Controlled synthesis of different types iron oxides nanocrystals in paraffin oil

Monodisperse Fe3O4 and FeO nanocrystals (NCs) with different sizes (from 10 nm to 50 nm) and different shapes (cube, sphere, and ellipsoid) were synthesized by simply adjusting reaction temperature or molar ratio of Fe/oleic acid (OA) during the decomposition of FeO(OH) in noncoordinating solvent. The concentration of OA affected the nucleation and growth of NCs by improving the chemical reaction driving force during the syntheses of different types of iron oxide NCs. It has been found that the reaction temperature influenced the reaction activity between FeO(OH) and OA. The structure of Fe oleate complexes was studied using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM) were used for structural and chemical characterization of as-prepared iron oxide NCs.     

The influence of oxygen on the fluorescence enhancement of fatty-acid-capped CdS nanocrystals

CdS nanocrystals were synthesized in 1-octadecene (ODE) solution with oleic acid (OA) as a capping agent. Freshly prepared CdS nanocrystals showed a weak orangelike fluorescence due to defects on the particle surface. After several weeks' storage, the bulk fluorescence of CdS nanocrystals was dramatically enhanced, which gave the nanocrystals a blue or violet appearance. UV and photoluminescence (PL) measurements were employed to investigate this process. It has been found that the oxygen in the air played the most important role. The oxygen atoms could absorb on the surface of particles and a layer of oxide was gradually formed, which effectively passivated the surface of CdS nanocrystals. Interestingly, this oxidative process had no relation to UV illumination.     

Effect of digestion time and alkali addition rate on physical properties of magnetite nanoparticles

We investigate the effect of digestion time and alkali addition rate on the size and magnetic properties of precipitated magnetite nanoparticles. It is observed that the time required to complete the growth process for magnetite nanocrystals is very short (approximately 300 s), compared to long digestion times (20-190 min) required for MnO and CdSe nanocrystals. The rapid growth of magnetite nanoparticles suggests that Oswald ripening is insignificant during the precipitation stage, due to the low solubility of the oxides and the domination of a solid-state reaction where high electron mobility between Fe2+ and Fe3+ ions drives a local cubic close-packed ordering. During the growth stage (0-300 s), the increase in the particle size is nominal (6.7-8.2 nm). The effect of alkali addition rate on particle size reveals that the nanocrystal size decreases with increasing alkali addition rate. The particle size decreases from 11 to 6.8 nm as the alkali addition rate is increased from 1 to 80 mL/s. During the size decrease, the lattice parameter decreases from 0.838 to 0.835 nm, which is attributed to an increase in the amount of Fe3+ atoms at the surface due to oxidation. As the alkali addition rate increases, the solution reaches supersaturation state rapidly leading to the formation of large number of initial nuclei at the nucleation stage, resulting in large number of particles with smaller size. When alkali addition rate is increased from 1 to 80 mL/s, the saturation magnetization of the particles decreases from 60 to 46 emu/g due to the reduced particle size.     

Precipitation polymerization in acetic acid: synthesis of monodisperse cross-linked poly(divinylbenzene) microspheres

This paper reports two important results with cross-linked precipitation polymerization. (1) Acetonitrile, a substance harmful to human health, is the most commonly used solvent for the synthesis of cross-linked polymeric microspheres by precipitation polymerization. Here, the much safer acetic acid replaced acetonitrile as a solvent in the precipitation polymerization of monodisperse cross-linked poly(divinylbenzene) (PDVB-55) microspheres. Pumpkin-like particles and microspheres were obtained. XPS results displayed a significant amount of double bonds on the surface of the particles. The effect of monomer content, temperature, and initiator amount on the formed particles were studied. For a DVB loading below 1 vol % at 70 degrees C, monodisperse microspheres with smooth surfaces and narrow diameters were successfully obtained. With a DVB loading of 2 vol % and by observing the shapes of particles obtained with three different temperature(60, 70, and 80 degrees C), we found that more spherical particles were obtained at higher temperatures and pumpkin-like particles were obtained at lower temperatures. No significant differences in morphology or the coefficient of variation (CV) of the particles were obtained for different initiator loadings, whereas the particle diameters could be increased with increased initiator concentrations. (2) In order to obtain a better understanding of the formation mechanism of these particles, time-dependent experiments, for the first time, were conducted in a hydrophobic monomer system. By tracing the whole polymerization process, some important results were found. First, with the polymerization time at 70 degrees C, the particle diameters were found to increase from 800 nm to 3.0 microm, the CV displayed a decrease, and the amount of spheres and the spherical evenness of the particle surfaces improved. Second, by quantitatively calculating the particle number from the yields and diameters data, it is found that starting from 3.1% yield or two hours reaction time the total amount of particles in the system is almost a constant (about 9.6 x 10 (8)/L), which means that no homocoagulation occurred and no new particles were generated after nucleation, and there is a linear relation between cubic diameters and yields. These two results give us a distinct impression that particle growth almost comes from capturing of newly formed oligomers. Based on the above results, a scheme for the particle formation is proposed, which shows that that pumpkin-like particles are caused by a prolonged nucleation including the homocoagulation of primary nuclei. The growth of the particles includes two modes, an in situ surface polymerization of monomer and the adsorption of PDVB-55 oligomers. The differences between results in acetonitrile and in acetic acid (higher yields, smaller size, not spherical but pumpkin-like particles in acetic acid) were due to the lower solubilizability of acetic acid which is the so-called proton-containing solvent with the hydrogen bonding structure.     

Ozonolysis of mixed oleic acid/n-docosane particles: the roles of phase, morphology, and metastable states

The reaction kinetics of ozone with oleic acid (OA) in submicron particles containing n-docosane has been studied using aerosol CIMS (chemical ionization mass spectrometry) to monitor changes in particle composition. Internally mixed particles with X(OA) > 0.72 were found to exist as supercooled droplets when cooled to room temperature. Partial reaction of the oleic acid was seen to completely inhibit further reaction and was attributed to the formation of a metastable solid rotator phase of the n-docosane at the surface. This reaction-induced phase change is believed to prevent further reaction by slowing ozone diffusion into the particle. When these particles were cooled to 0 degrees C before reaction, they reacted to a further extent and did not demonstrate such an inhibition. This shift in reactivity upon cooling is attributed to the formation of the thermodynamically stable form of n-docosane, the triclinic solid. This transition was accompanied by an increase in the n-docosane density, which led to the development of "cracks" through which ozone can diffuse into the particle. The aerosol with X(OA) < 0.72 consisted of an external mixture of particles containing n-docosane in either the rotator or the triclinic solid phase because of the stochastic nature of the rotator --> triclinic transition. The reactivity of the oleic acid was seen to increase with increasing n-docosane content as a larger fraction of the particles underwent the rotator --> triclinic transition and therefore contained cracks at the surface. These findings demonstrate the importance of transient, metastable phases in determining particle morphology and how such morphological changes can influence rates of reactions in organic aerosols.     

Highly luminescent lead sulfide nanocrystals in organic solvents and water through ligand exchange with poly(acrylic acid)

Hydrophobic lead sulfide quantum dots (PbS/OA) synthesized in the presence of oleic acid were transferred from nonpolar organic solvents to polar solvents such as alcohols and water by a simple ligand exchange with poly(acrylic acid) (PAA). Ligand exchange took place rapidly at room temperature When a colloidal solution of PbS/OA in tetrahydrofuran (THF) was treated with excess PAA, the PbS/PAA nanocrystals that formed were insoluble in hexane and toluene but could be dissolved in methanol or water, where they formed colloidal solutions that were stable for months. Ligand exchange was accompanied by a small blue shift in the band-edge absorption, consistent with a small reduction in particle size. While there was a decrease in quantum yield associated with ligand exchange and transfer to polar solvents, as is commonly found for colloidal quantum dots, the quantum yields determined were impressively high: PbS/OA in toluene (82%) and in THF (58%); PbS/PAA in THF (42%) and in water (24%). The quantum yields for the PbS/PAA solutions decreased over time as the solutions were allowed to age in the presence of air.     

一步湿化学法合成超细金纳米线

以氯金酸(HAuCl₄)为前驱物, 油胺同时作为溶剂、表面稳定剂和还原剂, 通过简单的一步湿化学法合成超细金纳米线. 制备出的超细金纳米线不仅产量高、纯度高, 而且纵横比大, 纳米线平均直径~2 nm, 长度可达数十微米. 如果添加另一种还原剂油酸并调节油胺和油酸的体积比为1:1, 将生成直径为~9 nm的金纳米线. 通过改变反应温度和还原剂用量, 对该种超细金纳米结构的生长机制进行阐述说明: 以油胺为模板, 在油胺和一价金卤化物(AuCl)亲金键合形成的一维聚合链作用下, 被还原的金原子附着在已成核颗粒表面, 一维地生长成超细金纳米线.     

Particle Production in Reflection and Transmission Mode Laser Ablation: Implications for Laserspray Ionization

Particles were ablated from laser desorption and inlet ionization matrix thin films with a UV laser in reflection and transmission geometries. Particle size distributions were measured with a combined scanning mobility particle sizer (SMPS) and aerodynamic particle sizer (APS) system that measured particles in the size range from 10 nm to 20 μm. The matrixes investigated were 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), sinapic acid (SA), 2,5-dihydroxy-acetophenone (DHAP), and 2-nitrophloroglucinol (NPG). Nanoparticles with average diameters between 20 and 120 nm were observed in both transmission and reflection geometry. The particle mass distribution was significantly different in reflection and transmission geometry. In reflection geometry, approximately equal mass was distributed between particles in the 20 to 450 nm range of diameters and particles in the 450 nm to 1.5 μm diameter range. In transmission mode, the particle mass distribution was dominated by large particles in the 2 to 20 μm diameter range. Ablation of inlet ionization matrices DHAP and NPG produced particles that were 3 to 4 times smaller compared with the other matrices. The results are consistent with ion formation by nanoparticle melting and breakup or melting and breakup of the large particles through contact with heated inlet surfaces.

Phase- and size-controllable synthesis of hexagonal upconversion rare-earth fluoride nanocrystals through an oleic acid/ionic liquid two-phase system

Herein, we introduce a facile, user- and environmentally friendly (n-octanol-induced) oleic acid (OA)/ionic liquid (IL) two-phase system for the phase- and size-controllable synthesis of water-soluble hexagonal rare earth (RE = La, Gd, and Y) fluoride nanocrystals with uniform morphologies (mainly spheres and elongated particles) and small sizes (<50?nm). The unique role of the IL 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF(6)) and n-octanol in modulating the phase structure and particle size are discussed in detail. More importantly, the mechanism of the (n-octanol-induced) OA/IL two-phase system, the formation of the RE fluoride nanocrystals, and the distinctive size- and morphology-controlling capacity of the system are presented. BmimPF(6) is versatile in term of crystal-phase manipulation, size and shape maintenance, and providing water solubility in a one-step reaction. The luminescent properties of Er(3+)-, Ho(3+)-, and Tm(3+)-doped LaF(3), NaGdF(4), and NaYF(4) nanocrystals were also studied. It is worth noting that the as-prepared products can be directly dispersed in water due to the hydrophilic property of Bmim(+) (cationic part of the IL) as a capping agent. This advantageous feature has made the IL-capped products favorable in facile surface modifications, such as the classic Stober method. Finally, the cytotoxicity evaluation of NaYF(4):Yb,Er nanocrystals before and after silica coating was conducted for further biological applications.     

A novel chelating acid-assisted thermolysis procedure for preparation of tin oxide nanoparticles

Pure tin dioxide (SnO₂) nanoparticles were synthesized via thermolysis of tin phthalate and tin oxalate in the presence of oleic acid (OA) as solvent. Oleic acid (OA) was employed as an organic solvent, which can be applied to control particle growth and to stabilize the particles. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. The orthorhombic phase SnO₂ nanoparticles with average size about 12 nm were synthesized through thermolysis of tin phthalate in the presence of oleic acid.     

Photoelectron spectroscopic investigations of chemical bonding in organically stabilized PbS nanocrystals

The surface structure of organically capped PbS nanocrystals using synchrotron radiation excited core-level photoelectron spectroscopy has been studied. The nanocrystallites prepared by methods of colloidal chemistry have average diameters of 3.1, 3.9, 4.6, and 7.6 nm with narrow size distributions and are stabilized either with oleic acid only or with a combination of trioctylphosphine and oleic acid as ligands. High resolution photoelectron spectroscopy measurements allowed the surface structure to be studied and in particular how the organic ligands bind to the surface of the PbS nanocrystals to be elucidated. The results indicate that the trioctylphosphine ligands passivate only the surface S sites while oleic acid ligands appear to bind mainly to Pb sites.     

From trifluoroacetate complex precursors to monodisperse rare-earth fluoride and oxyfluoride nanocrystals with diverse shapes through controlled fluorination in solution phase

We report the first systematic synthesis of monodisperse rare-earth (RE=La to Lu, Y) fluoride and oxyfluoride nanocrystals with diverse shapes (trigonal REF3 triangular, truncated-triangular, hexagonal, and polygonal nanoplates; orthorhombic REF3 quadrilateral and zigzag-shaped nanoplates; cubic REOF nanopolyhedra and nanorods) from single-source precursors (SSP) of [RE(CF(3)COO)(3)] through controlled fluorination in oleic acid (OA)/oleylamine (OM)/1-octadecene (ODE). To selectively obtain REF3 or REOF nanocrystals, the fluorination of the RE-O bond to the RE-F bond at the nucleation stage was controlled by finely tuning the ratio of OA/ODE or OA/OM, and the reaction temperature. For phase-pure REF3 or REOF naocrystals, their shape-selective syntheses could be realized by further modifying the reaction conditions. The two-dimensional growth of the REF3 nanoplates and the one-dimensional growth of the REOF nanorods were likely due to the selective adsorption of the capping ligands on specific crystal planes of the nanocrystals. Those well-shaped nanocrystals with diverse geometric symmetries (such as D(3h), D(6h), C(2h), O(h), and D(nh)) displayed a remarkable capability to form self-assembled superlattices. By manipulating the solvent-substrate combination, the plate-shaped REF3 nanocrystals could form highly ordered nanoarrays by means of either the face-to-face formation or the edge-to-edge formation. By using this SSP strategy, we also obtained high-quality LaF3:Eu and LaF3:Eu/LaF3 triangular nanoplates that showed photoluminescent red emissions of Eu3+ ions sensitive to the surface effect.     

Ultrasonic-Assisted Synthesis of Monodisperse Ag Nanoparticles and Their Applications in Surface Enhanced Raman Scattering and Fluorescence Enhancement

Monodisperse Ag nanoparticles with diameters of about 3.4 nm were synthesized by a facile ultrasonic synthetic route at room temperature with the reduction of borane-tert-butylamine in the presence of oleylamine (OAm) and oleic acid (OA). The reaction parameters of time, the molar ratios of OAm to OA were studied, and it was found that these parameters played important roles in the morphology and size of the products. Meanwhile, surface enhanced Raman spectrum (SERS) property suggested the Ag nanoparticles exhibited high SERS effect on the model molecule Rhodamine 6G. And also, two-photon fluorescence images showed that the silver nanoparticles had high performances in fluorescence enhancement.     

Structure of submonolayer oleic acid coverages on inorganic aerosol particles: evidence of island formation

A series of submonolayer deposition studies of oleic acid on both hydrophobic and hydrophilic surfaces has shown that oleic acid self-associates into islands rather than uniformly covering the surfaces. The studies were performed by vapor deposition on 1.6 mum diameter polystyrene aerosol particles as well as on polystyrene and silica surfaces. The surfaces were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), ellipsometry and contact-angle goniometry. After timescales of minutes to hours of vapor deposition at 70 degrees C, the oleic acid arranged itself in the form of islands with diameters of about 100 nm. Many of the islands are 25-30 A high, suggesting that the oleic acid sits vertically on the surface. The surface structure of oleic acid on particles is expected to impact on several atmospherically relevant properties such as the reactivity of the oleic acid and the hygroscopicity of the particles.     

Experimental and First‐Principles Characterization of Functionalized Magnetic Nanoparticles

Magnetic iron oxide nanoparticles synthesized by coprecipitation and thermal decomposition yield largely monodisperse size distributions. The diameters of the coprecipitated particles measured by X‐ray diffraction and transmission electron microscopy are between approximately 9 and 15 nm, whereas the diameters of thermally decomposed particles are in the range of 8 to 10 nm. Coprecipitated particles are indexed as magnetite‐rich and thermally decomposed particles as maghemite‐rich; however, both methods produce a mixture of magnetite and maghemite. Fourier transform IR spectra reveal that the nanoparticles are coated with at least two layers of oleic acid (OA) surfactant. The inner layer is postulated to be chemically adsorbed on the nanoparticle surface whereas the rest of the OA is physically adsorbed, as indicated by carboxyl O? H stretching modes above 3400 cm^?1. Differential thermal analysis (DTA) results indicate a double‐stepped weight loss process, the lower‐temperature step of which is assigned to condensation due to physically adsorbed or low‐energy bonded OA moieties. Density functional calculations of Fe–O clusters, the inverse spinel cell, and isolated OA, as well as OA in bidentate linkage with ferrous and ferric atoms, suggest that the higher‐temperature DTA stage could be further broken down into two regions: one in which condensation is due ferrous/ferrous– and/or ferrous/ferric–OA and the other due to condensation from ferrous/ferric– and ferric/ferric–OA complexes. The latter appear to form bonds with the OA carbonyl group of energy up to fivefold that of the bond formed by the ferrous/ferrous pairs. Molecular orbital populations indicate that such increased stability of the ferric/ferric pair is due to the contribution of the low‐lying Fe³⁺ t_2g states into four bonding orbitals between ?0.623 and ?0.410 a.u.     

Synthesis of P(AA‐SA)/ZnO composite latex particles via inverse miniemulsion polymerization and its application in pH regulation and UV shielding

Poly(acrylic acid‐co‐sodium acrylate)/zinc oxide, P(AA‐SA)/ZnO, composite latex particles were synthesized by inverse miniemulsion polymerization. The ZnO nanoparticles were prepared by hydrothermal synthesis and undergone oleic acid (OA) surface treatment. The X‐ray diffraction pattern and FT‐IR spectra characterized the crystal structure and functional groups of OA‐ZnO nanoparticles. An appropriate formulation in preparing P(AA‐SA) latex particles, ensuring the dominant in situ particle nucleation and growth, was developed in our experiment first. Sodium hydroxide was chosen as a costabilizer, because of its ability to increase the deprotonation of acylic acid and enhance the hydrophilicity of monomer, acrylic acid besides providing osmotic pressure. The growth mechanism of P(AA‐SA)/ZnO composite particles was proposed. The OA‐ZnO nanoparticles were adsorbed on or around the surface of P(AA‐SA) latex particles by hydrophobic interaction, thus enhanced the interfacial tension over latex particles. The P(AA‐SA)/ZnO composite latex particles owned better thermal stability than pure latex particles. The pH regulation capacity was excellent for both ZnO and P(AA‐SA) particles. Combining P(AA‐SA) and ZnO nanoparticles into composite particles, the performance in pH regulation and UV shielding was discussed from our experimental results. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8081–8090, 2008     

Effects of charge and size on condensation of supersaturated water vapor on nanoparticles of SiO2

The effects of size and charge on the condensation of a supersaturated water vapor on monodisperse nanoparticles of SiO(2) were investigated in a flow cloud chamber. The dependences of the critical supersaturation S(cr) on particle size at diameters of 10, 12, and 15 nm as well as on charge and charge polarity are determined experimentally. A novel electrospray aerosol generator was developed to generate a high concentration of SiO(2) nanoparticles of less than 10 nm by electrospraying silicon tetraethoxide (STE) ethanol solution followed by the thermal decomposition of STE. The effects of liquid flow rate, liquid concentration, flow rate of carrier gas, and liquid conductivity on the particle size distribution and concentration were examined. For charged particles, the nucleation occurs at a critical supersaturation S(cr) lower than that on neutral particles, and the charge effect fades away as particle size increases. The charge effect is stronger than the theoretical predictions. In addition, a sign preference is detected, i.e., water vapor condenses more readily on negatively charged particle, a trend consistent with those observed on ions. However, both effects of charge and charge polarity on S(cr) are stronger than that predicted by Volmer's theory for ion-induced nucleation.     

Controllable Synthesis and Study on Morphology of Copper Nanowires

High‐purity, large‐aspect‐ratio, and well‐dispersed copper nanowires (CuNWs) with an average diameter of 45 nm and length >100 μm were successfully synthesized by reducing a Cu(II) salt with glucose, with oleylamine (OM) and oleic acid (OA) serving as dual capping agents, through hydrothermal reduction. A systematic study of the effects of the copper salt, capping agents, reductant, and temperature on the morphology of CuNWs has been conducted. Our results indicate that CuNWs with different diameters can be obtained using different copper salts. The diameter of the as‐prepared CuNWs decreases with increasing amounts of OM/OA and glucose but increases with the increasing temperature of the reaction. By adjusting the experimental parameters, we could achieve controlled synthesis of CuNWs and obtain high‐quality CuNWs with different diameters of 45, 76, 85, 90, 100, 112, 135, and 175 nm.     

Large-scale synthesis of TiO2 nanorods via nonhydrolytic sol-gel ester elimination reaction and their application to photocatalytic inactivation of E. coli

A simple method of synthesizing a large quantity of TiO(2) nanorods was developed. A nonhydrolytic sol-gel reaction between titanium(IV) isopropoxide and oleic acid at 270 degrees C generated 3.4 nm (diameter) x 38 nm (length) sized TiO(2) nanocrystals. The transmission electron microscopic image showed that the particles have a uniform diameter distribution. X-ray diffraction and selected-area electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the TiO(2) nanorods are highly crystalline anatase crystal structure grown along the [001] direction. The diameters of the TiO(2) nanorods were controlled by adding 1-hexadecylamine to the reaction mixture as a cosurfactant. TiO(2) nanorods with average sizes of 2.7 nm x 28 nm, 2.2 nm x 32 nm, and 2.0 nm x 39 nm were obtained using 1, 5, and 10 mmol of 1-hexadecylamine, respectively. The optical absorption spectrum of the TiO(2) nanorods exhibited that the band gap of the nanorods was 3.33 eV at room temperature, which is 130 meV larger than that of bulk anatase (3.2 eV), demonstrating the quantum confinement effect. Oleic acid coordinated on the nanorod surface was removed by the reduction of the carboxyl group of oleic acid, and the Brunauer-Emmett-Teller surface area of the resulting naked TiO(2) nanorods was 198 m(2)/g. The naked TiO(2) nanorods exhibited higher photocatalytic activity than the P-25 photocatalyst for the photocatalytic inactivation of E. coli.     

Phosphine-free synthesis of CdSe nanocrystals

High quality CdSe nanocrystals have been prepared using elemental selenium as the chalcogenide precursor dispersed in 1-octadecene (ODE). The conditions used to prepare the Se precursor were found to be critical for successful nanocrystal synthesis. Systematic titration of the Se precursor solution with tri-n-octylphosphine (TOP) allowed the Se reactivity to be tuned and the final particle size to be controlled. Band-edge and surface related emission were observed for samples prepared in the presence and absence of added TOP. In the absence of a selenium passivant, the crystal structure of CdSe nanocrystals could be altered from zinc blende to wurtzite by the addition of bis(2,2,4-trimethylpentyl)phosphinic acid (TMPPA).