Hollow and cage-bell structured nanomaterials of noble metals

Mastery of the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the synthesis of metal nanomaterials with hollow interiors or cage-bell structures based on the inside-out diffusion of Ag in core-shell structured nanoparticles. It begins with the synthesis of core-shell Ag-M or core-shell-shell M(A)-Ag-M(B) nanoparticles in an organic solvent. Ag is then extracted from the core or the inner shell by bis(p-sulfonatophenyl)phenylphosphane, which binds strongly with Ag(I)/Ag(0) to allow the complete removal of Ag in 24-48 h, leaving behind an organosol of hollow or cage-bell structured metal nanomaterials. Because of their relatively lower densities, which usually translate to a higher surface area than their solid counterparts, the hollow and cage-bell structured metal nanomaterials are especially relevant to catalysis. For example, cage-bell structured Pt-Ru nanoparticles were found to display outstanding methanol tolerance for the cathode reaction of direct methanol fuel cells (DMFCs) as a result of the differential diffusion of methanol and oxygen in the cage-bell structure.     

CONDITIONS OF ORGANOSOL FORMATION FROM METAL SOAPS IN HIGHER ALCOHOLS AND THE SHAPE OF THE DISPERSED PARTICLES

Seven bivalent metal soaps and six trivalent metal soaps were prepared from the various kinds of fatty acids. Upon heating metal soap suspensions in organic solvents, organosols of metal oxides were formed and they showed the special characteristics in color. The scanning electron microscopic examination of the organosol particles showed the spherical, cubic, or irregular shape of 0.3~3.0 μm size. The shape and size of the particles were affected by the type of netal, the concentration of soaps, heating temperature, and the presence of a reducing agent. No relationship between the particles size of organosol and the carbon number of metal soaps was observed in this study. The stable organosol of monodispersed particles were successfully formed upon heating from Co, Mn and Fe metal soaps in 1-decanol containing a reducing agent.     

透明纳米CeO2的合成与表征

采用胶溶法合成了表面修饰十二烷基苯磺酸钠（DBS）的CeO2纳米粒子有机溶胶，探讨了制轩CeO2纳米有机溶胶的最佳实验条件TEM分析表明，CeO2（DBS）纳米粒子呈球形，约3nm，粒径分布均匀，无团聚现象。ED分析表明，CeO2（DBS）纳米粒子为多晶结构。     

Size-selective synthesis and stabilization of gold organosol in C(n)TAC: enhanced molecular fluorescence from gold-bound fluorophores

Gold nanoparticles of variable sizes have been synthesized in toluene employing two-phase (water-toluene) extraction of AuCl4- followed by its reduction with sodium borohydride in the presence of a series of cationic surfactants of a homologous series having the general formula C(n)TAC. The solubility features of the gold particles in the organic solvent have been accounted qualitatively by calculating the van der Waals interaction potential between the particles. The effect of thermal energy and medium dielectric constant on the stability of metal particles has been studied by measuring the surface plasmon resonance. The stabilization of surfactant-mediated gold particles as hydrosol or organosol has been elucidated by considering the double-layer interaction as a function of the dielectric constant of the solvent medium. The influence of the counterion of the phase transfer reagent and stabilizing ligand on the photochemical stability of the gold colloids has been investigated. The fluorescence probe 1-methylaminopyrene (MAP) was considered for the surface functionalization of the gold particles, and it has been found that there is an enhancement of molecular fluorescence from the gold-probe assembly.     

Conversion of the surface property of oleic acid stabilized silver nanoparticles from hydrophobic to hydrophilic based on host-guest binding interaction

This paper describes a general method to change the surface property of the oleic acid stabilized silver nanoparticles and successful tranferring of the silver nanoparticles from the organic phase into the aqueous phase. By vigorous shaking of a biphasic mixture of the silver organosol protected with oleic acid and p-sulfonated calix[4]arene (pSC4) aqueous solution, it is believed that an inclusion complex is formed between oleic acid molecules and pSC4, and the protective layer of the silver nanoparticles shifts from hydrophobic to hydrophilic in nature, which drives the transfer of silver nanoparticles from the organic phase into the aqueous phase. The efficiency of the phase transfer to the aqueous solution depends on the initial pSC4 concentration. The pSC4-oleic acid inclusion complex stabilized nanoparticles can be stable for long periods of time in aqueous phase under ambient atmospheric conditions. The procedure of phase transfer has been independently verified by UV-vis, transmission electron microscopy, Fourier transform infrared, and 1H nuclear magnetic resonance techniques.     

Formation of surfactant-stabilized silica organosols

Organosols comprising silica nanoparticles, stabilized by adsorbed surfactant layers in low dielectric organic solvents were formulated, and their properties studied. A range of different methods for organosol formation starting from aqueous sols were evaluated and compared, in order to determine the most reliable and reproducible approach. To understand the influence of surfactant type and solvent on stability, samples were prepared with a range of surfactants and in different solvents and solvent blends. Structural properties and interparticle interactions were probed using dynamic light scattering (DLS), zeta potentials were determined, and the surfactant layers were investigated with contrast-variation SANS. SANS data suggest that for systems stabilized by ionic surfactants, the nanoparticles are in equilibrium with a population of reverse micelles, but this is apparently not the case for those stabilized by nonionic surfactants. Low zeta potentials show evidence of a small amount of surface charging in these nonaqueous systems, although it is unlikely to have any significant effect on their overall stability.     

Oleic acid-assisted phase transfer of nanosized silver colloids

In this study, it is demonstrated that silver nanoparticles can be transferred from formamide to chloroform using oleic acid as a phase transfer agent with a transfer efficiency of 90–95%. The silver nanoparticles are initially formed as an organosol by the reduction of silver ions with formamide. On aging the complex, the particles self-assemble to form an ordered close-packed two-dimensional array of silver nanocrystals when dissolved in CHCl₃. The size distribution of the colloidal silver particles after transfer in different solvents remains almost the same. On the basis of IR spectroscopy, we discuss the adsorption of oleic acid over the silver particles.     

Synthesis and adsorption and luminescence properties of hydrophobic silver nanoparticles in the presence of pyrene

A procedure was developed for the synthesis of hydrophobic silver nanoparticles with an average size of 4 nm in two-phase water-organic emulsions. The physical properties of the obtained silver organosol were studied by molecular spectroscopy and electron microscopy. It was found that the synthesized silver nanoparticles had a specific surface of 60–110 m²/g. It was shown that chemically modified silver nanoparticles can be used as an adsorbent for preconcentrating polycyclic aromatic hydrocarbons (using pyrene as an example) from dilute n-hexane solutions followed by luminescence determination at room temperature.     

Metal Nodes of Metal-Organic Frameworks can Activate Molecular Hydrogen

Hydrogenation of multiple bonds are among the most general and important organic reactions. Typical heterogeneous catalysts are based on transition metal nanoparticles, including noble metals. Data are presented here showing that metal nodes of MIL-101(Cr) and UiO-66 in the absence of occluded metal nanoparticles can promote hydrogenation of polarized X=Y double bonds of nitro and carbonyl groups. The catalytic activity is a function of the composition of the metal node and the organic linker. It is proposed that the reaction mechanism is based on the operation of frustrated Lewis acid/base pairs.     

Dendrimer-encapsulated nanoparticle precursors to supported platinum catalysts

In this contribution, we report the successful preparation of supported metal catalysts using dendrimer-encapsulated Pt nanoparticles as metal precursors. Polyamidoamine (PAMAM) dendrimers were first used to template and stabilize Pt nanoparticles prepared in solution. These dendrimer-encapsulated nanoparticles were then deposited onto a commercial high surface area silica support and thermally activated to remove the organic dendrimer. The resulting materials are active oxidation and hydrogenation catalysts. The effects of catalyst preparation and activation on activity for toluene hydrogenation and CO oxidation catalysis are discussed.     

Metal Nanoparticles Syntheses on Ionic Liquids Functionalized Mesoporous Silica SBA‐15

Supported metal nanoparticles hold great promise in heterogeneous catalysis as active and reusable catalysts for various organic transformations. Preparation methods of metal nanoparticles with excellent control over size, shape, and morphology on supports has significantly advanced to improve the performances of the resulting catalysts. Here, we aim to discuss the development of supported metal nanoparticles on mesoporous silica SBA‐15 in the presence of immobilized ionic liquids mostly based on examples from the previously reported results. This review highlights the preparation methods for size‐controlled syntheses and the immobilization of metal nanoparticles on solid supports, especially SBA‐15 by various techniques.     

The Effects of Methylene Blue on the Optical Properties of Nanometer-sized CdS Organosol

The inverse micelle system of nanometer-sized CdS doped with Methylene Blue(MB) was synthesized and characterized by using absorption and fluorescence spectra. The results show that MB molecules were absorbed onto the surface of CdS nanoparticles and interacted with surfactants when its concentration was lower than 4×10^-6 mol/L. From the comparison of their spectra, MB molecules by adsorption have a strong quenched fluorescence emission of CdS nanoparticles with surface defect states. All responses and main mechanism are ascribed to the charge transfer between the CdS organosol and Methylene Blue molecules.     

On the origin of the efficient nanoparticle mediated electron transfer across a self-assembled monolayer

Recent advances in bioelectrochemistry came from the elaboration of conducting electrodes modified by an organic layer onto which nanoparticles are adsorbed. Self-assembled monolayers on noble-metal electrodes are known to hinder the electrochemical kinetics of fast-transfer redox systems. Surprisingly, fast kinetics are recovered when metal nanoparticles are deposited on top of the monolayer. We show that this surprising behavior can be fully accounted for when realizing that electron transfer from metal to metal is intrinsically easier than transfer between metal and redox system by many orders of magnitude.     

Recent advances in nanomaterial‐based capillary electrophoresis

This review gives a summary of applications of different nanomateials, such as gold nanoparticles (AuNPs), carbon‐based nanoparticles, magnetic nanoparticles (MNPs), and nano‐sized metal organic frameworks (MOFs), in electrophoretic separations. This review also emphasizes the recent works in which nanoparticles (NPs) are used as pseudostationary phase (PSP) or immobilized on the capillary surface for enhancement of separation in CE, CEC, and microchips electrophoresis.     

General approach for the synthesis of organic-inorganic hybrid nanoparticles mediated by supercritical CO2

We report in this paper novel chemistry that addresses the problem of surfactant solubility in supercritical CO2 for metal nanoparticle synthesis. This new approach for the preparation of organic-functionalized inorganic nanoparticles relies on the reduction of a metal precursor in a CO2-containing insoluble polymer. Reduction of the metal with H2 leads to small nanocrystals stabilized by the polymer with a relatively small polydispersity. The functionalized metal nanoparticles are recovered as a dry powder, free of any organic solvents, which can then be resuspended in an appropriate solvent. This approach limits the number of steps for the preparation of functional nanoparticles which are ready for use. To illustrate this, we report results of the preparation of palladium and silver nanoparticles of 3-5 nm size stabilized with hyperbranched polyamines, functionalized with perfluoroalkyl, perfluorooligoether, non-fluorinated alkyl, polysiloxane, or polyethylene glycol moieties.     

Using gold nanoparticles in spectrophotometry

Published data on the use of gold nanoparticles in spectrophotometry are summarized. Data on methods for preparing gold nanoparticles and their optical properties are presented. The main approaches on which spectrophotometic methods of substance determination using gold nanoparticles are based are discussed. Examples of determining of metal ions, anions, and organic compounds are presented.     

Use of silver nanoparticles in spectrophotometry

Published data on the application of silver nanoparticles to spectrophotometry are summarized. Data on methods of synthesis of silver nanoparticles and their optical properties are presented. The main approaches to the spectrophotometric determination of substances using silver nanoparticles are discussed. Examples of the determination of metal ions, anions, and organic compounds are given.     

Synthesis and characterization of N,N-dimethyldodecylamine-capped Aucore-Pdshell nanoparticles in toluene

In this paper a convenient route for synthesizing Au(core)-Pd(shell) bimetallic nanoparticles in toluene has been reported as a result of co-reduction of gold(III) and palladium(II) precursors in toluene. N,N-Dimethyldodecylamine was used as a capping agent for the core-shell particles, which not only imparts stability to the organosol but also controls morphology of the evolved particles. The particles were characterized using UV-visible, transmission electron microscopy, and X-ray diffraction measurements. All results substantiate the formation of core-shell structure of the synthesized particles.     

Using Sorbents modified by gold nanoparticles in chromatography

The use of sorbents modified by metal nanoparticles in HPLC for the separation of various organic substances is discussed. Authors’ data on the synthesis and study of silicas modified by gold nanoparticles stabilized by organic ligands are summarized. A possibility of the successful separation of nitroaniline, aminopyridine, hydrazines, water-soluble vitamins, β-blockers, and their enantiomers on the synthesized sorbents is shown.     

Detail review on chemical,physical and green synthesis,classification, characterizations and applications of nanoparticles

ABSTRACT

Nanotechnology is an emerging field of science. The base of nanotechnology is nanoparticles. The size of nanoparticles ranges from 1 to 100?nm. The nanoparticles are classified into different classes such as inorganic nanoparticles, organic nanoparticles, ceramic nanoparticles and carbon base nanoparticles. The inorganic nanoparticles are further classified into metal nanoparticles and metal oxide nanoparticles.similarly carbon base nanoparticles classified into Fullerene, Carbon nanotubes, Graphene, Carbon nanofiber and carbon black Nanoparticles are also classified on the basis of dimension such as one dimension nanoparticles, two-dimension nanoparticles and three-dimension nanoparticles. The nanoparticles are synthesized by using two approaches like top-down approach and bottom-up approach. In this review chemical, physical and green synthesis of nanoparticles is reported. The synthesized nanoparticles are synthesized using different qualitative and quantitative techniques. The Qualitative techniques include Fourier Transform Infrared Spectroscopy (FT-IR), UV-Vis spectrophotometry, Scanning electron microscope (SEM), X.ray diffraction (XRD) and Atomic Force Microscopy (AFM). The Quantitative techniques include Transmission Electron Microscopy (TEM), Annular Dark-Field Imaging (HAADF) and Intracranial pressure (ICP). The nanoparticles have different application which is reported in this review.