CuO nanostructures on copper foil by a simple wet chemical route at room temperature

Uniform CuO nanostructures have been synthesized on copper foil substrates by oxidation of Cu in alkaline condition by a simple wet chemical route at room temperature. By controlling the alkaline condition (pH value) different CuO nanostructures like nanoneedles, self-assembled nanoflowers and staking of flake-like structures were achieved. The phase formation and the composition of the films were characterized by X-ray diffraction and energy dispersive analysis of X-ray studies. X-ray photoelectron spectroscopic studies indicated that the samples were composed of CuO. The morphologies of the films were investigated by scanning electron microscopy. A possible growth mechanism is also proposed here. Band gap energies of the nanostructures were determined from the optical reflectance spectra. The different CuO nanostructures showed good electron field emission properties with turn-on fields in the range 6-11.3 V μm⁻¹. The field emission current was significantly affected by the morphologies of the CuO films.     

Reactive template assisted growth of one-dimensional nanostructures of titanium dioxide

TiCl₄ was employed to react with the reactive template Na@AAO, Na inside the channels of anodic aluminum oxide membranes, followed by O₂ oxidation at 623 K and annealed at 723 and 873 K to form one-dimensional nanostructures of TiO₂. Free standing polycrystals of anatase TiO₂ (diameter = 200–400 nm, length = 60 μm) were obtained after the template was removed.     

Hierarchical nanostructures of ZnO obtained by spray pyrolysis

A two step spray pyrolysis deposition method was applied in order to grow ZnO nanorod core/ZnO shell hierarchical nanostructures with various surface morphologies, such as a highly organised platelet network on the side facets of the ZnO rod and bundles of nanoneedles on the top plane of the rod. First, well-shaped ZnO nanorods with lengths of ca. 1 μm and average diameters of 150–300 nm were deposited from zinc chloride (ZnCl₂·2H₂O) aqueous solutions onto TCO/glass substrates. Then, zinc acetate (Zn(CH₃COO)₂·2H₂O) solution was pulverised over the surface of the sprayed ZnO nanorods at a growth temperature of approximately 330 °C within 6–10 min. The obtained structures were characterised by high resolution SEM, UV–VIS and XRD. To estimate the surface areas and photocatalytic ability of the bare rods and hierarchical structures, their adsorption ability and activity of photocatalytic oxidation of doxycycline were measured. It was found that the surface area of hierarchical structures comprised of a network of platelets is at least 4 times larger than that of a bare rod. The structural and morphological properties of sprayed hierarchical structures largely depend on the spraying rate of the zinc acetate solution and on the ZnO nanorod top plane shape.     

The effects of different acids on the preparation of TiO2 nanostructure in liquid media at low temperature

Titania of different crystalline structures and morphology was prepared by the low temperature dissolution–reprecipitation process (LTDRP) of amorphous precursors in various acidic mediums at 70 °C for 8 h. The effects of different acids on the crystalline and morphology of titania nanostructures were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results showed that HCl, HNO₃ and their mixture favored the formation of rod-like rutile TiO₂, while H₂SO₄ and its mixture with HCl or HNO₃ retarded the formation of rutile but favored the formation of the anatase phase of with an irregular shape. The mechanism of the formation of various titania nanostructures was also discussed.     

Low temperature synthesis of nanocrystalline lithium ferrite by a modified citrate gel precursor method

Single phase nanocrystalline lithium ferrite is synthesized by a modified citrate gel precursor technique. Ferrite nanoparticles of average size of 8 nm, obtained after calcination of the citrate gel made by the usual method at 450 °C, show superparamagnetic behavior. However, small amounts of -Fe₂O₃ is formed as an impurity phase due to the initial formation of some -Fe₂O₃ phase. On the other hand, when the pH of the mixed solution is increased to 7 after the addition of ammonia solution, a lower calcination temperature of 200 °C is sufficient for the formation of single phase lithium ferrite nanoparticles of size 30 nm. No impurity phases are detected when the nanocrystalline powders are calcined at higher temperatures. The magnetic properties of the ferrite nanoparticles of different sizes obtained by calcining the powders at different temperatures are studied.     

Shape and size-controlled synthesis of Ni Zn ferrite nanoparticles by two different routes

Monodisperse Ni–Zn ferrite nanoparticles of different compositions have been synthesized using two different routes, such as sonochemical and polyol methods. In both the cases, the process was attempted in a single reaction in the absence of any surfactant and deoxygenated conditions. X-ray diffraction data on the samples confirmed formation of pure ferrite phase with spinel structure, and indicated that the sonochemical method produces highly crystalline particles compared to the polyol process. Transmission electron microscopy images reveal formation of different shapes, such as cubic, spherical, flower-like and amorphous depending on the method and composition of the ferrite. The magnetic properties of the synthesized Ni–Zn ferrite nanoparticles, measured by vibrating sample magnetometer at room temperature, show that the highest magnetization value was obtained for the composition of Ni_0.5 Zn_0.5 Fe₂O₄ in both the synthesis methods. The results of both the methods were discussed by correlating the structure to the magnetism at nanoscales.     

Synthesis and characterizations of manganese ferrites for hyperthermia applications

In the last few years, magnetic nanoparticles have turned out to offer great potential in biomedical applications. This study was focused on Mn_xFe_1−xFe₂O₄ ferrite particles series with x ranging between 0 and 1. Manganese ferrites nanoparticles were prepared by co-precipitation method that allows a good control of their shape and size. The X-ray analysis indicated a crystallite size of the particles in the nanometers domain increasing with the Mn cation substitution level. Average grain size of the nanoparticles calculated from transmission electron microscopy images of the samples was ranging between 10.5 and 19.0 nm suggesting that the majority of the nanoparticles are monodomain. The hydrodynamic diameter of the water dispersed nanoparticles measured by dynamic light scattering was ranging between 60 and 105 nm proving the tendency of agglomeration. Vibrating sample magnetometer measurement confirmed the superparamagnetic behavior of the powders. The magnetic properties were analyzed considering the proposed cation distribution and Yafet–Kittel angles, while the specific absorption rate (SAR) measurement at 1.95 MHz frequency confirmed the influence of substitution level on magnetic properties and thermal transfer rate. From our results the highest value for specific absorption rate was 148.4 W g⁻¹ for Mn₂Fe₂O₄ at an AC field of 4500 A m⁻¹.     

Shape-controlled synthesis of manganese oxide nanoplates by a polyol-based precursor route

Manganese oxide nanoplates with different shapes have been prepared based on an ethylene glycol-mediated route. The first step consists of precipitating manganese alkoxide precursor in a polyol process from the reaction of manganese acetate with ethylene glycol. During this process, the morphologies of the prepared precursor could be tuned from disc-shaped to hexagonal nanoplates by introducing different organic additives. The second step involves the treatment of the precursor under different conditions. Crystalline Mn₂O₃ with the same morphology was readily obtained by calcination of the manganese alkoxide precursor. Furthermore, Mn₃O₄ nanoplates could be obtained by immersing the precursor into the deionized water.     

Novel low temperature synthesis of ZnO nanostructures and its efficient field emission property

We have developed a novel, simple and cost effective wet chemical synthetic route for the production of ZnO nanoneedles and nanoflowers at low temperature. The synthesis process does not require any surfactant, template or pre-seeding. The synthesized ZnO nanoneedles have very sharp tips with their lengths in the range 2-3 μm, while for the case of nanoflowers, the nanoneedles were bunched together. X-ray diffraction study and X-ray photoelectron spectroscopic studies confirmed the formation of pure ZnO phase. Studies on the electron field emission property of the grown nanostructures showed that they are very efficient field emitter. The turn-on fields and the threshold fields are 3.6 V/μm, 4.4 V/μm and 5.4 V/μm, 6.8 V/μm for the ZnO nanoneedles and ZnO nanoflowers, respectively. The enhanced field emission property was attributed to the presence of sharp tips of the nanostructures.     

Synthesis of La0.5A0.5MnO3 (A = Sr, Ba) by a hydrothermal method at low temperature

A mild hydrothermal method has been adopted to prepare La_0.5Sr_0.5MnO₃ and La_0.5Ba_0.5MnO₃, which is of interest for a number of possible applications. The results from X-ray diffraction (XRD) indicate that in the present work the temperature of 200 and 240 °C are sufficient to prepare phase pure La_0.5Sr_0.5MnO₃ and La_0.5Ba_0.5MnO₃ crystals. At 200 °C, La_0.5Sr_0.5MnO₃ nanowires are obtained. The average width and length of the nanowires are 40 nm and 4 μm, respectively. At 240 °C, La_0.5Ba_0.5MnO₃ powders obtained have a cubic structure with the average size of 3-5 μm.     

Microwave-assisted synthesis and magnetic studies of cobalt oxide nanoparticles

An efficient microwave-assisted route has been used to synthesize nanoparticles of cobalt oxide. The particles were well characterized by transmission electron microscopy (TEM) which showed that the average diameter of the particles is around 6 nm. X-ray diffraction (XRD) studies further confirmed the formation of the spinel Co₃O₄. Purity of the products was detected by Fourier transform infrared spectroscopy (FTIR) combined with thermal gravimetric analysis (TG/DTG). The magnetic measurements revealed a small hysteresis loop at room temperature indicating a weak ferromagnetic nature of the synthesized Co₃O₄ nanoparticles. The magnetic moment of the particles was measured to be 4.27 μ_eff.     

Preparation and pseudo-capacitance of birnessite-type MnO2 nanostructures via microwave-assisted emulsion method

A microwave-assisted emulsion process has been developed to synthesize birnessite-type MnO₂ one-dimensional (1D) nanostructures. The prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). TEM images confirmed that the particles were composed of nanowires and nanobelts. As a consequence of the small size, such MnO₂ nanostructures exhibit a high specific capacitance of 277 F g⁻¹ at the current density of 0.2 mA cm⁻². Furthermore, the simple synthetic approach may provide a convenient route for the preparation of birnessite-type MnO₂ nanowires and other 1D nanostructured materials on a large scale.     

Preparation polystyrene/multiwalled carbon nanotubes nanocomposites by copolymerization of styrene and styryl-functionalized multiwalled carbon nanotubes

Styryl-functionalized multiwalled carbon nanotubes (p-MWNTs) were prepared by esterification based on the carboxylate salt of carbon nanotubes and p-chloromethylstyrene in toluene. Then in situ radical copolymerization of p-MWNTs and styrene initiated by 2,2′-azobis(isobutyronitrile) (AIBN) was applied to synthesize composites of styryl-functionalized multiwalled carbon nanotubes and polystyrene (PS) (p-MWNTs/PS). Characterizations carried out by FT-IR, ¹H NMR, UV–vis show that styryl group covalently bond to the surface of MWNTs. The results of UV showed that the solutions of p-MWNTs/PS in chloroform have the hyperchromic effect. Transmission electron microscopy (TEM) images of p-MWNTs/PS composites and scanning electron microscopy (SEM) images of fracture surface of p-MWNTs/PS composites showed the functionalized nanotubes had a better dispersion than that of the unfunctionalized MWNTs in the matrix. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) suggested that the thermal stability of p-MWNTs/PS composites improved in the presence of MWNTs.     

Synthesis of polypyrrole coated manganese nanowires and their application in hydrogen peroxide detection

This study focuses on the synthesis and application of polypyrrole coated manganese nanowires (Mn/PPy NWs) as an enzyme-less sensor for the detection of hydrogen peroxide (H₂O₂). The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) results confirm a core–shell structure with the Mn nanowires encapsulated by the PPy. An electrochemical sensor based on the Mn/PPy NWs for amperometric determination of H₂O₂ is prepared. The electrochemical behaviour of H₂O₂ is investigated by cyclic voltammetry with the use of modified glassy carbon electrode (GCE) with Mn/PPy NWs film. The modified glassy carbon electrode (GCE) with Mn/PPy NWs shows enhanced amperometric response for the detection of H₂O₂. This is due to the high available surface area of Mn/PPy NWs which can provide a suitable area for the reaction of H₂O₂. The detection limit and limit of quantification (S/N = 3) for two linear segments (low and high concentration of H₂O₂) are estimated to be 2.12 μmol L⁻¹, 7.07 μmol L⁻¹ and 22.3 μmol L⁻¹, 74.5 μmol L⁻¹, respectively. In addition, the sensitivity for these two linear segments is 0.4762 μA mM⁻¹ and 0.0452 μA mM⁻¹ respectively.     

Solution synthesis and electrochemical capacitance performance of Mn3O4 polyhedral nanocrystals via thermolysis of a hydrogen-bonded polymer

Hausmannite Mn₃O₄ polyhedral nanocrystals have been successfully synthesized via a simple solution-based thermolysis route using a three-dimensional hydrogen-bonded polymer as precursor. The as-obtained product was characterized by means of powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Possible formation mechanism of polyhedral nanocrystals was proposed based on the role of organic ligand dissociation from the polymer precursor at elevated temperature. The electrochemical capacitance performance of Mn₃O₄ electrode was investigated by cyclic voltammetry and galvanostatic charge/discharge measurements. A maximum specific capacitance of 178 F g⁻¹ was obtained for the nanocrystals in a potential range from −0.1 to 0.8 V vs. SCE in a 0.5 M sodium sulfate solution at a current density of 0.2 A g⁻¹.     

Anions effect on the low temperature growth of ZnO nanostructures

Seed mediated aqueous chemical growth (ACG) route was used for the growth of ZnO nanostructures on Si substrate in four different growth mediums. The growth medium has shown to affect the morphology and the size of the different nanostructures. We observed that the medium containing zinc nitrate anions yields the nanorods, in a medium containing zinc acetate anions nano-candles are obtained. While in a medium containing zinc chloride anions ZnO nano-discs were obtained and in a medium containing zinc sulfate anions nano-flakes are achieved. Growth in these different mediums has also shown effect on the optical emission characteristics of the different ZnO nanostructures.     

Effect of bead milling on heat generation ability in AC magnetic field of FeFe2O4 powder

Nano-sized FeFe₂O₄ ferrite powder having a heat generation ability in an AC magnetic field was prepared by bead milling for a thermal coagulation therapy application. A commercial powder sample (non-milled sample) of ca. 2.0 μm in particle size showed a temperature enhancement (ΔT) of 3 °C in an AC magnetic field (powder weight 1.0 g, 370 kHz, 1.77 kA m⁻¹) in ambient air. The heat generation ability in the AC magnetic field improved with the milling time, i.e., due to a decrease in the average crystallite size for all the examined ferrites. The highest heat ability (ΔT = 26 °C) in the AC magnetic field in ambient air was for the fine FeFe₂O₄ powder with a 4.7 nm crystallite size (the samples were milled for 6 h using 0.1 mm? beads). However, the heat generation ability decreased for the excessively milled FeFe₂O₄ samples having average crystallite sizes of less than ca. 4.0 nm. The heat generation of the samples showed some dependence on the hysteresis loss for the B–H magnetic property. The reasons for the high heat generation properties of the milled samples would be ascribed to an increase in the Néel relaxation of the superparamagnetic material. The hysteresis loss in the B–H magnetic curve would be generated as the magnetic moment rotates (Néel relaxation) within the crystal. The heat generation ability (W g⁻¹) can be estimated using a 1.07 × 10⁻⁴fH² frequency (f, kHz) and the magnetic field (H, kA m⁻¹) for the samples milled for 6 h using 0.1 mm? beads. Moreover, an improvement in the heating ability was obtained by calcination of the bead-milled sample at low temperature. The maximum heat generation (ΔT = 59 °C) ability in the AC magnetic field in ambient air was obtained at ca. 5.6 nm for the sample calcined at 500 °C. The heat generation ability (W g⁻¹) for this heat treated sample was 2.54 × 10⁻⁴fH².     

Two types of ZnO-tubular nanostructures fabricated by stepped gas-phase reaction

Two types of zinc oxide (ZnO)-tubular nanostructures have been fabricated by stepped gas-phase reaction of a mixture of Zn–ZnO powders. Tubular structures of Type I vaporized from the top of ZnO nanorods with several hundreds nanometer in diameter. Tubular structures of Type II-coalesced ZnO nanowires with 2–4 μm in diameter. The formation of these two types of ZnO-tubular nanostructures is governed by different reaction conditions such as temperature, atmosphere, pressure, etc., and their growth mechanisms are discussed in detail.     

Synthesis of naturally cross-linked polycrystalline ZrO2 hollow nanowires using butterfly as templates

Butterfly wing skeleton is a widely used hard-template in recent years for fabricating photonic crystal structures. However, the smallest construction units for the most species of butterflies are commonly larger than ∼50 nm, which greatly hinders their applications in designing much smaller functional parts down to real “nano scale”. This work indicates, however, that hollow ZrO₂ nanowires with ∼2.4 μm in length, ∼35 nm in diameter and ∼12 nm in wall thickness can be synthesized via the selection of suitable butterfly bio-templates followed by heat processing. Especially, the successful fabrication of these naturally cross-linked ZrO₂ nanotubes suggests a new optional approach in fabricating assembled nano systems.     

Modification of dispersibility of nanodiamond by grafting of polyoxyethylene and by the introduction of ionic groups onto the surface via radical trapping

To improve the dispersibility of polycrystalline nanodiamond (ND) in solvents, the grafting of polymers and introduction of ionic groups onto ND surface via radical trapping by ND surface were investigated. The grafting of polyoxyethylene (POE) onto ND surface by trapping of POE radicals formed by the thermal decomposition of POE macro azo-initiator (Azo-POE) was examined. The polymer radicals formed by the thermal decomposition of Azo-POE were successfully trapped by ND surface to give POE-grafted ND. The effect of temperature on the grafting of POE onto ND was discussed. In addition, the introduction of cationic protonated amidine groups onto ND was achieved by the trapping of radicals bearing protonated amidine groups formed by thermal decomposition of 2,2′-azobis(2-methylpropionamidine)dihydrochloride (AMPA). The anionic carboxylate groups was introduced onto ND surface by the trapping of the radicals bearing carboxyl groups formed by thermal decomposition of 4,4′-azobis(4-cyonovaleric acid) (ACVA) followed by the treatment with NaOH aqueous solution. The dispersibility of ND in water was remarkably improved by the grafting of POE, based on the steric hindrance of polymer chains and by the introduction of ionic groups, based on the ionic repulsion, onto ND surface.