Structural analysis of cobalt titanate nanoparticles obtained by sol–gel process

In this work we report the synthesis of nanocomposites based on nanoparticles of cobalt titanate and titanium dioxide in their anatase crystalline phase by a sol–gel process. The synthesized nanoparticles of titanate vary from 1 to 6 nm in size. They are embedded in the anatase matrix, and they were obtained from TiO₂ monoliths doped with Co²⁺. The formation of cobalt titanate nanoparticles showed a linear dependence on the cobalt concentration. The cobalt titanate nanocrystals are very stable even at temperatures higher than 1000 °C. The crystalline structures of the samples were examined using high-resolution transmission electron microscopy and X-ray diffraction. Molecular simulation methods were utilized for a better understanding and for improving the analytical data interpretation of the experimental results. PACS 61.16.Bg; 79.60.Jv; 61.46.+w; 61.50.Ah     

Effect of drying temperature on sizes and morphology of goethite nanoparticles

The morphology, structure, and size distribution of goethite nanoparticles, which are obtained by chemical precipitation of iron salt and alkali in aqueous solutions with different surfactants and are dried at 100°C and room temperature, have been investigated in order to develop technology for obtaining goethite (α-FeOOH) nanoparticles of minimum sizes. It is found that the samples dried at a temperature of 100°C have a different phase state and increased sizes as compared to the samples dried at room temperature.     

Self assembly of inorganic nanocrystals in 3D supra crystals: Intrinsic properties

Here we describe how arrangements of nanocrystals can self-organize in 3D arrays called supra crystals. The 3D arrays can fall into the familiar categories of face centered cubic (fcc), hexagonal compact packing (hcp) crystals, and body centered (bcc) crystals. Intrinsic collective properties of these 3D arrangements are different from the properties of individual nanoparticles and from particles in bulk.We demonstrate by two various processes and with two types of nanocrystals (silver and cobalt) that when nanocrystals are self ordered in 3D superlattices, they exhibit a coherent breathing mode vibration of the supra crystal, analogous to a breathing mode vibration of atoms in a nanocrystal.Comparison between the approaches to saturation of the magnetic curve for supra crystals and disordered aggregates produced from the same batch of nanocrystals is similar to that observed with films or nanoparticles either highly crystallized or amorphous.     

Role of ions in the colloidal synthesis of gold nanowires

Gold nanocrystals of different shapes have been made by a wet chemical approach based on a two-step, seed-mediated synthesis. In this paper, we demonstrate a one-step synthetic method for achieving simple and systematic control over the shape of gold nanoparticles. Gold nanowires, which have been prepared by multi-step approaches, are produced in very high yield in this single-step technique. The width of the rods can be varied over a broader range compared to previously reported methods. Rectangle-, cube- or tetrapod-like gold nanocrystals can also be prepared in aqueous solution at room temperature. The formation of various shapes, in the presence of silver nitrate, requires bromide ion and alkylammonium surfactant ion of appropriate hydrocarbon tail length. The shape, dimension and yield of the nanocrystals depend on the nature and concentrations of the stabilizing cationic surfactants and other additives, such as salts, in addition to the reactants.     

Cobalt nanoparticles synthesis from Co(CH3COO)2 by thermal decomposition

Nontoxic cobalt acetate tetrahydrate was used as a precursor to prepare cobalt nanoparticles of 8–200 nm in average diameter by thermal decomposition. The different combinations of trioctylphosphine, oleylamine and oleic acid were added as surfactants to control the particle size. These combinations resulted in the particles with saturation magnetization and coercive force ranging from 55.0 to 100.1 emu/g and from 0 to 459.3 Oe, respectively.     

Nanocomposites of magnetic cobalt nanoparticles and cellulose

Polymeric matrices with stabilized metallic nanoparticles constitute an important class of nanostructured materials, because polymer technology allows fabrication of components with various electronic, magnetic and mechanical properties. The porous cellulose matrix has been shown to be a useful support material for platinum, palladium, silver, copper and nickel nanoparticles. In the present study, nanosized cobalt particles with enhanced magnetic properties were made by chemical reduction within a microcrystalline cellulose (MCC) matrix. Two different chemical reducers, NaBH₄ and NaH₂PO₂, were used, and the so-formed nanoparticles were characterized with X-ray absorption spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These experimental techniques were used to gain insight into the effect of different synthesis routes on structural properties of the nanoparticles. Magnetic properties of the nanoparticles were studied using a vibrating sample magnetometer. Particles made via the NaBH₄ reduction were amorphous Co-B or Co oxide composites with diminished ferromagnetic behaviour and particles made via the NaH₂PO₂ reduction were well-ordered ferromagnetic hcp cobalt nanocrystals.     

Mössbauer and MCD spectroscopy of the Fe3S4 nanoparticles synthesized by the thermal decomposition method with two different surfactants

Greigite (Fe₃S₄) nanoparticles (NPs) were fabricated by the thermal decomposition method using two different surfactants: oleylamine (OLA) and 1-hexadecylamine (HDA). In both cases, the synthesized NPs were characterized as the Fe₃S₄ nanocrystals with minor inclusions of Fe₉S₁₁ phase. FT-IR spectroscopy and thermo-gravimetric analysis allow concluding about OLA or HDA shells covering magnetic core of NPs. Mössbauer spectra has revealed deviations of iron ions distribution among crystal positions from that presented in literature for pure greigite. In accordance with these deviations, the pronounce changes are observed in the magnetic circular dichroism (MCD) spectra which manifest themselves as the spectrum shift to higher energies of electromagnetic waves and redistribution of the MCD maximum intensities. These effects are associated with a change in the density of electronic states in the samples due to the redistribution of iron ions between octahedral and tetrahedral positions in nanocrystals under the influence of surfactants.     

Morphologies and magnetic properties of FeCo nanoparticles modulated by changing the types of ligands of Co

A new way of preparing FeCo nanoparticles has been developed using the co-precipitation technique based on the appropriate Co precursors of different types of ligands. These new precursors have been prepared by the reaction of cobalt acetate with three various coordination compositions for forming cobalt complex types. This technique provides proper control on nanoparticle size distribution after annealing to 500 °C. The variation of the magnetic properties with the type of ligands of Co can arise from the changes of the microstructures and crystalline anisotropies. Maximum coercivity values of 480 Oe were obtained. It is found that the precursors with special structures can prevent from agglomeration without presence of any surfactants.     

Formation and microstructure of carbon encapsulated superparamagnetic Co nanoparticles

Carbon encapsulated magnetic cobalt nanoparticles have been synthesized by the modified arc-discharge method. Both high resolution transmission electron microscopy (HREM) and powder X-ray diffraction (XRD) profiles reveal the presence of 8–15 nm diameter crystallites coated with 1–3 carbon layers. In particular, HREM images indicate that the intimate and contiguous carbon fringe around those Co nanoparticles is good evidence for complete encapsulation by carbon shell layers. The encapsulated phases are identified as hcp α-Co, fcc β-Co and cobalt carbide (Co₃C) nanocrystals using X-ray diffraction (XRD), nano-area electron diffraction (SAED) and energy dispersive X-ray analysis (EDX). However, some fcc β-Co particles with a significant fraction of stacking faults are observed by HREM and confirmed by means of numerical fast Fourier transform (FFT) of HREM lattice images. The carbon encapsulation formation and growth mechanism are also reviewed.     

Cobalt induced nanocrystals on Ge(001)

The deposition of several monolayers of cobalt on germanium (001) substrates results in the formation of two types of clusters: flat-topped and peaked nanocrystals. Scanning tunneling spectroscopy and helium ion microscopy measurements reveal that these nanocrystals contain cobalt. The shape evolution of the flat-topped and peaked nanocrystals as a function of their size is investigated with scanning tunneling microscopy. For small sizes the nanocrystals are compact. Beyond a critical size, however, the peaked nanocrystals exhibit an elongated shape, whilst the flat-topped nanocrystals remain compact. The shape transition of the peaked nanocrystals is driven by a competition between boundary and strain energies. For small sizes the boundary energy is the dominant term leading to a minimization of the peaked nanocrystal's perimeter, whereas at larger sizes the strain energy wins resulting in a maximization of the perimeter. On the top facet of the flat-topped nanocrystals one-dimensional structures are observed that are comprised of small square shaped units of about 1 nm². Time-resolved scanning tunneling microscopy measurements reveal that these square shaped units are dynamic at room temperature.     

Ionic magnetic fluid based on cobalt ferrite nanoparticles: Influence of hydrothermal treatment on the nanoparticle size

Magnetic fluid based on cobalt ferrite nanoparticles was obtained using a hydrothermal treatment added to the Massart procedure. This treatment increases the average size of the nanoparticles from 11.9 to 18.7 nm and also improves the dispersity and crystallinity of the cobalt ferrite particles. The nanoparticles obtained after the hydrothermal treatment were dispersed in aqueous solvent by the classical procedure for ionic magnetic fluids. The ferrofluid thus obtained is stable at pH 7 and may be useful for hyperthermia applications.     

Morphology effects in nanocrystalline CuInSe<Subscript>2</Subscript>-conjugated polymer hybrid systems

We investigated blends of poly hexylthiophene (P3HT) with copper indium diselenide nanocrystals for photovoltaic applications. Depending on the synthesis, the particles were shielded by different organic surfactants. Different concentrations of these nanoparticles were suspended in the polymer solutions and spin cast onto ITO glass. Morphological studies have been performed by atomic force microscopy and transmission electron microscopy. Films consisting of tri-n-octylphosphine oxide-capped CISe:P3HT show photovoltaic response. The best performance we obtained is an open-circuit voltage of about 1 V and a photocurrent of 0.3 mA/cm² using a white light illumination intensity of 80 mW/cm². PACS 78.66.Sq     

The effect of solvent on the crystal structure and size distribution of cadmium sulfide nanocrystals

CdS nanocrystals with different structures were synthesized by the method of solution precipitation using thiourea and cadmium acetate as starting materials in different solvents: water, methanol and N,N-dimethylformamide (DMF). Our results show that the solvent has direct effect on the structure and size of the final nanoparticles. It was found that using DMF, as a solvent, results in producing smaller nanoparticles with the cubic structures, while using the other solvents gives rise to larger nanoparticles with the hexagonal structure. It was also found that using heat during washing the precipitate results in a more homogenous size distribution of CdS nanocrystals. On the basis of our experimental results we also suggest a critical structure transformation size.     

Preparation of Co3O4 nanoparticles by nonhydrolytic thermolysis of [Co(Pht)(H2O)]n polymers

Benzenedicarboxylate complexes, especially phthalate ones, can be significant precursors for the preparation of nano-sized metal and metal oxides. The injection of organic surfactants such as oleic acid (OA) and triphenylphosphine into molecular precursors has yielded samples with size control, narrow size distributions and crystallinity of individual nanocrystals. Fourier transform infrared and X-ray photoelectron spectroscopy revealed that the OA molecules were adsorbed on the ferromagnetic nanoparticles by chemisorption. The temperature-dependent magnetization curve in zero-field-cooled and field-cooled exhibit weak ferromagnetism of the Co₃O₄ nanoparticles. At 300 K the remanent magnetization is 0.02 emu/g, the coercive field is 441 Oe and the magnetization at saturation is 1.05 emu/g.     

Fluorescence spectroscopy of semiconductor CdTe nanocrystals: preparation effect on photostability

We report on continuous-wave and time-resolved fluorescence spectroscopy studies of CdTe water-soluble nanocrystals at room temperature. For nanocrystals spread directly on the substrate we observe large variation both in fluorescence maximum energy and fluorescence lifetime. We attribute this to the influence of the surface of the nanocrystals on the stability of excitations in the nanocrystals. As the fluorescence lifetime of the nanocrystals is monitored, we find it increases with time from 6 to 18 ns and then saturates. Placing the nanocrystals in a polymer matrix remarkably improves the photostability and all the above-mentioned effects are diminished. Upon mixing the nanocrystals with gold spherical nanoparticles we observe a decrease of the fluorescence intensity due to efficient energy transfer to the nanoparticles.     

Intrinsic behavior of face-centered-cubic supra-crystals of nanocrystals self-organized on mesoscopic scale

We describe intrinsic behavior due to the high ordering of nanocrystals at the mesoscopic scale. The first example shows well-defined columns in the formation of cobalt nanocrystals when an applied magnetic field is applied during the evaporation process. Collective breathing properties between nanocrystals are demonstrated. In both cases, these features are observed when the nanocrystals are highly ordered in fcc supra-crystals.     

Internal Structure and Magnetic Properties in Cobalt Ferrite Nanoparticles: Influence of the Synthesis Method

The design of novel nanostructured magnetic materials requires a good understanding of the variation in the magnetic properties due to different synthesis conditions. In this work, four different procedures for fabricating Co‐ferrite nanoparticles with similar sizes between 7 and 10 nm are compared by studying their structural and magnetic properties. Non‐aqueous methods based on the thermal decomposition of metal acetylacetonates at high temperatures, either with or without surfactants, provide highly crystalline nanoparticles with large saturation magnetization values and a coherent reversal of the magnetic moment. However, variations in the density of defects and in the shape of the nanocrystals determine the distribution of switching fields and the effective magnetic anisotropy, which reaches up to ≈1 × 10⁷ erg cm^?3 for oleic acid‐capped 9 nm nanoparticles. It is shown that the saturation magnetization values for nanoparticles produced by different methods are in the range between 49 and 95 emu g^?1 due to differences in the stoichiometry, in the cation occupancy, in the magnetic disorder and in the spin canting of the magnetic sub‐lattices, the latter evaluated by in‐field Mössbauer spectroscopy.     

Facile controlled synthesis of micro/nanostructure MCrO4 (M = Ba, Pb) by using Gemini surfactant C12-PEG-C12 as a soft template

Gemini surfactants, double sodium α-sulfonic polyethylene glycol laurate (abbreviated C₁₂-PEG-C₁₂), were prepared and applied as soft templates in the controlled synthesis of BaCrO₄ and PbCrO₄ micro/nanocrystals. The template effects were investigated by adjusting the length of the spacer, using PEG400 and PEG4000, of the Gemini surfactant. The results indicated that the size and morphology of BaCrO₄ and PbCrO₄ micro/nanocrystals varied with the change in spacer length of C₁₂-PEG-C₁₂, suggesting that the different lengths of the polyethylene glycol group spacers in the Gemini surfactants played a key role in determining the size and shape of the MCrO₄ micro/nanoparticles. The dynamic process of the formation of the novel morphology BaCrO₄ crystals showed that the morphology grew from a round-bar polyhedron, to regular polyhedron, to approximate octahedron to a uniform pistachio nut shape. The growth mechanism of the BaCrO₄ micro/nanocrystals was explained that C₁₂-PEG-C₁₂ had a greater interfacial adsorption and would effectively control the shape evolution during the crystal growth, while PbCrO₄ could be explained that the Gemini surfactants can undergo liquid-crystalline phase transitions with long channels providing a soft template effect and derived the nanorods formation. Room temperature fluorescence spectra were studied and these showed that the pistachio-shaped BaCrO₄ microcrystals and PbCrO₄ nanorods possess photoactive luminescence properties with emission peaks at 470 and 549 nm, respectively.     

Studies on the electrochemical and dopamine sensing properties of AgNP-modified carboxylated cellulose nanocrystal-doped poly(3,4-ethylenedioxythiophene)

Ionics - Carboxylated cellulose nanocrystals (CNCC) were synthesized by treating microcrystalline cellulose with ammonium persulfate. Silver nanoparticles (AgNPs) were prepared on the surface of...     

Sonochemical synthesis, size controlling and gas sensing properties of NiO nanoparticles

Nanoparticles of NiO (NP-NiO) were prepared by a novel sonochemical route from Ni acetate and sodium hydroxide without any requirement of calcinations steps at high temperature and without surfactants. Drop casting of the nanocrystals onto alumina substrates allowed the fabrication of gas sensing devices, which were tested towards NO₂ and CO and showed promising results. At low working temperature, the NiO nanoparticles based sensors are selective to nitrogen oxide; in fact a good sensitivity is shown at 200 °C at low concentration (2 ppm), while at temperature above 350 °C, high responses are obtained for carbon monoxide. The results obtained are stimulating for further developing of NP-NiO based sensor devices.