Synthesis and characterisation of silver nanoparticles in viscous solvents and its transfer into non-polar solvents

Room temperature synthesis of silver nanoparticles has been successfully achieved by adding NaOH acting as an accelerator for the reduction of silver ions in ethylene glycol and glycerol without adding any external reducing agent. Highly monodisperse silver particles are obtained in the presence of various stabilisers such as PVP, SiO₂ and SDS. Nanoparticles with a mean diameter of 25 nm and a mean deviation of 2 nm could be obtained under experimental conditions. The silver nanoparticles so obtained could be easily transferred to chloroform containing CTAB, giving rise to CTAB stabilised silver nanoparticles having sizes of around 25 nm. The newly found role of OH⁻ stabilisation was used to formulate a mechanism for the formation of silver nanoparticles in ethylene glycol and glycerol. In this mechanism, silver nanoparticles are stabilised in ethylene glycol by the adsorbed OH⁻ ions.     

Synthesis of nanosized silver colloids by microwave dielectric heating

Silver nanosized crystallites have been synthesized in aqueous and polyols viz., ethylene glycol and glycerol, using a microwave technique. Dispersions of colloidal silver have been prepared by the reduction of silver nitrate both in the presence and absence of stabilizer poly(vinylpyrolidone) (PVP). It was observed that PVP is capable of complexing and stabilizing Ag nanoparticles formed through the reduction of Ag⁺ ions in water and ethylene glycol. In the case of ethylene glycol, it has been shown that the use of PVP leads to particles with a high degree of stability. The colloids are stable in glycerol for months even in the absence of stabilizer.     

聚合物存在下纳米银复合材料的制备与表征

以聚丙烯腈聚乙二醇嵌段共聚物PAN-b-PEG-b-PAN为稳定剂, 在超声辐照下成功地制备了分散性较好、尺寸均匀的纳米银颗粒. 用X射线衍射(XRD)、红外光谱(FTIR)、透射电镜(TEM)、紫外-可见吸收光谱(UV-Vis)和热分析(TGA)等对制备的纳米银复合材料进行了表征. 红外结果表明超声辐照并没有破坏聚合物的链结构. 聚合物的引入, 对纳米银颗粒起到了很好的分散保护作用. 用低浓度的硝酸银溶液, 得到粒径较小的纳米银颗粒; 随着硝酸银浓度增大, 纳米银颗粒粒径也增大. 而聚合物的浓度增大时, 所得银纳米颗粒粒径减小. 对银纳米颗粒的形成机理进行了讨论.     

Bimodal Size Distribution of Gold Nanoparticles under Picosecond Laser Pulses

The evolution of size distributions of gold nanoparticles under pulsed laser irradiation (Nd:YAG, lambda = 355 nm, pulse width 30 ps) was carefully observed by transmission electron microscopy. Interestingly, the initial monomodal size distribution of gold nanoparticles turned into a bimodal one, with two peaks in the number of particles, one at 6 nm and the other at 16-24 nm. The sizes for small particles depended very little on the irradiated laser energy. This change is attributed to laser-induced size reduction of the initial gold nanoparticles followed by the formation of small particles. In our analysis, we extracted a characteristic value for the size-reduction rate per one pulse and revealed that laser-induced size reduction of gold nanoparticles occurred even below the boiling point. When laser energy is insufficient for the boiling of particles, formation of gold vapor around liquid gold drops is thought to cause the phenomenon. With enough laser energy for the boiling, the formation of gold vapor around and inside liquid gold drops is responsible for the phenomenon. We also observed particles with gold strings after one pulse irradiation with a laser energy of 43 mJ cm(-2) pulse(-1), which is sufficient energy for the boiling. It is considered that such particles with gold strings are formed by the projection of gaseous gold from liquid gold drops with some volume of liquid gold around the bubble. On the basis of comparison with previous work, picosecond laser pulses are thought to be the most efficient way to cause laser-induced size reduction of gold nanoparticles.     

High immobilization of antibacterial moieties onto monodisperse microspheres by dispersion polymerization using bicationic viologen surfmer

In order to achieve monodisperse particles with high content of antibacterial groups covalently bonded on surface, a bicationic viologen,N-hexyl-N’-(4-vinylbenzyl)-4,4’-bipyridinium bromide chloride(HW) was devised as a surfmer in dispersion polymerization of styrene(St) using a mixture of methanol(or ethylene glycol) and water as media.Effects of content of HW,its addition profile and composition of reaction media on particles size and incorporation of HW moieties were mainly investigated.The attachment of silver and gold nanoparticles on particle surface under UV irradiation ascertained the surface-bonded HW segments.SEM,TEM observations and XPS,zata potential measurements indicated that increase of initial HW contents and addition of HW(when polymerization had been performed for 3 h) led to grown particles and enhanced immobilization of HW moieties.Using a mixture of ethylene glycol and water as reaction media, small particles(520-142 nm) with highly attached HW moieties were prepared.Furthermore,antibacterial efficacy of the resultant particles against S.aureus was assayed,and particles with more HW moieties anchored on surface demonstrated greater efficiency of antibacterial activity.     

Specific features of polyol synthesis of silver nanoparticles with the use of solid carboxylates as precursors

Electron microscopy, X-ray diffraction, and chromatography-mass spectrometry have been employed to investigate the reduction of solid silver caprylate in ethylene glycol with the formation of silver nanoparticles. The structural characteristics of silver nanoparticles have been studied as depending on the conditions of their synthesis, including temperature, reduction time, and silver salt concentration. It has been found that, in the studied range of parameters under the conditions, when solid silver caprylate is dispersed in ethylene glycol, the characteristics of resulting nanoparticles are almost independent of the synthesis temperature. This peculiarity is related to the fact that the formation and growth of nanoparticles occur on the surface of silver salt crystals and are accompanied by gradual dissolution thereof. In this system, ethylene glycol plays the roles of a reductant and a solvent for liquid reaction products.     

Monodispersity and size control in the synthesis of 20-100 nm quasi-spherical silver nanoparticles by citrate and ascorbic acid reduction in glycerol-water mixtures

A simple two-step seed-mediated synthesis of monodisperse quasi-spherical silver nanoparticles by citrate and ascorbic acid reduction is presented. Control over monodispersity is achieved by a variety of compounds with hydroxyl groups such as glycerol, ethylene glycol, agarose, or sucrose. The latter can also be used as a matrix for storage.     

Study of polyol synthesis reaction parameters controlling high yield of silver nanocubes

The influence of the parameters and conditions of sodium sulfide-induced reaction of polyol synthesis of silver nanoparticles on the yield of cube-shaped particles and the optical properties of colloids is studied. The protocol proposed by Skrabalak et al. for the synthesis of nanocubes in small volumes (Nature Protocols, 2007, vol. 2, p. 2182) is taken as an initial variant for optimization. The effects of the reagent concentrations, degree of ethylene glycol oxygenation, the presence of impurities, reaction time, and temperature are studied. Suspensions containing nanoparticles with different shapes and sizes, including polydisperse particles of irregular shapes, silver nanocubes with a yield of 0 to 97%, nanoprisms, and nanorods, can be produced by varying the synthesis parameters. The key parameters controlling the yield of nanocubes are the degree of ethylene glycol oxygenation and the presence of trace amounts of ions of other metals (not silver). It is established that variations in the reaction time make it possible to vary the sizes of nanocubes in the range of 30–60 nm. Suspensions with high contents of cube-shaped particles are shown to exhibit three maxima in the plasmon extinction resonance spectrum at wavelengths of 350, 390, and, depending on the particle size, 435–470 nm.     

Ag Nanocomposite Particles: Preparation,Characterization and Application

Summary Herein, we report that different core-shell particles could be successfully used as the carrier systems for the deposition of silver nanoparticles. Firstly, thermosensitive core-shell microgel particles have been used as the carrier system for the deposition of Ag nanoparticles, in which the core consists of poly (styrene) (PS) whereas the shell consists of poly (N-isopropylacrylamide) (PNIPA) network cross-linked by N, N′-methylenebisacrylamide (BIS). Immersed in water the shell of these particles is swollen. Heating the suspension above 32 °C leads to a volume transition within the shell, which is followed by a marked shrinking of the network of the shell. Secondly, “nano-tree” type polymer brush can be used as “nanoreactor” for the generation of silver nanoparticles also. This kind of carrier particles consists of a solid core of PS onto which bottlebrush chains synthesized by the macromonomer poly (ethylene glycol) methacrylate (PEGMA) are affixed by “grafting from” technique. Thirdly, silver nanoparticles can be in-situ immobilized onto polystyrene (PS) core-polyacrylic acid (PAA) polyelectrolyte brush particles by UV irradiation. Monodisperse Ag nanoparticles with diameter of 8.5 nm, 7.5 nm and 3 nm can be deposited into thermosensitive microgels, “nano-tree” type polymer brushes and polyelectrolyte brush particles, respectively. Moreover, obtained silver nano-composites show different catalytic activity for the catalytic reduction of p-nitrophenol depending on the carrier system used for preparation.     

Synthesis of Ag nanospheres particles in ethylene glycol by electrochemical-assisted polyol process

The synthesis of monodispersed Ag nanosphere particles from silver nitrite in ethylene glycol at room temperature essentially promoted with the use of an electrochemical method was demonstrated. Poly(N-vinylpyrrolidone) (PVP) behaves electrochemically stable and facilitates the formation of well-defined Ag nanospheres of average size in the range of 11 nm. Further characterization by high-resolution transmission electron microscopy (HRTEM) image and nano-beam electron diffraction (NBED) pattern indicate that the growth direction of Ag nanosphere particles is the 1 1 1 direction. The time evolution of absorption spectra by UV–Vis spectroscopy illustrates that silver nanoparticles in the electrolyte increase rapidly upon electrochemical process.     

Microwave-Assisted Coating of PMMA beads by silver nanoparticles

Microwave (MW) irradiation was found to be a new technique for coating silver nanoparticles with an average size of approximately 31 nm onto the surface of poly(methyl methacrylate) PMMA beads (3 mm diameter). The microwave polyol reduction was carried out under an argon atmosphere. Silver nanoparticles were obtained by the MW irradiation of a solution mixture containing silver nitrate (or silver acetate), poly(ethylene glycol), ethanol, water, and 24 wt % aqueous ammonia for 5 min in the presence of PMMA beads, yielding a PMMA-nanosilver composite. By controlling the atmosphere and reaction conditions, we could achieve the deposition of silver nanoparticles onto the surface of poly(methyl methacrylate) and vary the amount of the silver anchored to the surface. The resulting silver-deposited PMMA samples were characterized using X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray analysis, high-resolution scanning electron microscopy, X-ray photoelectron spectroscopy, and volumetric titration with potassium thiocyanate (KSCN) according to the Folgard method.     

Photochemical synthesis of silver and gold nanoparticles in polyhydric alcohols

A procedure was developed for the synthesis of gold and silver nanoparticles in the presence of polyols like ethylene glycol, diethylene glycol, triethylene glycol, and 1,2-propylene glycol. Spectral characteristics of the obtained nanocomposites were mesured and kinetics of the formation of the colloidal phase was studied. The influence of the polyol nature and concentration on the photoinitiated formation of silver and gold nanoparticles was studied. The 1,2-propylene glycol is shown to exhibit maximal stabilizing effect.     

Spectroscopy property of Ag nanoparticles

Three silver nanoparticles of different size characterized by the UV-vis absorbance spectra and TEM images were prepared by citrate reduction and laser ablation with excitation of 532 and 248 nm. It is proved that all of them are effective SERS-active substrates, whereas, enhancement effect of silver colloids has not too much relation with the size and shape of the Ag nanoparticles. However, different photoluminescence spectra were observed from these three particles, indicating that the photoluminescence property of silver nanoparticles is dependent on the size. The spectra shift to higher energies with decreasing particle size. In addition, we also tentatively give the assignment of the luminescence bands.     

Controlled Synthesis of Narrow-Dispersed Copper Nanoparticles

A controlled synthesis method for preparing narrow-dispersed copper nanoparticles, using water and ethylene glycol as the reaction media respectively, has been reported. In order to obtain pure-phase copper nanoparticles using water, the reaction time of 8 h is essential. Owing to the reduction property of ethylene glycol, the reaction rate using ethylene glycol is higher. In addition, the amount of reduction agent can reduce largely. Polyvinyl pyrrolidone plays great role on the size of copper particles, and the increasing of polyvinyl pyrrolidone concentration attributes to the smaller dimension particles. The mean diameter is about 4 nm when the concentration of polyvinyl pyrrolidone is 0.5 mmol/L. Polyvinyl pyrrolidone acts as the polymeric capping agents in the reaction, preventing the agglomeration of the copper nanoparticles. When water is the reaction medium, Cu²⁺ complex is reduced to Cu⁺ complex firstly, and the further reduction of Cu⁺ forms the pure copper nanoparticle.     

Synthesis of Pt, Pd, Pt/Ag and Pd/Ag nanoparticles by microwave-polyol method

Pt, Pd, Pt-Ag and Pd-Ag bimetallic nanoparticles were synthesized in ethylene glycol and glycerol using the microwave technique in the presence of a stabilizer poly(N-vinylpyrrolidone) (PVP). It has been observed that PVP is capable of complexing and stabilizing nanoparticles. Mixed clusters were formed by simultaneous reduction of the metal ions. The clusters were characterized using UV-Vis spectra, XRD and dynamic light scattering. To understand the mechanism of formation of mixed nanoparticles, several experimental parameters such asin situ irradiation of mixed metal salts and mixing of individual sols were attempted.     

Electrocatalytic oxidation of ethylene glycol on Pt and Pt-Ru nanoparticles modified multi-walled carbon nanotubes

The synthesis and characterization of catalysts based on nanomaterials, supported on multi-walled carbon nanotubes (CNT) for ethylene glycol (EG) oxidation is investigated. Platinum (Pt) and platinum-ruthenium (Pt-Ru) nanoparticles are deposited on surface-oxidized multi-walled carbon nanotubes [Pt/CNT; Pt-Ru/CNT] by the aqueous solution reduction of the corresponding metal salts with glycerol. The electrocatalytic properties of the modified electrodes for oxidation of ethylene glycol in acidic solution have been studied by cyclic voltammetry (CV), and excellent activity is observed. This may be attributed to the small particle size of the metal nanoparticles, the efficacy of carbon nanotubes acting as good catalyst support and uniform dispersion of nanoparticles on CNT surfaces. The nature of the resulting nanoparticles decorated multiwalled carbon nanotubes are characterized by scanning electron microscopy (SEM) and transmission electron microscopic (TEM) analysis. The cyclic voltammetry response indicates that Pt-Ru/CNT catalyst displays a higher performance than Pt/CNT, which may be due to the efficiency of the nature of Ru species in Pt-Ru systems. The fabricated Pt and Pt-Ru nanoparticles decorated CNT electrodes shows better catalytic performance towards ethylene glycol oxidation than the corresponding nanoparticles decorated carbon electrodes, demonstrating that it is more promising for use in fuel cells.     

Gold nanoparticle formation from photochemical reduction of Au3+ by continuous excitation in colloidal solutions. A proposed molecular mechanism

A photochemical reduction of Au3+ with continuous 250-400 nm excitation is studied in ethylene glycol, and poly(vinylpyrrolidone) (PVP) is used as a capping material. After the absorption of Au3+ disappears, excitation is stopped. The surface plasmon absorption of gold as well as the thermal reappearance of the Au3+ absorption are found to increase as a function of time. The rates of these changes are studied as a function of the mole fraction of ethylene glycol in water. Experimental results show that a small amount of ethylene glycol increases the formation of gold nanoparticles and decreases the reformation of the Au3+ absorption after irradiation. Increasing the glycol concentration first increases the rate of formation of gold nanoparticles to a maximum at a mole fraction 0.40. As the glycol concentration is further increased, the rate of formation of the gold nanoparticles and the rate of re-formation of Au3+ decrease. A mechanism is proposed that involves the reduction of the excited Au3+ to Au2+ by ethylene glycol. This is followed by the disproportionation of Au2+ to Au3+ and Au1+. Both the reduction of Au1+ by ethylene glycol and its disproportionation lead to the formation of Au0, which upon nucleation and growth form Au nanoparticles.     

Amphiphilic polymers as pseudotemplates in the synthesis of metal sols

The effects of poly(ethylene glycol) and its amphiphilic polymers on the products of copper ion reduction in aqueous solutions are studied. Whereas coarse metal dispersions are formed in poly(ethylene glycol) solutions, stable sols of metal nanoparticles with diameters of 2 nm and above are produced in the presence of poly(ethylene glycol monolaurate) and poly(ethylene glycol monostearate). A poly(ethylene glycol)-poly(propylene glycol) block copolymer (Pluronic) also stabilizes copper nanoparticles; however, the interaction product of this copolymer with nanoparticles forms a precipitate. According to the electron microscopy data, sol particles comprise polymer micelles containing included copper nanoparticles.     

In situ formation and size control of gold nanoparticles into chitosan for nanocomposite surfaces with tailored wettability

The in situ formation of gold nanoparticles into the natural polymer chitosan is described upon pulsed laser irradiation. In particular, hydrogel-type films of chitosan get loaded with the gold precursor, chloroauric acid salt (HAuCl(4)), by immersion in its aqueous solution. After the irradiation of this system with increasing number of ultraviolet laser pulses, we observe the formation of gold nanoparticles with increasing density and decreasing size. Analytical studies using absorption measurements, atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy of the nanocomposite samples throughout the irradiation procedure reveal that under the specific irradiation conditions there are two competing mechanisms responsible for the nanoparticles production: the photoreduction of the precursor responsible for the rising growth of gold particles with increasing size and the subsequent photofragmentation of these particles into smaller ones. The described method allows the localized formation of gold nanoparticles into specific areas of the polymeric films, expanding its potential applications due to its patterning capability. The size and density control of the gold nanoparticles, obtained by the accurate increase of the laser irradiation time, is accompanied by the simultaneously controlled increase of the wettability of the obtained gold nanocomposite surfaces. The capability of tailoring the hydrophilicity of nanocomposite materials based on natural polymer and biocompatible gold nanoparticles provides new potentialities in microfluidics or lab on chip devices for blood analysis or drugs transport, as well as in scaffold development for preferential cells growth.     

Thermal and morphological investigation of the effect of POSS-(PEG2000)8 addition to UV curable PEGMEA/PEGDA formulation and simultaneously in situ formed silver nanoparticles

In this study, hybrid nanocomposites were synthesized by photo-crosslinking of poly (ethylene glycol) methyl ether acrylate/poly (ethylene glycol) diacrylate monomer system using 2- (carboxymethoxy) thioxanthone and POSS-(PEG₂₀₀₀)₈. Additionally, AgNO₃ was added to this formulation and in situ formation of silver nanoparticles onto hybrid nanocomposites were achieved in one-step. UV–Vis spectroscopy technique was used as a very useful tool for surface plasmon resonance band detection of silver nanoparticles. In addition to thermogravimetric analyses which were performed in nitrogen atmosphere to determine the thermal stability of the nanocomposites, dynamic light scattering, and scanning electron microscopy techniques were also used for size and morphology of silver nanoparticles in a hybrid network. TGA analyses proved that even the addition of a very low amount of POSS-(PEG₂₀₀₀)₈ made noteworthy contribution to thermal stability especially in the presence of silver nanoparticles in the hybrid network. The swelling capacities of the prepared films were examined at 1, 3 and 24 h in phosphate buffer solution (pH = 7.4). It was found that film containing only POSS-(PEG₂₀₀₀)₈ had the highest swelling ratio in the shortest time.