Silver metal nanosized particles: Control of particle size,self assemblies in 2D and 3D superlattices and optical properties

Water in oil droplets are used to control the size of silver metal nanoparticles. After synthesis, the silver metal particles are extracted from reverse micelles and redispersed in a non polar solvent. By increasing the size of the water droplets the average size of silver nanoparticles increases from 2 nm to 7 nm with a rather high size distribution. To narrow the panicle distribution a size selected precipitation method is used. By deposition of a dilute solution containing the coated particles on a carbon grid, the particles arrange themselves in a monolayer organized in a hexagonal network. At high particle concentration, the particles are organized in multilayers forming microcrystals arranged in a face centered cubic structure. The optical properties of the silver nanoparticles isolated in micellar solution or self-assembled in 2D or 3D supperlattices are reported.     

Synthesis and optical properties of silver nanoparticles and arrays.

This Minireview systematically examines optical properties of silver nanoparticles as a function of size. Extinction, scattering, and absorption cross-sections and distance dependence of the local electromagnetic field, as well as the quadrupolar coupling of 2D assemblies of such particles are experimentally measured for a wide range of particle sizes. Such measurements were possible because of the development of a novel synthetic method for the size-controlled synthesis of chemically clean, highly crystalline silver nanoparticles of narrow size distribution. The method and its unique advantages are compared to other methods for synthesis of metal nanoparticles. Synthesis and properties of nanocomposite materials using these and other nanoparticles are also described. Important highlights in the history of the field of metal nanoparticles as well as an examination of the basic principles of plasmon resonances are included.     

溶液体系中的纳米金属粒子形状控制合成*

纳米尺度的金属粒子由于量子尺寸效应等原因而表现出不同于宏观金属块体的电学、磁学、光学和热学等性质.纳米金属粒子的性质不仅受到尺寸的影响,还与粒子的形状密切相关.不同形状的纳米金属粒子通常具有不同的表面结构和性质.近年来,纳米金属粒子的形状控制合成正受到越来越多的关注;其中,Ⅷ族和IB族金属的研究已取得一定进展.本文评述了纳米金属粒子的合成以及尺寸和形状控制的方法,分别介绍了铂、钯、镍、金、银、铜以及钴等金属的形状控制合成的近期研究进展.     

Synthesis and applications of silver nanoparticles

Over the past few decades, nanoparticles of noble metals such as silver exhibited significantly distinct physical, chemical and biological properties from their bulk counterparts. Nano-size particles of less than 100 nm in diameter are currently attracting increasing attention for the wide range of new applications in various fields of industry. Such powders can exhibit properties that differ substantially from those of bulk materials, as a result of small particle dimension, high surface area, quantum confinement and other effects. Most of the unique properties of nanoparticles require not only the particles to be of nano-sized, but also the particles be dispersed without agglomeration. Discoveries in the past decade have clearly demonstrated that the electromagnetic, optical and catalytic properties of silver nanoparticles are strongly influenced by shape, size and size distribution, which are often varied by varying the synthetic methods, reducing agents and stabilizers. Accordingly, this review presents different methods of preparation silver nanoparticles and application of these nanoparticles in different fields.     

Tailoring surface plasmons through the morphology and assembly of metal nanoparticles

Metal nanoparticles can be used as building blocks for the formation of nanostructured materials. For the design of materials with specific (optical) properties, several approaches can be followed, even when starting from the very same basic units. In this article, a survey is provided of the optical properties of noble metal nanoparticles, specifically gold, silver, and their combinations, prepared in solution through colloid chemical methods. The optical properties are shown to be mainly influenced by the surface plasmon resonance of conduction electrons, the frequency of which is not only determined by the nature of the metal but also by a number of other parameters, such as particle size and shape, the presence of a capping shell on the particle surface, or the dielectric properties of the surrounding medium. Recent results showing how these various parameters affect the optical properties are reviewed. The results highlight the high degree of control that can now be achieved through colloid chemical synthesis.     

One-step synthesis of FePt nanoparticles with tunable size

A one-step synthesis of FePt nanoparticles is reported. The size, composition, and shape of the particles are controlled by varying the synthetic parameters such as molar ratio of stabilizers to metal precursor, addition sequence of the stabilizers and metal precursors, heating rate, heating temperature, and heating duration. An assembly of large (6 nm or greater) FePt nanoparticles, especially oxide-coated FePt nanoparticles, can sustain higher temperature (up to 650 degrees C) annealing without noticeable particle sintering. Room temperature coercivity of an assembly containing discrete FePt dots can reach as high as 1.3 T, a value that is suitable for hard magnetic applications.     

Geometry dependent features of optically induced forces between silver nanoparticles

A recently devised, discrete-dipole approximation (DDA) based method for computing optical forces is used to explore geometry dependent aspects of the light induced interactions between pairs of silver nanoparticles, including the influence of particle shape, relative positioning of the particles, and incident field orientation. The interactions are observed to have a large degree of generic character, independent of the details of the particle shape. The size of the optical forces is also compared to estimates for the van der Waals forces, and the results are used to assess the potential importance of radiation forces on recent experiments demonstrating photoinduced self-assembly of triangular silver nanoprisms.     

Critical phenomena in particles of mesoscopic size

Anomalous optical properties of small silver particles and some silver halides are discussed as displays of critical phenomena due to particle size decreasing or to their interaction with each other in an ensemble. Special consideration is given to weak localization of conduction electrons in a small metal particle, to plasmon delocalization in ensemble of metal particles, to the effect of zero- dimensional percolation in a small dielectric particle, and to the effect of size on the superionic transition in small AgI particles and thin envelopes.     

Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries

Sub-nanometre sized metal clusters, with dimensions between metal atoms and nanoparticles, have attracted more and more attention due to their unique electronic structures and the subsequent unusual physical and chemical properties. However, the tiny size of the metal clusters brings the difficulty of their synthesis compared to the easier preparation of large nanoparticles. Up to now various synthetic techniques and routes have been successfully applied to the preparation of sub-nanometre clusters. Among the metals, gold clusters, especially the alkanethiolate monolayer protected clusters (MPCs), have been extensively investigated during the past decades. In recent years, silver and copper nanoclusters have also attracted enormous interest mainly due to their excellent photoluminescent properties. Meanwhile, more structural characteristics, particular optical, catalytic, electronic and magnetic properties and the related technical applications of the metal nanoclusters have been discovered in recent years. In this critical review, recent advances in sub-nanometre sized metal clusters (Au, Ag, Cu, etc.) including the synthetic techniques, structural characterizations, novel physical, chemical and optical properties and their potential applications are discussed in detail. We finally give a brief outlook on the future development of metal nanoclusters from the viewpoint of controlled synthesis and their potential applications.     

Silica-metal core-shell nanostructures

Silica-metal nanostructures consisting of silica cores and metal nanoshells attract a lot of attention because of their unique properties and potential applications ranging from catalysis and biosensing to optical devices and medicine. The important feature of these nanostructures is the possibility of controlling their properties by the variation of their geometry, shell morphology and shell material. This review is devoted to silica-noble metal core-shell nanostructures; specifically, it outlines the main methods used for the preparation and surface modification of silica particles and presents the major strategies for the formation of metal nanoshells on the modified silica particles. A special emphasis is given to the St?ber method, which is relatively simple, effective and well verified for the synthesis of large and highly uniform silica particles (with diameters from 100 nm to a few microns). Next, the surface chemistry of these particles is discussed with a special focus on the attachment of specific organic groups such as aminopropyl or mercaptopropyl groups, which interact strongly with metal species. Finally, the synthesis, characterization and application of various silica-metal core-shell nanostructures are reviewed, especially in relation to the siliceous cores with gold or silver nanoshells. Nowadays, gold is most often used metal for the formation of nanoshells due to its beneficial properties for many applications. However, other metals such as silver, platinum, palladium, nickel and copper were also used for fabrication of core-shell nanostructures. Silica-metal nanostructures can be prepared using various methods, for instance, (i) growth of metal nanoshells on the siliceous cores with deposited metal nanoparticles, (ii) reduction of metal species accompanied by precipitation of metal nanoparticles on the modified silica cores, and (iii) formation of metal nanoshells under ultrasonic conditions. A special emphasis is given to the seed-mediated growth, where metal nanoshells are formed on the modified silica cores with deposited metal nanoparticles. This strategy assures a good control of the nanoshell thickness as well as its surface properties.     

Shape-controlled synthesis of copper colloids with a simple chemical route

The new electrical and optical properties of nanomaterials depend sensitively on both size and shape, which are of both fundamental and technological interest. This paper introduces a simple chemical method to produce copper particles, which has the ability to shape the particle without using any capping agent or template. In our synthetic procedure, the reactant concentration and temperature exerted a strong influence on the shape of the copper particles. At low reactant concentrations, the particles were cubic; at high reactant concentrations, obtained particles were spherical. The number of hollow particles greatly increased when the synthesis was performed at low temperature. We also synthesized a copper cubic ring at lower temperature, and it has been rarely reported. The absorption spectrum of hollow particles showed obvious red shifts, which suggests the possible assembly of novel optical materials.     

Synthesis of silver nanoparticles with different shapes

Today the synthesis of silver nanoparticles is very common due to their numerous applications in various fields. Silver nanoparticles have unique properties such as: optical and catalytic properties, which, depend on the size and shape of the produced nanoparticles. So, today the production of silver nanoparticles with different shapes which have various uses in different fields such as medicine, are noted by many researchers. This article, is an attempt to present an overview of the shape-controlled synthesis of silver nanoparticles using various methods.     

Optimal design and characterization of superparamagnetic iron oxide nanoparticles coated with polyvinyl alcohol for targeted delivery and imaging

Superparamagnetic iron oxide nanoparticles (SPION) with narrow size distribution and stabilized by polyvinyl alcohol (PVA) were synthesized. The particles were prepared by a coprecipitation technique using ferric and ferrous salts with a molar Fe3+/Fe2+ ratio of 2. Using a design of experiments (DOE) approach, the effect of different synthesis parameters (stirring rate and base molarity) on the structure, morphology, saturation magnetization, purity, size, and size distribution of the synthesized magnetite nanoparticles was studied by various analysis techniques including X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) with differential scanning calorimetry (DSC) measurements, vibrating-sample magnetometer (VSM), transmission electron microscopy (TEM), UV-visible, and Fourier transform infrared (FT-IR) spectrometer. PVA not only stabilized the colloid but also played a role in preventing further growth of SPION followed by the formation of large agglomerates by chemisorption on the surface of particles. A rich behavior in particle size, particle formation, and super paramagnetic properties is observed as a function of molarity and stirring conditions. The particle size and the magnetic properties as well as particle shape and aggregation (individual nanoparticles, magnetic beads, and magnetite colloidal nanocrystal clusters (CNCs) are found to be influenced by changes in the stirring rate and the base molarity. The formation of magnetic beads results in a decrease in the saturation magnetization, while CNCs lead to an increase in saturation magnetization. On the basis of the DOE methodology and the resulting 3-D response surfaces for particle size and magnetic properties, it is shown that optimum regions for stirring rate and molarity can be obtained to achieve coated SPION with desirable size, purity, magnetization, and shape.     

Influence of surfactant surface coverage and aging time on physical properties of silica nanoparticles

The experimental results on the influence of surfactant surface coverage and aging time on physical properties of silica nanoparticles were reported. The spherical silica nanoparticles have been synthesized using polyethylene glycol (PEG) as the surfactant and oil shale ash (OSA) as a new silica source. In order to identify the optimal condition for producing the best quality silica nanoparticles with the good dispersion and uniformity, the effects of surfactant surface coverage and aging time were investigated. It was found that the particle size and distribution of silica nanoparticles depend on the concentration of PEG in dispersion. At relatively low concentration, 0–2 wt.%, the existing PEG is not sufficient to prevent further growth of the initially formed silica nanoparticles, leading to large aggregates of silica particles. When the PEG concentration increases to 3 wt.%, self-assembled PEG layer on the surface stabilizes the initially formed silica nanoparticles and the silica particles with average diameter of 10 nm are uniformly distributed. With further increasing the concentration of PEG, the number of PEG aggregates increases and silica nanoparticles are mainly formed inside the entangled PEG chains, resulting in an observation of clusters of silica nanoparticles. Moreover, it was found that as the aging time increased, the shape of silica nanoparticles becomes regular and the particle size distribution becomes narrow.     

A Universal Approach for the Reversible Phase Transfer of Hydrophilic Nanoparticles

The ability to engineer the surface properties of magnetic nanoparticles is important for their various applications, as numerous physical and chemical properties of nanoscale materials are seriously affected by the chemical constitution of their surfaces. For some specific applications, nanoparticles need to be transferred from a polar to a nonpolar environment (or vice versa) after synthesis. In this work we have developed a universal method for the phase transfer of magnetic nanoparticles that preserves their shape and size. Octadecyltrimethoxysilane was used to cap the surfaces of the aqueous magnetic nanoparticles, thereby allowing their transfer into nonpolar solution. The resulting hydrophobic magnetic nanoparticles were transferred back into aqueous solution by subsequently covering them with an egg‐PC lipid monolayer. The superparamagnetic properties of the particles were retained after the phase transfer. The maximum transfer yields are dependent on their particle size with a maximum value of 93.16±4.75 % for magnetic nanoparticles with a diameter of 100 nm. The lipid‐modified magnetic particles were stable over 1 week, and thus they have potential applications in the field of biomedicine. This work also provides a facile strategy for the controllable engineering of the surface properties of nanoparticles.     

Immobilized silver nanoparticles on silica gel as an efficient catalyst in nitroarene reduction

<正>Nanoparticles have properties that can be fine-tuned by their size as well as shape.Hence,there is significant current interest in preparing nano-materials of small size dispersity and to arrange them in close-packed aggregates.This letter describes a way of synthesising silver nanoparticles and their protection to aggregate by silica gel.The combination of catalytic quantities of immobilized silver nanoparticles with reductive ability of NaBH_4 efficiently reduces aromatic nitroarenes to the corresponding amines in aqueous medium.Noteworthy is that highly chemoselective reactions were achieved in the presence of other functional groups such as halogen and carboxylic acid groups.The silver particles immobilized on silica gel are stable in the presence of oxygen for several months.     

Synthesis,Characterization, and Applications of Copper Nanoparticles

Copper nanoparticles with different structural properties and effective biological effects may be fabricated using new green protocols. The control over particle size and in turn size-dependent properties of copper nanoparticles is expected to provide additional applications. Various methods for the synthesis of copper nanoparticles have been reported including chemical methods, physical methods, biological methods, and green synthesis. Biological methods involve the use of plant extracts, bacteria, and fungi. Commendable work has been done regarding the synthesis and stability of copper nanoparticles. There is a need to summarize the behavior of copper nanoparticles in different media under various conditions. Here, a complete list of the literature on the synthesis of copper nanoparticles, their properties, stabilizing agents, factors affecting the morphology, and their applications is presented. The importance of copper nanoparticles compared to other metal nanoparticles are due to high conductivity. Methods for the synthesis of copper nanoparticles, including green protocols using plants and micro-organisms compared chemical methods, have also been reviewed.     

Electrodynamics of Noble Metal Nanoparticles and Nanoparticle Clusters

In this paper we examine the electrodynamics of silver nanoparticles and of clusters of nanoparticles, with an emphasis on extinction spectra and of electric fields near the particle surfaces that are important in determining surface-enhanced Raman (SER) intensities. The particles and clusters are chosen to be representative of what has been studied in recent work on colloids and with lithographically prepared particles. These include spheres, spheroids, truncated tetrahedrons, and clusters of two or three of these particles, with sizes that are too large to be described with simple electrostatic approximations but small compared to the wavelength of light. The electrodynamics calculations are mostly based on the discrete dipole approximation (DDA), which is a coupled-finite element approach which produces exact or nearly exact results for particles of arbitrary size and shape if fully converged. Mie theory results are used to study the validity of the DDA for spherical particles, and we also study the validity of the modified long wavelength approximation (MLWA), which is based on perturbative corrections to the electrostatic limit, and of the single dipole per particle approximation (SDA). The results show how the dipole plasmon resonance properties and the electric field contours around the particle vary with particle shape and size for isolated particles. For clusters of particles, we study the effect of interparticle spacing on plasmon resonance characteristics. We also show that the quadrupole resonance is much less sensitive to particle shape and interparticle interactions than the dipole plasmon resonance. These results provide benchmarks that will be used in future comparisons with experiment.     

Nanostructure of silver metal produced photocatalytically in TiO2 films and the mechanism of the resulting photochromic behavior

The optical activity of composite films created by the photocatalytic reduction of silver or gold ions in TiO(2) upon irradiation by UV light has up to now been discussed in terms of the formation and light-induced destruction of distinct nanoparticles molded inside the porous nanocrystalline film. We present results from classical light scattering calculations and a logical analysis of experimental observations to add detail to the mechanism. As opposed to large, solid metal nanoparticles, coatings and small particles in heterogeneous external dielectric environments account for observations such as the broad optical spectrum and multiwavelength photochromic responses. For some steps of the photochromic process, we propose that visible light permits an equilibrium promoting the growth of small metal features or suspended particles. We use a new expression for the restricted path length in our size-dependent broadening corrections of metal shells and discuss this briefly. We conclude by discussing the consequence of plasmon absorption in the proximity of the electronically active TiO(2) surrounding matrix, leading to mass transfer and shape change of the metal and photochromic properties of the film.     

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.