper nanoparticles were produced by an ecologically safe metal vapor synthesis (MVS) method using acetone as an organic dispersion medium. Transmission electron microscopy (TEM) showed that the specimens are spherical and polydisperse, and their average size is 2.5 nm for silver nanoparticles (Ag NPs) and 2.6 nm for copper nanoparticles (Cu NPs). X-ray photoelectron spectroscopy analyses showed that the state of silver in the nanoparticles is close to that of silver in the Ag⁰ state, whereas copper black contains two oxidized states of the metal—Cu⁺ and Cu²⁺. Biological in vitro studies demonstrated that the nanoparticles have antibacterial activity against Gram-positive and Gram-negative bacterial species. Cu NPs exhibited more prominent antibacterial effects and induced significant growth inhibition of Bacillus cereus and Escherichia coli. Both types of nanoparticles showed anticancer properties in vitro. Cu NPs induced intense cytotoxicity in cancer and normal fibroblasts in vitro cultures, but their inhibitory effect against noncancerous cells was milder compared with cancer cell lines. Ag NPs demonstrated selective cytotoxicity against human lung and cervical adenocarcinoma cell lines. Further in vitro studies indicated that the mechanism of Ag NPs and Cu NPs anticancer effects involves induction of apoptosis. The present study describes a green synthesis approach for production of biologically active silver and copper nanoparticles and highlights their potential for medical application.     

Biosynthesis, purification and characterization of silver nanoparticles using Escherichia coli

The application of nanoscale materials and structures, usually ranging from 1 to 100 nanometers (nm), is an emerging area of nanoscience and nanotechnology. Nanomaterials may provide solutions to technological and environmental challenges in the areas of solar energy conversion, catalysis, medicine, and water-treatment. The development of techniques for the controlled synthesis of nanoparticles of well-defined size, shape and composition, to be used in the biomedical field and areas such as optics and electronics, has become a big challenge. Development of reliable and eco-friendly processes for synthesis of metallic nanoparticles is an important step in the field of application of nanotechnology. One of the options to achieve this objective is to use ‘natural factories’ such as biological systems. This study reports the optimal conditions for maximum synthesis of silver nanoparticles (AgNPs) through reduction of Ag⁺ ions by the culture supernatant of Escherichia coli. The synthesized silver nanoparticles were purified by using sucrose density gradient centrifugation. The purified sample was further characterized by UV–vis spectra, fluorescence spectroscopy and TEM. The purified solution yielded the maximum absorbance peak at 420 nm and the TEM characterization showed a uniform distribution of nanoparticles, with an average size of 50 nm. X-ray diffraction (XRD) spectrum of the silver nanoparticles exhibited 2θ values corresponding to the silver nanocrystal. The size-distribution of nanoparticles was determined using a particle-size analyzer and the average particle size was found to be 50 nm. This study also demonstrates that particle size could be controlled by varying the parameters such as temperature, pH and concentration of AgNO₃.     

Preparation and properties of silica–gold core–shell particles

Silica-metal core–shell particles, as for instance those having siliceous core and nanostructured gold shell, attracted a lot of attention because of their unique properties resulting from combination of mechanical and thermal stability of silica and magnetic, electric, optical and catalytic properties of metal nanocrystals such as gold, silver, platinum and palladium. Often, the shell of the core–shell particles consists of a large number of metal nanoparticles deposited on the surface of relatively large silica particles, which is the case considered in this work. Namely, silica particles having size of about 600 nm were subjected to surface modification with 3-aminopropyltrimethoxysilane. This modification altered the surface properties of silica particles, which was demonstrated by low pressure nitrogen adsorption at ?196 °C. Next, gold nanoparticles were deposited on the surface of aminopropyl-modified silica particles using two strategies: (i) direct deposition of gold nanoparticles having size of about 10 nm, and (ii) formation of gold nanoparticles by adsorption of tetrachloroauric acid on aminopropyl groups followed by its reduction with formaldehyde.The overall morphology of silica–gold particles and the distribution of gold nanoparticles on the surface of modified silica colloids were characterized by scanning electron microscopy. It was shown that direct deposition of colloidal gold on the surface of large silica particles gives more regular distribution of gold nanopartciles than that obtained by reduction of tetrachloroauric acid. In the latter case the gold layer consists of larger nanoparticles (size of about 50 nm) and is less regular. Note that both deposition strategies afforded silica–gold particles having siliceous cores covered with shells consisting of gold nanoparticles of tunable concentration.     

Preparation, characterization, and optical properties of gold, silver, and gold-silver alloy nanoshells having silica cores

This report describes the structural and optical properties of a series of spherical shell/core nanoparticles in which the shell is comprised of a thin layer of gold, silver, or gold-silver alloy, and the core is comprised of a monodispersed silica nanoparticle. The silica core particles were prepared using the St?ber method, functionalized with terminal amine groups, and then seeded with small gold nanoparticles (approximately 2 nm in diameter). The gold-seeded silica particles were coated with a layer of gold, silver, or gold-silver alloy via solution-phase reduction of an appropriate metal ion or mixture of metal ions. The size, morphology, and elemental composition of the composite nanoparticles were characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA), dynamic light scattering (DLS), and transmission electron microscopy (TEM). The optical properties of the nanoparticles were analyzed by UV-vis spectroscopy, which showed strong absorptions ranging from 400 nm into the near-IR region, where the position of the plasmon band reflected not only the thickness of the metal shell, but also the nature of the metal comprising the shell. Importantly, the results demonstrate a new strategy for tuning the position of the plasmon resonance without having to vary the core diameter or the shell thickness.     

Phytochemical fabrication and characterization of silver nanoparticles by using Pepper leaf broth

The Pepper leaves extract acts as a reducing and capping agent in the formation of silver nanoparticles. A UV–Vis spectrum of the aqueous medium containing silver nanoparticles demonstrated a peak at 458 nm corresponding to the plasmon absorbance of rapidly synthesized silver nanoparticles that was characterized by UV–Vis spectrophotometer. The morphology and size of the benign silver nanoparticles were carried out by the transmission electron microscope (TEM) and field emission scanning electron microscope (FE-SEM). The sizes of the synthesized silver nanoparticles were found to be in the range of 5–60 nm. The structural characteristics of biomolecules hosted silver nanoparticles were studied by X-ray diffraction. The chemical composition of elements present in the solution was determined by energy dispersive spectrum. The FTIR analysis of the nanoparticles indicated the presence of proteins, which may be acting as capping agents around the nanoparticles. This study reports that synthesis is useful to avoid toxic chemicals with adverse effects in medical applications rather than physical and chemical methods.     

Effective catalysis and antibacterial activity of silver and gold nanoparticles biosynthesized by Phlogacanthus turgidus

In this work, an environmentally friendly and cost-effective synthetic method of silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) was successfully performed using aqueous extract of Phlogacanthus turgidus (PT) leaves. The biosynthesis of nanoparticles was optimized for reaction conditions including concentration of metallic ions, temperature, and time using the measurement of UV–Vis spectroscopy. The nanoparticles were well characterized by analytic techniques such as Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), and selected area electron diffraction (SAED). The morphological data showed that PT-AgNPs possessed the spherical shape with the size distribution ranging from 5 to 15 nm with a mean size of 10 nm while PT-AuNPs existed in the multiple shape with the size distribution ranging from 5 to 20 nm with a mean size of 12 nm. The antibacterial behavior showed that PT-AgNPs possessed high bioactivity against four bacterial strains including Bacillus subtilis, Staphylococcus aureus, Salmonella typhi, and Escherichia coli. Moreover, the catalytic activity of the biogenic nanoparticles was investigated for catalytic reduction of 2-nitrophenol, 3-nitrophenol, and rhodamine B. The kinetic data showed that the nanoparticles were excellent catalysts with potential applications for environmental treatment.

Graphical abstract

     

Magnetite nanoparticles with tunable gold or silver shell

Fe3O4 nanoparticles with size approximately 13 nm have been prepared successfully in aqueous micellar medium at approximately 80 degrees C. To make Fe3O4 nanoparticles resistant to surface poisoning a new route is developed for coating Fe3O4 nanoparticles with noble metals such as gold or silver as shell. The shell thickness of the core-shell particles becomes tunable through the adjustment of the ratio of the constituents. Thus, the route yields well-defined core-shell structures of size from 18 to 30 nm with varying proportion of Fe3O4 to the noble metal precursor salts. These magnetic nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FTIR, differential scanning calorimetry (DSC), Raman and temperature-dependent magnetic studies.     

Sol–gel synthesis of nanosilver embedded hybrid materials using combined organosilica precursors

A facile sol–gel route to the fabrication of size-controllable nanosilver embedded hybrid materials at room-temperature is presented. The preparation process involves using three kind of organosilica precursors, i.e. tetraethoxysilane, 3-mercaptopropyltrimethoxysilane and polymethylhydrosiloxane, which behaved as framework constructor, complexing agent toward metal ions and in situ reducing agent for Ag⁺ ions, respectively, under alcohol-rich synthesis conditions. The prepared hybrid materials were characterized by Ultraviolet–visible diffuse reflectance spectra, Fourier transform infrared, transmission electron microscopy, X-ray diffraction, nitrogen adsorption–desorption measurements. It was shown that well-dispersed silver nanoparticles (AgNPs) with small particle size were successfully embedded in the hybrid skeleton, and the mean particle size of AgNPs could be controlled at ca. 2–5 nm.     

On the Formation of TiO<Subscript>2</Subscript> Nanoparticles Via Submerged Arc Discharge Technique: Synthesis,Characterization and Photocatalytic Properties

We report a simple and inexpensive synthesis route of TiO₂ nanoparticles using electrical arc discharge between titanium electrodes in oxygen bubbled deionized (DI) water followed by heat treatment. The resulting nanoparticles were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD patterns demonstrate formation of TiO₂ phase in oxygen bubbled water after heat treatment and dominance of rutile to anatase phase. The size and morphology of TiO₂ nanoparticles were studied using different arc currents as a crucial parameter in properties of final product. Microscopic studies reveal nanosize spherical particles. DLS results indicate that at 20 A arc current, the size of the particles is about 37 nm and increases to 59 nm by increasing the arc current up to 40 A. Photodegradation of Rhodamine B (Rh. B) as a standard pollution shows that heat treated samples in oxygen bubbled water for 2 h at 500 °C, have more photocatalytic activity due to enhancement in crystallinity.     

Green biosynthesis of silver nanoparticles using Torreya nucifera and their antibacterial activity

Silver nanoparticles were biosynthesized with the aid of a novel and eco-friendly biological material Torreya nucifera. Temperature and extract concentration were found to influence the size and shape of the biosynthesized silver nanoparticles. Morphological images of biosynthesized nanomaterials revealed that the particles are in spherical shape and size ranging between 10 and 125 nm. Crystalline nature of nanoparticles in face centered cubic (fcc) structure was ensured by diffraction pattern peaks corresponding to (1 1 1), (2 0 0), (2 2 0) and (3 1 1) planes. Characterization of the biosynthesized nanoparticles was performed by the X-ray diffraction and Fourier Transform Infrared spectroscopy analyses. FT-IR analysis indicates that nanoparticles are bound to proteins through amine groups of the aminoacid. Furthermore the biosynthesized nanoparticles were found to be highly effective against Salmonella typhimurium bacterium, which validates its potential applications as antibacterial agents in drinking water treatment and in food packagings.     

Green synthesis and characterization of silver nanoparticles by Allium cepa L. to produce silver nano‐coated fabric and their antimicrobial evaluation

This research work was proposed to study the antimicrobial activity of the silver nanocoated fabric with the purpose of producing good dressing and clothing material. We synthesized simple, ecofriendly, cost‐effective and sustainable silver nanoparticles by using the aqueous extract of Allium cepa L. Here, A. cepa L. acts as a good reducing and capping agent that produced stable silver nanoparticles having particle size of range 36 ± 1 to 98 ± 2 nm, Poly dispersiblity index 0.234 ± 0.61 to 1.023 ± 0.33 and Zeta potential ‐12 ± 1.5 mV to ‐26 ± 1.2 mV. The effect of temperature and extract volume used was considered for optimization of synthetic procedure. The nanocoated fabric was characterized for morphological study, size (using transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE‐SEM) and zeta‐potential (Zeta Potentiometer). The presence of functional groups were observed by using attenuated total reflection‐Fourier transform infrared (ATR‐FTIR) and Raman spectroscopy. The crystallinity and structural property of the synthesized silver nanoparticles were studied in terms of Powder X‐ray diffraction (PXRD). An IC₅₀ value and zone of inhibition was studied which demonstrate that the silver nanocoated fabric have an excellent antibacterial property against Gram‐negative (Escherichia coli) and Gram‐positive (Staphylococcus aureus) bacteria. Further nanocoated fabric material was washed (with function of time 0, 10, 25, and 50 laundry cycles) and still retained their anti‐bacterial activity towards both strain. Initially there was 52 μg/ml of silver nanoparticles on the cotton fabric but after 50 laundry cycle in 500 ml of distilled water the fabric showed 92% efficiency against gram positive and 90% efficacy toward gram negative bacteria. It was found that 4.16 μg/ml nano particles leached in case of S. Aureus and 5.2 μg/mL silver nanoparticles leached in case of E. coli. Nanocoated fabric material synthesized using green synthesis was found to be economical with good resistance to washing.     

Facile synthesis, stabilization, and anti-bacterial performance of discrete Ag nanoparticles using Medicago sativa seed exudates

The biogenic synthesis of metal nanomaterials offers an environmentally benign alternative to the traditional chemical synthesis routes. Colloidal silver (Ag) nanoparticles were synthesized by reacting aqueous AgNO(3) with Medicago sativa seed exudates under non-photomediated conditions. Upon contact, rapid reduction of Ag(+) ions was observed in <1 min with Ag nanoparticle formation reaching 90% completion in <50 min. Effect of Ag concentration, quantity of exudate and pH on the particle size and shape were investigated. At [Ag(+)]=0.01 M and 30°C, largely spherical nanoparticles with diameters in the range of 5-51 nm were generated, while flower-like particle clusters (mean size=104 nm) were observed on treatment at higher Ag concentrations. Pre-dilution of the exudate induced the formation of single-crystalline Ag nanoplates, forming hexagonal particles and nanotriangles with edge lengths of 86-108 nm, while pH adjustment to 11 resulted in monodisperse Ag nanoparticles with an average size of 12 nm. Repeated centrifugation and redispersion enhanced the percentage of nanoplates from 10% to 75% in solution. The kinetics of nanoparticle formation were monitored using ultraviolet-visible spectroscopy and the Ag products were characterized using transmission electron microscopy, selected-area electron diffraction, scanning electron microscopy, X-ray powder diffraction, and atomic force microscopy. X-ray photoelectron spectroscopy was used to investigate the elements and chemical environment in the top layers of the as-synthesized Ag nanoparticles, while the metabolites in the exudate were analyzed using gas chromatography-mass spectroscopy. To our knowledge, this is the first account of M. sativa seed exudate assisted synthesis and stabilization of biogenic Ag nanoparticles; the nanoplates are notably smaller and better faceted compared with those synthesized by vascular plant extracts previously reported. Stabilized films of exudate synthesized Ag nanoparticles were effective anti-bacterial agents.