Microwave and UV Assisted Methods for Obtaining Novel Composites Based on Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> with Embedded Gold Nanoparticles

Metallic nanoparticles embedded into the structure of metal oxides may play a role of catalytic substances. Such composites are mostly applied in oxidation reactions. The paper presents two one-step-methods for obtaining nanocomposites of gold embedded in the structure of iron oxide matrices (nanoAu/Fe₂O₃). Gold nanoparticles were formed in situ in the process of iron hydroxide dehydration. Thanks to the use of tannic acid it was possible to effectively reduce gold ions and stabilize the forming metal nanoparticles. The composites were prepared in the fields of microwave, ultraviolet radiation. The physicochemical properties of products were determined by scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray analysis and high-resolution transmission electron microscopy technique with EDS and elemental mapping mode. Also, the catalytic activity of the nanocomposites obtained was evaluated based on the process of methyl orange degradation. It was observed that products obtained according to the microwave radiation method are characterized by improved applying properties.     

Fabrication,characterization of polyaniline intercalated NiO nanocomposites and application in the development of non-enzymatic glucose biosensor

Determination of glucose plays very important part in diagnostics and management of diabetes. Nowadays, determination of glucose is necessary in human health. In order to develop the glucose biosensor, polymer modified catalytic composites were fabricated and used to detect glucose molecules. In this work, NiO nanostructure metal oxide (NMO) was fabricated via thermal decomposition method and polyaniline (wt% = 2, 4 and 6) assisted nanocomposites (NiO/PANI) were also prepared. The morphology and structure of synthesized nanocomposites were characterized by UV–visible diffusion reflectance spectroscopy (UV–vis-DRS), Fourier transform- infra red spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), high resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and N₂ adsorption-desorption isotherm measurement. The modified NiO/6%PANI/GCE had higher catalytic activity toward the oxidation of glucose than NiO/GCE, PANI/GCE, NiO/2%PANI/GCE and NiO/4%PANI/GCE. This is due to the larger surface area of NiO/6%PANI nanocomposites provide a ploform for faster electron transfer to the detection of glucose. The constructed glucose biosensor have been exhibited a high sensitivity of 606.13 µA mM⁻¹ cm⁻², lowest detection limit of 0.19 µM, high selectivity, stability, simplicity and low cost for the quick detection of glucose in real sample as well.     

Polypyrrole/γ-Fe2O3 magnetic nanocomposites synthesized in supercritical fluid

Polypyrrole/iron oxide (PPy/γ-Fe₂O₃) nanocomposites were synthesized by in situ oxidative polymerization of pyrrole in the presence of surface modified γ-Fe₂O₃ in supercritical carbon dioxide (scCO₂). The structural properties of nanocomposite particles thus obtained were characterized by FT-IR, thermal analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). It was found that ca. 50 nm γ-Fe₂O₃ nanoparticles were well dispersed in PPy powder in TEM pictures. X-ray photoelectron spectroscopy (XPS) analysis also support that all γ-Fe₂O₃ nanoparticles are encapsulated by PPy. Magnetic property of the nanocomposites was measured by SQUID, which indicated that the nanocomposites are superparamagnetic. The effects of different loadings of γ-Fe2O3 on the polymerization were also investigated.     

Jingle-bell-shaped ferrite hollow sphere with a noble metal core: Simple synthesis and their magnetic and antibacterial properties

In this paper, a simple strategy is developed for rational fabrication of a class of jingle-bell-shaped hollow structured nanomaterials marked as Ag@MFe₂O₄ (M=Ni, Co, Mg, Zn), consisting of ferrite hollow shells and metal nanoparticle cores, using highly uniform colloidal Ag@C microspheres as template. The final composites were obtained by direct adsorption of metal cations Fe³⁺ and M²⁺ on the surface of the Ag@C spheres followed by calcination process to remove the middle carbon shell and transform the metal ions into pure phase ferrites. The as-prepared composites were characterized by X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis spectroscopy and SQUID magnetometer. The results showed that the composites possess the magnetic property of the ferrite shell and the optical together with antibacterial property of the Ag core.     

Influence of borohydride concentration on the synthesized Au/graphene nanocomposites for direct borohydride fuel cell

Au/graphene nanocomposites are prepared via a one-pot chemical reduction process at room temperature, using graphene oxide (GO) and chloroauric acid (HAuCl₄) as precursors. The obtained Au/graphene nanocomposites are characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). TEM shows that the Au nanoparticles with size of approximately 8.7 nm disperse randomly on the surface of graphene. XPS confirms that the Au/graphene nanocomposites show a higher atomic percentage of C/O (6.3/1), in contrast to its precursor GO (2.2/1). Electrochemical studies reveal that the Au/graphene nanocomposites have electrochemically active surface area of 9.82 m² g^?1. Besides, the influence of borohydride concentration on the as-prepared Au/graphene nanocomposites is investigated in details by cyclic voltammetry, chronoamperometry, and chronopotentiometry. The results indicate that high concentration of borohydride can significantly improve the electrochemical performance of the Au/graphene catalyst.     

Preparation,properties, and catalytic activity of platinum-modified plasma electrolytic oxide structures on aluminum

Catalytically active Pt-containing oxide composites on aluminum have been prepared by plasma electrolytic oxidation (PEO) and by additional modification of the resulting coating by impregnation with an aqueous solution of chloroplatinic acid followed by calcination. The oxide film/metal composites have been characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and electron microscopy. The modified films contain the γ-Al₂O₃ and Pt crystalline phases. Platinum in the surface and subsurface layers is in the Pt⁰ state. There are platinum-rich areas on the surface of the PEO films. A higher catalytic activity in CO oxidation into CO₂ is shown by the samples whose oxide film contains nickel and copper along with platinum.     

Catalytic Etching of Platinoid Gauzes during the Oxidation of Ammonia by Air. Reconstruction of Surface of Platinoid Gauzes at 1133 K in Air,in Ammonia,and in an NH<Subscript>3</Subscript> + O<Subscript>2</Subscript> Reaction Medium

The structure, morphology, and chemical composition of the surface and near-surface layers of platinoid wires of polycrystalline gauzes, containing Pt (81 wt %), Pd (15 wt %), Rh (3.5 wt %), and Ru (0.5 wt %) after treatment at 1133 K in various media—in air, in ammonia, and after NH3 oxidation in air—are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). A thin film is found on the surface of the initial gauze containing an oxide layer of Rh₂O₃ with a thickness of ~2 nm, on the surface of which an inhomogeneous graphite-like layer 10–50 nm thick is located. It is shown that the heat treatment of gauzes in air leads to the partial removal of the surface graphite-like film that forms the reticulated structure on the wire surface. The treatment of gauzes in an ammonia atmosphere leads to the complete removal of the graphite-like and oxide layers and to the growth of metal grains of ~10 μm. After the catalytic reaction of NH3 oxidation, a deep structural rearrangement of the surface layer of the wire takes place, as a result of which crystalline metal agglomerates of ~10 μm are formed. It is supposed that the reaction of NH3 molecules with oxygen atoms penetrated on the defects leads to the local increase of temperature, due to which the metal atoms emerge on the surface and form large crystalline agglomerates and pores in the region of the grain boundaries.     

氧化钛/氧化石墨纳米复合材料的制备、表征及性能

采用四氯化钛(TiCl₄)和氧化石墨为主要原料, 通过原位复合的方法制备了氧化钛/氧化石墨(TiO₂/GO)纳米复合材料. 采用傅里叶变换红外(FTIR)光谱仪、X射线衍射(XRD)仪、热重-差热分析(TG-DTA)仪、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和扫描电子显微镜(SEM)等手段研究了TiO₂/GO纳米复合材料的结构和性能. 结果表明, 石墨在氧化过程中结构层键合大量含氧官能团, 部分含氧官能团进一步与纳米TiO₂以化学键结合; 复合后氧化石墨原有衍射峰消失. 将TiO₂/GO添加到水性聚氨酯(WPU)中, 制备了TiO₂/GO-WPU复合涂膜. 紫外吸收光谱表明, 随着氧化石墨含量的增加, 复合涂膜的紫外吸收能力增强, 当GO含量达到一定数值时, 涂膜的紫外吸收最强, 随着GO含量继续增加吸收又呈下降趋势, 存在一较优浓度值. TiO₂/GO的添加显著提高了聚氨酯涂层的抗紫外线性能, 耐磨损性能和热稳定性能.     

A general electrochemical approach to deposition of metal hydroxide/oxide nanostructures onto carbon nanotubes

This communication describes a new and relatively general electrochemical approach to the deposition of transition metal hydroxide/oxide nanostructures onto multi-walled carbon nanotubes (MWNTs) based on the precipitation of metal hydroxide/oxide nanostructures onto MWNTs by increasing the local pH values at the electrode/electrolyte interface induced by the proton-consuming electrochemical reduction of hydrogen peroxide (H₂O₂). The results obtained with cyclic voltammetry, scanning electron microscopy, and X-ray photoelectron spectroscopy of the synthetic nanocomposites substantially suggest the deposition of the metal hydroxides/oxides onto MWNTs induced by the electrochemical reduction of H₂O₂. This study essentially offers a facile but effective and relatively general electrochemical approach to the synthesis of the nanocomposites consisting of metal hydroxides/oxides and MWNTs.     

Impact of graphene on the enhancement of electrochemical and photocatalytic performance of Gd2O3 - Graphene nanocomposites

Gadolinium oxide - Graphene (Gd₂O₃-G) nanocomposites were prepared with different weight ratio of graphene using low temperature solution process. The structural, morphological, electrochemical and photocatalytic properties of the composites were investigated by X-ray diffraction, Raman, FE-SEM, HRTEM, Cyclic voltammetric and photo-degradation analysis. The chemical composition of the composites was studied by elemental mapping analysis using EPMA. The binding states of various elements present in the composites were analyzed by XPS. Cyclic voltammetric studies revealed that the nanocomposite with 5% graphene exhibits the specific capacitance of 26 F g⁻¹, which is higher than that of pure Gd₂O₃ (18 F g⁻¹). The presence of graphene has greatly enhanced the photocatalytic performance of Gd₂O₃G composites as the rate of degradation of MB dye is relatively higher in the composites compared to pure Gd₂O₃. The significant increase in the specific capacitance and rate of degradation of dye suggest that the Gd₂O₃G is a promising material for energy storage and environmental applications.     

XPS study of nanorods of doped vanadium oxide MxV2O5 · nH2O (M = Na, K, Rb, Cs)

Nanorods of vanadium oxide doped with alkali metal ions M _x V₂O₅ · nH₂O (M = Na, K, Rb, Cs, x = 0.31–0.44) have been obtained under hydrothermal conditions. The particles are 30–80 nm in diameter and a few micrometers in length. The chemical state of atoms and their concentration ratios have been studied by XPS. It has been shown that vanadium atoms are in two oxidation states V⁵⁺ and V⁴⁺ and the concentration of vanadium(IV) ions directly depends on the alkali metal. The X-ray photoelectron spectra of the valence bands of M _x V₂O₅ · nH₂O (M = Na, K, Rb, Cs) nanorods have been measured and interpreted.     

XPS study of the oxidation of nanosize Ni/Si(100) films

The XPS (X-ray photoelectron spectroscopy) study of nickel oxide nanolayers obtained by magnetron sputtering of the metal and its subsequent oxidation in air at different temperatures (400°C and 1000°C) was performed. Silicon(100) was used as a substrate. Surface of the initial Ni/Si structure was shown to contain not only Ni metal, but also the NiO oxide. Annealing at 400°C results in a complete oxidation of the metal film. At a high-temperature annealing (1000°C), nickel interacts both with oxygen and silicon substrate to form NiSi silicide and a composite Ni-Si-O phase in transition layer. Electronconductivity of NiO films is determined by intercrystallite barriers. Activation energies of film electroconductivity in model gases (O₂, Ar, H₂) were found.     

XPS and XANES studies of SnO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanolayers

This paper presents the results of our XPS (X-ray photoelectron spectroscopy) and XANES (X-ray absorption near edge structure) studies of tin oxide nanolayers obtained by magnetron spraying of the metal and its further oxidation in air at different temperatures. It was shown that at 240°C (annealing temperature), tin monoxide was dominant in the surface layer of the samples. When the temperature was increased to 450°C, the phase composition corresponded to tin dioxide. Increased sorption ability was found for the samples oxidized at 450°C. The band structure model of SnO _x nanolayers obtained by superposition of the XANES and XPS data revealed cross transitions with energy ～3.7 eV in the presence of the SnO and SnO₂ phases. Surface doping of nanolayers with palladium gave the Pd, PdO, and PdO₂ components, among which PdO was most intense. Alternate treatments with O₂ and H₂ gases led to the disappearance of palladium dioxide and the reduction of PdO to the Pd metal. After the volume doping of nanoplayers with palladium, the surface layer contained PdO and PdO₂; the latter was represented by two types of particles with different sizes.     

Nanocomposites based on opal matrices and iron subgroup metal nanoparticles

Three-dimensional nanocomposites based on ordered opal matrices (OMs) and metal nanoparticles were prepared by the reduction of salts and oxides of iron subgroup metals (M = Ni, Co, and Fe) and their binary and ternary mixtures with isopropanol in a supercritical state. The effect of the composition of the initial salts (nitrates or chlorides) on the phase composition of OM/M composites was determined. For a binary system of Ni and Co nitrates (1 : 1), the particles of a NiCo solid solution in a cubic modification were formed in an opal matrix after treatment in supercritical isopropanol. For the Ni-Fe and Co-Fe systems, the nanoparticles of solid solutions based on nickel or ??-, ??-cobalt metal and also oxides or an MFe₂O₄ phase with the spinel structure were formed in opal matrices with the use of iron trichloride. The nanoparticles of iron metal and Ni₃Fe, NiFe, and CoFe intermetallic compounds with regular distributions of metal atoms were detected for the first time in addition to spinel phases upon the reduction of composites with Fe, Ni-Fe, and Co-Fe nitrates with supercritical isopropanol. The reduction of composites obtained by the thermal treatment of a ternary mixture of nickel and cobalt nitrates and iron chloride in supercritical isopropanol led to the formation of solid solution nanoparticles based on Ni, Co, and Fe with an fcc structure and an oxide phase with the spinel structure in the voids of opal matrices. In the composite based on an opal matrix and a ternary system of Ni-Co-Fe nitrates (1 : 1 : 1), the complete reduction of spinel phases to the intermetallic phases of Ni₃Fe, NiFe, and CoFe was noted.     

Photoelectron spectroscopy and diffraction of surface nanoscale NbO/Nb(110) structures

X-ray photoelectron spectroscopy and diffraction (XPS and XPD) are applied to analyze oxygen-induced surface structures on the Nb(110) face formed due to oxygen segregation from the crystal bulk on thermal annealing to 2000 K in vacuum and/or oxygen adsorption in situ at temperatures above 1100 K. The Nb3d, O1s electronic states and valence band spectra of the NbO _x /Nb(110) surface are studied by XPS, and the results are compared with data for NbO, NbO₂, and Nb₂O₅ oxides. It is shown that niobium atoms entering the composition of surface oxide structures on Nb(110), from the standpoint of the nearest environment and chemical bond, are similar to metal states in NbO. The NbO _x layer thickness is estimated to be 0.5 nm. Two chemically inequivalent oxygen states are distinguished on Nb(110), which are, presumably, atomic chemisorbed oxygen on the parts of the clean surface of the Nb monolayer with hexagonal packing and oxygen in the composition of NbO _x -like linear clusters on Nb(110). A model of the NbO _x /Nb(110) surface takes into account a distortion of the structure of NbO _x clusters: a periodic vertical shift of metal atoms in Nb-chains and changes in Nb-O bond angles. Original Russian Text Copyright ? 2009 by M. V. Kuznetsov, A. S. Razinkin, and E. V. Shalaeva __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 536–543, May–June, 2009.     

Optical and electrical properties of copper alumina nanoparticles reinforced chlorinated polyethylene composites for optoelectronic devices

The incorporation of transition metal oxide fillers into the polymer matrix through solution mixing polymerization imparts enhanced electrical and thermal properties. The present work focused on the optical properties, crystallinity, thermal stability, temperature-dependent conductivity, dielectric constant and modulus of chlorinated polyethylene/copper alumina (CPE/Cu–Al₂O₃) nanocomposites. Optical absorption measured using an ultraviolet–visible (UV–visible) spectrometer shows enhanced intensity and a blue shift for CPE/Cu–Al₂O₃ nanocomposites. The bandgap energy of CPE/Cu–Al₂O₃ nanocomposites was lower than pure CPE and minimum bandgap energy was recorded for a 7 wt% composites. The X-ray diffraction demonstrates that Cu–Al₂O₃ nanoparticles were uniformly introduced into the CPE matrix. Thermogravimetric analysis (TGA) manifests improved thermal stability of nanocomposites. Dielectric properties decrease with frequency, whereas AC conductivity increases with frequency, and both AC conductivity and dielectric properties increase with temperature. The maximum AC conductivity and dielectric constant were obtained for 7 wt % nanofiller loaded sample. For all systems, the activation energy for electrical conductivity decreases with rising temperatures. The experimental dielectric constant values of CPE nanocomposites were correlated with different theoretical models. The Bruggeman model was in good agreement with the experimental permittivity. The impedance experiments showed a decreasing trend with temperature, indicating the semiconducting nature of prepared nanocomposites.     

Structure and morphology of HDPE-g-MA/organoclay nanocomposites: Effects of the preparation procedures

Nanocomposites comprising high density polyethylene (HDPE) or maleic anhydride-grafted HDPE (HDMA) as the host polymers and Cloisite^® 20A (20A) as the organoclay filler were prepared by melt-compounding, solution-blending and static annealing of polymer/clay powder mixtures. The dependence of their structure and morphology on the preparation conditions was studied by X-ray diffraction (XRD and SAXS), polarized optical microscopy (POM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was shown that intercalated nanocomposites based on HDPE or HDMA cannot be obtained by solution-blending, as long as solvent removal is made at room temperature. In fact, wide angle XRD patterns of solution blended composites are similar to those of mechanical blends of clay and polymer. However, as demonstrated by XRD and SAXS, fast intercalation or even complete delamination was obtained when the HDMA composites prepared from solution were annealed statically at temperatures higher than the polymer melting point. This implies that solution-blending causes efficient fragmentation of the clay agglomerates into thin tactoids (though unintercalated) homogeneously dispersed in the polymer matrix. This conclusion, supported by the finding that annealing mechanical blends of polymer and clay powders only leads to intercalated structures, was confirmed by TEM and SEM analyses. Morphology investigation revealed that, in contrast to melt-compounding, solution-blending followed by static annealing fails to produce significant orientation of clay platelets and polymer crystallites. However, repeated compression molding cycles were shown by XRD and SAXS to cause increasing levels of orientation of the platelets and the polymer matrix parallel to the sample flat surface.     

Ni@NiO核-壳纳米球的合成及其电化学生物传感应用研究

利用无模板水热法合成了镍纳米球,并通过部分氧化制备了Ni@NiO核壳结构的纳米复合物。合成的镍球和Ni@NiO复合物的尺寸可以通过简单调节反应条件来控制。运用XRD、EDS、TEM和SEM等测试方法对合成样品的形貌和组成进行了表征。Ni和Ni@NiO复合材料均有较好的磁性,其磁性用磁滞回线进行了表征。此外,Ni@NiO纳米复合物可以和血红蛋白结合构建过氧化氢生物传感器,该生物传感器对过氧化氢表现出很好的生物电催化活性,且具有较低的检测限和较宽的线性响应范围。该复合材料对于血红蛋白催化还原过氧化氢具有米氏响应和较小的米氏常数,表明Ni@NiO能较好地保持血红蛋白原有的活性。     

Electrochemical and XPS study of LiFePO4 cathode nanocomposite with PPy/PEG conductive network

High performance PPy/PEG-LiFePO₄ nanocomposites as cathode materials were synthesized by solvothermal method and simple chemical oxidative polymerization of pyrrole (Py) monomer on the surface of LiFePO₄ particles. The samples were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS) and charge-discharge tests. PPyPEG hybrid layers decrease particle to particle contact resistance while the impedance measurements confirmed that the coating of PPy-PEG significantly decreases the charge transfer resistance of the electrode material. The initial discharge capacities of this sample at C/5 and 1C are 150 and 128 mAh/g, respectively. The results show that PPy/PEGLiFePO₄ composites are more effective than bare LiFePO₄ as cathode material.     

XPS study of the electronic structure of heterometallic complexes Fe2MO(Piv)6(HPiv)3 (M = Ni, Co)

Heterometallic complexes Fe₂MO(Piv)₆(HPiv)₃ (M = Ni, Co) have been studied by XPS. The complexes are identified as high-spin complexes with metal atoms in oxidation states M(II) and M(III). A change in the ligand environment of metal atoms has an effect on both the energetic state of metal atoms and the XPS pattern. The substitution of a Co atom for the nickel atom in the heterometallic complexes changes the XPS pattern of iron and their magnetic state. For the Fe₂MO(Piv)₆(HPiv)₃ complexes, quantum-chemical calculations have been performed at the density functional theory (DFT) level. In combination with XPS and magnetochemistry data, the quantum-chemical calculation demonstrates that the Fe, Ni, and Co atoms in the trinuclear complexes are in the high-spin local state and that the ground state is dominated by antiferromagnetic exchange interaction.