Cellulose scaffolds modulated synthesis of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocrystals: preparation,characterization and properties

Magnetic Co₃O₄ nanoparticles were prepared by using microporous regenerated cellulose films as sacrificial scaffolds. The cellulose macromolecules and the porous structure of the films made them used as spatially confined reacting sites where Co(OH)₂ nanoparticles could be synthesized in situ. When the cellulose matrix was removed by sintering at 500 °C, Co₃O₄ nanoparticles were obtained. XRD and XPS indicated that the prepared nanoparticles were pure Co₃O₄ without any impurity. TEM and SEM images revealed that the particle size of the nanoparticles was smaller than 100 nm. The nanoparticles had weak ferromagnetic properties at 25 °C. Furthermore, the pronounced quantum confinement effects of the synthesized nanoparticles have been observed, the optical bandgap energies determined were about 1.92 ~ 2.12 and 2.74 ~ 2.76 eV for O²⁻ → Co³⁺ and O²⁻ → Co²⁺ charge-transfer processes, respectively. Furthermore, the resulted Co₃O₄ nanoparticles behaved stable electrochemical performance with promising applications in the electrode for lithium ion battery.     

In situ synthesis of plate-like Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles in porous cellulose films with obvious magnetic anisotropy

Nanocomposite cellulose films with obvious magnetic anisotropy have been prepared by in situ synthesis of plate-like Fe₂O₃ nanoparticles in the cellulose matrix. The influence of the concentrations of FeCl₂ and FeCl₃ solutions on the morphology and particle size of the synthesized Fe₂O₃ nanoparticles as well as on the properties of the composite films has been investigated. The Fe₂O₃ nanoparticles synthesized in the cellulose matrix was γ-Fe₂O₃, and its morphology was plate-like with size about 48 nm and thickness about 9 nm, which was totally different from those reported works. The concentration of FeCl₂ and FeCl₃ solution has little influence on the particle size and morphology of the Fe₂O₃ nanoparticles, while the content of Fe₂O₃ nanoparticles increased with the increase of the concentration of the precursor solution, indicating that porous structured cellulose matrix could modulate the growth of inorganic nanoparticles. The unique morphology of the Fe₂O₃ nanoparticles endowed the composite films with obvious magnetic anisotropy, which would expand the applications of the cellulose based nanomaterials.     

Microwave synthesis and phase transitions in nanoscale BiFeO<Subscript>3</Subscript>

Nanosized multiferroic BiFeO₃ powders were synthesized by a microwave combustion method. The average crystallite sizes of the samples stay at a same level with the ratio of fuel glycine 0.5 ≤ G/N ≤ 1.5 and it increases significantly with G/N = 2.0. An inhomogeneity of amorphous and microcrystallites is observed directly by HRTEM. A ferromagnetic hysteresis loop with a saturation magnetization (M _S) of ~0.09 μ _B /Fe has been observed at room temperature in the sample with a crystallite size of 53 nm, whereas other powders with much smaller crystallite size (~20 nm) will not saturate even at 20 kOe. These magnetic behaviors were ascribed to a combination of the magnetic enhancement effect of a decreased crystallite size and superparamagnetic mechanism.     

Effect of Cr doping on the ac electrical properties of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles

Magnesium aluminate nanoparticles with different chromium concentration (0–12%) have been synthesized by a citrate–nitrate sol–gel route. X-ray diffraction studies confirmed the formation of single-phase cubic spinel structure excluding the presence of any secondary phase. Crystallite size of the synthesized nanoparticles was found to increase from 8.5 to 19.8 nm with the increase in Cr concentration. Fourier transformed infrared spectroscopic studies confirmed the presence of AlO₆ group which led to the formation of MgAl₂O₄ spinel structure. Surface morphology of the sintered pellets was investigated with the help of a field emission scanning electron microscope which revealed the existence of both grain and grain boundary along with their aggregates. The dielectric constant, dielectric loss and ac conductivity were studied as a function of frequency of the applied electric field for different composition and their nature of variation with frequency has been elucidated on the basis of Maxwell–Wagner interfacial model. Impedance spectroscopy technique has been used to study the effect of grain and grain boundary on the electrical properties of this spinel oxide. All the electrical parameters showed strong dependence on the nanostructural properties and were found to vary consistently with the increase of doping concentration.     

Synthesis of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> nanoparticles by modified Pechini method and their enhanced rate capability

Layered LiNi_1/3Co_1/3Mn_1/3O₂ nanoparticles were prepared by modified Pechini method and used as cathode materials for Li-ion batteries. The pyrolytic behaviors of the foamed precursors were analyzed by use of simultaneous thermogravimetric and differential thermal analysis (TG-DTA). Structure, morphology and electrochemical performance characterization of the samples were investigated by X-ray diffraction (XRD), field emission scanning electron macroscopy(SEM), Brunauer-Emmett-Teller (BET) specific surface area and charge–discharge tests. The results showed that the samples prepared by modified Pechini method caclined at 900 °C for 10 h were indexed to pure LiNi_1/3Co_1/3Mn_1/3O₂ with well hexagonal structure. The particle size was in a range of 100–300 nm. The specific surface area was larger than that of the as-obtained sample by Pechini method. Initial discharge capacity of 163.8 mAh/g in the range 2.8–4.4 V (vs. Li/Li⁺) and at 0.1C for LiNi_1/3Co_1/3Mn_1/3O₂ prepared by modified Pechini method was obtained, higher than that of the sample prepared by Pechini method (143.5 mAh/g). Moreover, the comparison of electrochemical results at different current rates indicated that the sample prepared by modified Pechini method exhibited improved rate capability.     

Ultrasound technique as a tool for high-rate incorporation of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in NiCo layers

NiCo–Al₂O₃ composite coatings were prepared by electrodeposition in a sulfamate plating bath containing Al₂O₃ particles to be co-deposited under sonication. For reliable determination of the microstructure, detailed studies on composite cross-sections were carried out by energy-dispersive spectrometer (matrix composition, particle content) and FE-SEM/electron backscattered diffraction data (particle distribution, grain size), accompanied by XRD analyses concerning texture, lattice parameter, grain size, and residual stress. The NiCo matrix with a Co/Co + Ni ratio up to 0.4 is a face-centered cubic solid solution with <100> and <110> fiber textures. The distribution of the particles (size 250 nm) was well-dispersed and enhanced up to 15 wt.% by ultrasound application during plating. Vickers hardness increased up to 50% by dispersion hardening. First-order residual stress in the matrix increased with rising Co content, thus decreasing wear resistance and revealing the complex of composite properties with partially opposite effects.     

On the Formation of TiO<Subscript>2</Subscript> Nanoparticles Via Submerged Arc Discharge Technique: Synthesis,Characterization and Photocatalytic Properties

We report a simple and inexpensive synthesis route of TiO₂ nanoparticles using electrical arc discharge between titanium electrodes in oxygen bubbled deionized (DI) water followed by heat treatment. The resulting nanoparticles were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD patterns demonstrate formation of TiO₂ phase in oxygen bubbled water after heat treatment and dominance of rutile to anatase phase. The size and morphology of TiO₂ nanoparticles were studied using different arc currents as a crucial parameter in properties of final product. Microscopic studies reveal nanosize spherical particles. DLS results indicate that at 20 A arc current, the size of the particles is about 37 nm and increases to 59 nm by increasing the arc current up to 40 A. Photodegradation of Rhodamine B (Rh. B) as a standard pollution shows that heat treated samples in oxygen bubbled water for 2 h at 500 °C, have more photocatalytic activity due to enhancement in crystallinity.     

Preparation and characterization of pure single-phase BiFeO3 nanoparticles through thermal decomposition of the heteronuclear Bi[Fe(CN)6]·5H2O complex

The heteronuclear Bi[Fe(CN)₆]·5H₂O complex was synthesized and single-phase perovskite-type BiFeO₃ nanoparticles with an average size of 30 nm were obtained by its decomposition at 600 °C. The complex and its decomposition products were analyzed using elemental analysis, thermal analysis (TGA/DTA/DSC), X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), UV–Vis spectroscopy, BET specific surface area measurement, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and magnetic measurements. The magnetic measurement confirms that the product shows a ferromagnetic order at room temperature, which may be ascribed to the size confinement effect. The DTA and DSC results confirm the multiferroic nature of the BiFeO₃ nanoparticles with Neel and Curie points at 372 and 825 °C, respectively. The BiFeO₃ prepared by this method could be an appropriate visible-light photocatalytic material due to its strong absorption band in the visible region. This method is simple, low-cost, safe and also suitable for industrial production of high purity perovskite-type BiFeO₃ nanoparticles for electromagnetic applications.     

Sucrose chelated auto combustion synthesis of BiFeO3 nanoparticles: Magnetically recoverable catalyst for the one‐pot synthesis of polyhydroquinoline

Sucrose chelated Bismuth ferrite (BiFeO₃) nanoparticles as a novel heterogeneous catalyst was synthesized by an auto combustion route. Different calcination temperatures (150 °C, 450 °C, 550 °C, 650 °C, 750 °C and 850 °C) have been employed to obtain single phased BiFeO₃ nanoparticles. The perovskite structure formation and disappearance of organic phase (sucrose) was obtained by Fourier transform infrared spectroscopy (FT‐IR). Phase determination and structural characterization was carried out by powder X‐ray diffraction (XRD). The magnetic properties were analyzed by vibrating sample magnetometer (VSM) whereas surface area/pore volume was obtained by Brunauer–Emmett–Teller (BET). Transmission electron microscope (TEM) analyzed the particles size and morphology. Thermal stability was investigated by thermogravimetric analysis (TGA) and determination of constituent elements was carried out by X‐ray Photo‐Electron Spectroscopy (XPS). Raman spectroscopy confirmed the perovskite structure of the synthesized materials. The BiFeO₃ nanoparticles so obtained were employed as heterogeneous catalyst for the synthesis of polyhydroquinoline derivatives. All the polyhydroquinoline derivatives were characterized by Fourier transform infrared spectroscopy (FT‐IR) and Nuclear magnetic resonance spectroscopy (¹H NMR). For the very first time ever we have used BiFeO₃ as a recyclable magnetic nanocatalyst in the one‐pot four component cyclization reaction of benzaldehyde, ethylacetoacetate/methylacetoacetate, dimedone/cyclohexane‐1,3‐dione, and ammonium acetate for the synthesis of polyhydroquinoline derivatives without solvent under refluxing conditions to provide excellent yields of products. BiFeO₃ nanocatalyst (without any functionalization/surface coatings) shows easy magnetic separation, recyclability, reusability along with excellent yield of polyhydroquinoline derivatives in an economic and benign way.     

Surface chemistry of nanoscale Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> dispersed in magnetic fluids

The interaction between stabilizers and nanoparticles is one of the important factors to prepare stable magnetic fluids. The magnetic nano-size Fe₃O₄ core with single domain and the average grain size around 8–12 nm were prepared by chemical precipitation method. The O/Fe molar ratio of the particle surface was measured by X-ray photoelectron spectroscopy (XPS). The heat effects of stabilizers adsorption on nanoparticles were measured by solution calorimetry. The excess amount of oxygen was possibly the result of the hydroxygen formed on the surface of the nanoparticles. The heat effects showed that compounds containing carboxyl groups can be adsorbed chemically on magnetite by forming chemical bonds. The other stabilizers involving NH-groups, such as polyethylene-imine, can be adsorbed physically. The exothermic value is about half of the former case. Supported by the National Natural Science Foundation of China (Grant No. 50476039), and Guangdong Provincial Department of Science and Technology (Grant No. 2004A10-703001)     

Effect of yttrium on the formation of nanostructured mesoporous CeO<Subscript>2</Subscript>

Mesoporous CeO₂ and yttrium doped CeO₂ (YDC) were prepared by a sol–gel process and characterized by a variety of techniques. XRD patterns showed that the undoped and doped samples had a cubic fluorite structure. The grain size decreased from 24.8 to 6.1 nm at 500 °C for pure CeO₂ and YDC, respectively. N₂ adsorption–desorption isotherms showed that the samples possessed typical mesopore characteristics. The BET specific surface area of the samples increased from 23.04 to 151.49 m²/g for 300 °C calcination after mesoporous CeO₂ was doped with Y. It is found that the introduction of Y can inhibit the grain growth, and the presence of the pores also can be related to this obstacle to grain growth. These results are of great significance for the control of porous microstructure, crystallinity, and applications for the development of nanostructured mesoporous materials.     

Preparation of nanocrystalline TiO<Subscript>2</Subscript> powders for photocatalytic oxidation of phenol

Nanocrystalline TiO₂ powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl₄ solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m²/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO₂ nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic mixed-phase TiO₂ powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO₂ (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated that rutile TiO₂ crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after the photocatalytic process over the rutile TiO₂ photocatalysts of larger crystallite size.     

Structural evolution and magnetic properties of SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanofibers by electrospinning

The SrFe₁₂O₁₉/poly (vinyl pyrrolidone) (PVP) composite fiber precursors were prepared by the sol-gel assisted electrospinning with ferric nitrate, strontium nitrate and PVP as starting reagents. Subsequently, the M-type strontium ferrite (SrFe₁₂O₁₉) nanofibers were derived from calcination of these precursors at 750–1,000 °C.The composite precursors and strontium ferrite nanofibers were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and vibrating sample magnetometer. The structural evolution process of strontium ferrite consists of the thermal decomposition and M-type strontium ferrite formation. After calcined at 750 °C for 2 h the single M-type strontium ferrite phase is formed by reactions of iron oxide and strontium oxide produced during the precursor decomposition process. The nanofiber morphology, diameter, crystallite size and grain morphology are mainly influenced by the calcination temperature and holding time. The SrFe₁₂O₁₉ nanofibers characterized with diameters of around 100 nm and a necklace-like structure obtained at 900 °C for 2 h, which is fabricated by nanosized particles about 60 nm with the plate-like morphology elongated in the preferred direction perpendicular to the c-axis, show the optimized magnetic property with saturation magnetization 59 A m² kg⁻¹ and coercivity 521 kA m⁻¹. It is found that the single domain critical size for these M-type strontium ferrite nanofibers is around 60 nm.     

Electrorheological property and microstructure of acetamide-modified TiO<Subscript>2</Subscript> nanoparticles

A sol–gel method has been proposed to prepare uniform TiO₂ nanoparticles whose average size is about 30 nm. The prepared nanometer TiO₂ particles are modified by acetamide via different self-assembled processes. X-ray diffraction analyses, scanning electron microscopy, and Fourier transform infrared spectrometry are used to determine the structure of the nanoparticles. The results indicate that the different synthesis processes do not change the morphology of the TiO₂/acetamide nanoparticles; nevertheless, they affect the interaction between amide and acetamide. The electrorheological (ER) activity is studied by shear stress under DC electric field. The acetamide-modified TiO₂ ER fluid shows notable ER activity with shear stress about 45 kPa (at 5 kV/mm), which outclasses the shear stress (2 kPa) of unmodified TiO₂ ER fluid. It is also found that the ER effect is very sensitive to the interaction of molecules on TiO₂ particles. The chemical bond between core and shell can enhance the ER activity of the sample.     

Preparation of nanocrystalline BiFeO<Subscript>3</Subscript> via a simple and novel method and its kinetics of crystallization

The precursor of nanocrystalline BiFeO₃ was obtained by solid-state reaction at low heat using Bi(NO₃)₃·5H₂O, FeSO₄·7H₂O, and Na₂CO₃·10H₂O as raw materials. The nanocrystalline BiFeO₃ was obtained by calcining the precursor. The precursor and its calcined products were characterized by differential scanning calorimetry (DSC), Fourier transform-infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM). The data showed that highly crystallization BiFeO₃ with rhombohedral structure (space group R3c (161)) was obtained when the precursor was calcined at 873 K for 2 h. The thermal process of the precursor experienced three steps, which involve the dehydration of adsorption water, hydroxide, and decomposition of carbonates at first, and then crystallization of BiFeO₃, and at last decomposition of BiFeO₃ and formation of orthorhombic Bi₂Fe₄O₉. The mechanism and kinetics of the crystallization process of BiFeO₃ were studied using DSC and XRD techniques, the results show that activation energy of the crystallization process of BiFeO₃ is 126.49 kJ mol⁻¹, and the mechanism of crystallization process of BiFeO₃ is the random nucleation and growth of nuclei reaction.     

Highly transparent UV absorption TiO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> films without oxidation catalytic activity prepared by a room temperature sol–gel route

TiO₂-SiO₂-Fe₂O₃ films as new UV absorption material were prepared through an epoxide derived sol–gel route. The films were formed at room temperature by doping of a little amount of γ-Fe₂O₃ nanoparticles in TiO₂-SiO₂. The obtained films show advantages such as high stability, efficient absorption in the UV region, high transparency in the visible range, and low oxidation catalytic activity to organic materials. It was found that 2.3 nm γ-Fe₂O₃ nanoparticles doped films exhibit stronger UV absorption than the films doped with 5.1 nm particles because of the increased grain strain of the nanoparticles with smaller size. These advantages of the films guarantee the broad application of this inorganic UV absorption film in the protection of heat sensitive organic materials such as artworks.     

Glycol-assisted autocombustion synthesis of spinel ferrite CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles: magnetic and electrochemical performances

Uniform spinel ferrite CoFe₂O₄ nanoparticles with average diameter of 40 nm were fabricated by a novel glycol-assisted autocombustion method. The as-prepared powders were characterized by X-ray diffraction, transmission electron microscopy and Raman spectrum. The room temperature magnetic property of the nanoparticles was examined, indicating the presence of an ordered magnetic structure in the spinel system. The electrochemical tests show that the as-prepared nanoparticles exhibits excellent electrochemical cycleability. The simple synthetic route can be applied to as a general method for the fabrication of other functional nanomaterials.     

Influence of pH on the incorporation and growth of Pb<Subscript>2</Subscript>CrO<Subscript>5</Subscript> crystallites in silica matrix

Pb₂CrO₅ nanoparticles were embedded in an amorphous SiO₂ matrix by the sol–gel process. The pH and heat treatment effects were evaluated in terms of structural, microstructural and optical properties from Pb₂CrO₅/SiO₂ compounds. X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), and diffuse reflectance techniques were employed. Kubelka–Munk theory was used to calculate diffuse reflectance spectra that were compared to the experimental results. Finally, colorimetric coordinates of the Pb₂CrO₅/SiO₂ compounds were shown and discussed. In general, an acid pH initially dissolves Pb₂CrO₅ nanoparticles and following heat treatment at 600 °C crystallized into PbCrO₄ composition with grain size around 6 nm in SiO₂ matrix. No Pb₂CrO₅ solubilization was observed for basic pH. These nanoparticles were incorporated in silica matrix showing a variety of color ranging from yellow to orange.     

Rapid synthesis of DyFeO<Subscript>3</Subscript> nanopowders by auto-combustion of carboxylate-based gels

EDTA and citric acid as two typical chelating reagents with multi-carboxyl groups were used to prepare DyFeO₃ nanopowders, respectively. The experimental results show that all of the carboxylate-based gels exhibited auto-propagating combustion behaviors. The XRD results indicate that DyFeO₃ single phase can be formed directly with CA/MN (citric acid to metal nitrate mole ratio) = 1 when the calcination temperature was above 700 °C. The specimen with EA/MN (EDTA to metal nitrate mole ratio) = 1 had the minimum crystallite size of 33 nm. The SEM images show that the as-burnt powders prepared with EDTA had more excellent dispersibility feature and clearer grain boundaries than that of citric acid. The magnetic measurement results show that DyFeO₃ nanopowders displayed antiferromagnetism characteristics at low temperatures due to the strong exchange interaction between Fe sublattice. As the ambient temperature increased, there was a transition from antiferromagnetism to paramagnetism in DyFeO₃ nanopowders.     

Enhanced ferroelectric properties of Ce-substituted BiFeO<Subscript>3</Subscript> thin films prepared by sol–gel process

Ce-substituted BiFeO₃ film (BCFO film) have been prepared by sol–gel process on F doped SnO₂ (FTO)/glass substrates. The effects of Ce substitution on the structural and electrical properties have been reported. X-ray diffraction data confirmed the R3c structure with the elimination of all secondary phases. We observed an increase in the remnant polarization (Pr) with Ce substitution and obtained a maximum value of ∼84 μC/cm² in 5% Ce-substituted film. The dielectric constant of the films was increased from 280 to about 420 for the BiFeO₃ film and 5% Ce-substituted BCFO film, respectively and the films showed excellent dielectric loss behavior. Moreover, the leakage current was substantially reduced by the Ce substitution.