Synthesis mechanisms of lithium cobalt oxide prepared by hydrothermal–electrochemical method

Thermodynamic calculation method was adopted to predict the reaction mechanism of LiCoO₂ prepared by hydrothermal–electrochemical process. It was found that in the Co–LiOH–H₂O system, Co was oxidized to HCoO₂⁻, Co(OH)₂ (100 °C) or CoO (150 °C), CoOOH in sequence with the increase of electrode potential, then the ion-exchange reaction of CoOOH and lithium ion occurred and LiCoO₂ came into being. The optimum synthesis parameter was obtained through thermodynamic calculation and it was validated experimentally by cyclic voltammogram method.     

Improvement of optical properties of nanocrystalline Fe-doped ZnO powders through precipitation method from citrate-modified zinc nitrate solution

Nanocrystalline Zn_1−xFe_xO (where x = 0, 0.01 and 0.02) powders were successfully synthesized by a precipitation method from citrate-modified zinc nitrate solution. X-ray powder diffraction, Fourier transformed infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy were used to study the structural properties. The optical properties were determined by UV–vis spectrophotometer and luminescent spectrometer. In this study, the optical band gap of nanocrystalline ZnO powder increased from 3.170 eV to 3.214 eV when the Fe concentration in the solution was increased up to 2 mol. %.     

The effect of dopant Cu, Fe, Ni or La on the structures and properties of mesoporous Co-Ce-O compound catalysts

A series of Co-Ce-O mesoporous catalysts doped with Cu, Fe, Ni or La and the undoped one were synthesized by using tri-block copolymer P-123 as the template. These catalysts show wormhole-like structures, high surface areas (144–167 m²/g) and uniform meso-pore size distributions (4.0–4.8 nm) after calcination at 500 °C. The activity for low-temperature CO oxidation and the thermal stability of the mesoporous Co-Ce-O catalyst are largely modified by the dopant Cu, Fe, Ni or La in different ways. It is revealed by in situ diffuse reflectance infrared spectroscopy that CO oxidation over all the samples except the Ni-doped one undergoes carbonates pathway. In this case, the oxidation activities of the catalysts are mainly determined by the mobility of surface lattice oxygen species, which is indicated by the temperature-programmed reduction and desorption results. Doping with Cu greatly enhances the oxidation activity of Co-Ce-O catalyst at the calcination temperatures of 500 °C and 650 °C, and doping with La significantly improves its activity at the calcination temperature of 800 °C. However, doping with Fe always decreases the activity of Co-Ce-O catalyst regardless of the calcination temperature. Largely different from other dopants, the addition of Ni induces a change of the mechanism for CO oxidation and results in a remarkable decrease in the activity.     

Surface modification of zinc oxide nanoparticles by aminopropyltriethoxysilane

Commercial zinc oxide nanoparticles (20–30 nm) were coated by aminopropyltriethoxysilane (APTES) under varying environments. Three different processes, acidic, basic and toluene were used. The effects of coating conditions (acidic, basic and toluene) on the grafting, structural and optical properties of these nanoparticles were studied. In the three cases, it was possible to control the coating and according to X-ray diffraction, BET, TEM and SEM results, it is clear that the APTES coating plays a role of growth inhibitor even at 800 °C. From diffuse reflectance measurements, one can notice that the grafting process did not modify the transmittance spectra of ZnO.     

Synthesis of layered birnessite-type manganese oxide thin films on plastic substrates by chemical bath deposition for flexible transparent supercapacitors

Layered birnessite-type manganese oxide thin films are successfully fabricated on indium tin oxide coated polyethylene terephthalate substrates for flexible transparent supercapacitors by a facile, effective and inexpensive chemical bath deposition technology from an alkaline KMnO₄ aqueous solution at room temperature. The effects of deposition conditions, including KMnO₄ concentration, initial molar ratio of NH₃·H₂O and KMnO₄, bath temperature, and reaction time, on the electrochemical properties of MnO₂ thin films are investigated. Layered birnessite-type MnO₂ thin films deposited under optimum conditions display three-dimensional porous morphology, high hydrophilicity, and a transmittance of 77.4% at 550 nm. A special capacitance of 229.2 F g⁻¹ and a capacitance retention ratio of 83% are obtained from the films after 1000 cycles at 10 mV s⁻¹ in 1 M Na₂SO₄. Compressive and tensile bending tests show that as-prepared MnO₂ thin film electrodes possess excellent mechanical flexibility and electrochemical stability.     

Solvothermal synthesis and characterization of tungsten oxides with controllable morphology and crystal phase

Tungsten oxides with various morphologies and crystal phases were synthesized by solvothermal reactions at 200 °C for 7-12 h using different solvents. The morphology and crystal phase of tungsten oxides changed depending on the solvents, i.e., spherical particles of ca. 1 μm in diameter consisting of nanowires, spindle shaped bundles of ca. 1 μm in length consisting of nanowires and accumulations consisting of micrometer sized plates and/or rods of tungsten oxides were obtained using ethanol, 1-propanol and water-ethanol mixed solution, respectively. When water-ethanol mixed solution was used, the crystallinity of tungsten oxide increased but the specific surface area greatly decreased. Crystallinity of tungsten oxides had more important effects on the NO degradation under light irradiation. The product using 42.9 vol.% water-ethanol mixed solvent consisted of the mixture of anhydrous tungsten oxide and hydrous tungsten oxide with preferential orientation of (0 0 2) plane and small band gap energy (2.43 eV), and showed higher photocatalytic degradation of NO even though it had a much smaller specific surface area than those prepared using ethanol and 1-propanol.     

Crystallization of magnesium niobate from mechanochemically derived amorphous phase

The effect of high-energy ball milling and subsequent annealing on the mixture of MgO and Nb₂O₅ has been investigated. X-ray diffraction (XRD) measurement indicates that an amorphous phase is produced after milling for 5 h, while traces of MgNb₂O₆ crystallized from the amorphous phase during prolonged milling. Significant crystallization of MgNb₂O₆ from the amorphous state is observed after annealing at 500 °C, while the reaction of the remaining MgO and Nb₂O₅ does not take place at this temperature. Single phase MgNb₂O₆ can be achieved for all the milled samples at 700 °C. No significant grain growth is observed when the milled powders were annealed at temperature below 900 °C. Almost fully dense MgNb₂O₆ ceramics are obtained after annealing at 1100 °C from the as-milled powders.     

One-dimensional growth of zinc oxide nanostructures from large micro-particles in a highly rapid synthesis

Large and irregularly-shaped zinc oxide (ZnO) micro-particles commonly found in a high-temperature vapor-phase process known as the catalyst-free combust-oxidized mesh (CFCOM) process, play a crucial role as nucleation hosts for ZnO one-dimensional (1D) nanostructures, especially nanometric wires and rods. Nanowires and nanorods tend to grow from the hillocks of the large micro-particles whereby these hillocks serve as nucleation sites for the acicular structures. Nanowires with aspect ratios exceeding 5 are the most common 1D structures that grow from pillar-like hillocks, while triangular hillocks are probable nucleation hosts for nanorods. The ZnO nanostructures possess a polycrystalline nature with photoluminescent emission in the UV band-edge and visible regimes. A novel and non-destructive electrical resistance measurement method is introduced in that the 1D ZnO nanostructures exhibited very high GΩ resistance that is over five times higher than that of commercial ZnO. A growth model is proposed to offer a probable explanation for the fascinating rapid growth of 1D nanostructures originating from large ZnO micro-particles. The ZnO particles in this work were synthesized using 5-ton industrial furnaces via a university-industry joint effort.     

Synthesis of MnO/C composites through a solid state reaction and their transformation into MnO2 nanorods

MnO nanospheres encapsulated in carbon (MnO/C) composites were synthesized through a one-step solid state reaction between potassium permanganate and salicylic acid at 700 °C, which could be transformed into MnO₂ nanorods after being annealed in ambient atmosphere. Their formation mechanisms and electrochemical performances as anodes in Li-ion batteries (LIBs) were investigated. The first discharge capacity of MnO/C composites was 585.9 mA h g⁻¹, while that of MnO₂ was 1269 mA h g⁻¹, indicating their potential applications in LIBs.     

Structural-controlled synthesis of manganese oxide nanostructures and their electrochemical properties

A structural-controlled synthesis of manganese oxide nanostructures from single Mn₃O₄ precursor via hydrothermal method is presented. The obtained products include α- and β-MnO₂ nanorods, γ-MnO₂ urchin-like microspheres, birnessite nanowires and nanosheets. The morphology evolution process and the effect of varying reaction parameter to the phase and morphology are systematically investigated. The formation mechanisms have been rationalized. The obtained nanostructures are as the model system for studying the electrochemical capacitance performances, which have been investigated by cyclic voltammetry.     

The growth of carbon coating layers on iron particles and the effect of alloying the iron with silicon

Magnetic fine particles of metallic Fe coated with graphitic carbon layers were synthesized by annealing Fe₂O₃ particles with carbon powders at 1673 K in nitrogen atmosphere. For comparison, SiC was added to Fe₂O₃. X-ray diffraction measurement showed that the lattice constants of Fe changed depending on the Si contents. Mössbauer spectroscopy confirmed that Fe-Si alloys were formed by the Si addition and that the iron carbide disappeared. Electron microscope images revealed that the thickness of carbon coating layers increased from 24 nm to 36 nm as a result of the Si addition. Soaking tests showed that the corrosion resistance of the carbon-coated Fe particles was improved by the addition of Si. The results suggest that Si caused C to leave the Fe cores and move to the surface to form a carbon coating.     

Electrical and optical properties of tantalum oxide thin films prepared by reactive magnetron sputtering

Tantalum oxide thin films were prepared by using reactive dc magnetron sputtering in the mixed atmosphere of Ar and O₂ with various flow ratios. The structure and O/Ta atom ratio of the thin films were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The optical and dielectric properties of the Ta₂O₅ thin films were investigated by using ultraviolet-visible spectra, spectral ellipsometry and dielectric spectra. The results reveal that the structure of the samples changes from the amorphous phase to the β-Ta₂O₅ phase after annealing at 900 °C. The XPS analysis showed that the atomic ratio of O and Ta atom is a stoichiometric ratio of 2.50 for the sample deposited at Ar:O₂ = 4:1. The refractive index of the thin films is 2.11 within the wavelength range 300-1000 nm. The dielectric constants and loss tangents of the Ta₂O₅ thin films decrease with the increase of measurement frequency. The leakage current density of the Ta₂O₅ thin films decreases and the breakdown strength increases with the increase of Ar:O₂ flow ratios during deposition.     

Synthesis and optical properties of Yb0.6Y1.4O3 transparent ceramics

Transparent yttrium oxide ceramics doped with 30 at.% ytterbium were successfully produced by a combination of pre-sintering and hot isostatic pressing. The influence on the final transparency of different densification states and porosity configurations obtained by varying pre-sintering conditions were investigated by optical and electron microscopy. Our results show that densification prior to the final stage of sintering is necessary to limit final porosity. Samples showing open porosity were found to lead to pore entrapment because of the diffusion of argon inside the glass capsule during hot isostatic pressing. Transmittance measurements showed that the valence charge of the ytterbium ions was 3+ at the end of the process, indicating no effect of reduction when pre-sintering in vacuum was employed.     

Oxidation of etched Zn foil for the formation of ZnO nanostructure

Oxidation of Zn foil at temperatures of 100-400 °C was carried out in air to produce ZnO with various nanostructures. The final morphology of the oxidised Zn foil is largely dependent on the oxidation temperatures. At less than 300 °C, spherical oxide grains are seen. At 400 °C, 50 nm thick, porous nanosheets were formed after 30 min of oxidation. In portions of the samples, nanorods can be seen with diameters <10 nm and lengths reaching 1 μm. The nanosheets were formed in accordance to a vapour-solid mechanism whereas the nanorods were formed by diffusion of Zn through a certain path leading to the rod structure. At 450 °C, the nanorods became much more uniform. Oxidation at 500 °C resulted in ZnO nanorods. The rods are also blunt with smaller rods seen to branch out from the main rod. The luminescence properties of the ZnO were investigated as a function of the morphology of the oxide. Both green and blue emissions are seen for the samples with nanosheets whereas the nanorods ZnO has mostly green emission.     

Advanced synthesis of nanostructured materials for environmental applications

The present study deals with Aerosol Spray Pyrolysis (ASP) synthesis of two families of nanostructured redox materials targeted to two different environmental applications: transition-metal-doped ferrites and base metal-doped cerium oxide, used for hydrogen production through solar-assisted water splitting and for catalytic soot oxidation, respectively. The synthesized powders were characterized with respect to their phase composition, morphology and particle size distribution by XRD, SEM and TEM analysis, which have shown their nanostructured character. Doped ferrites were evaluated, with respect to their hydrogen production activity from water dissociation, in an in-house built water-splitting testing rig. ASP materials proved to be very active water splitters demonstrating higher water conversion and hydrogen yields than materials of the same composition synthesized through Solid State Synthesis (SSS), with material performance depending on the dopants’ kind and stoichiometry. Base metal-doped cerium oxides were evaluated with respect to their direct soot oxidation activity, via Thermogravimetric Analysis (TGA), as well as on a diesel engine bench under realistic conditions. It was found that doping improves their activity and that they enhance soot oxidation at lower temperatures compared to materials synthesized through Liquid Phase Self-propagating High temperature Synthesis (LPSHS).     

Synthesis of spherical CoAl_2O_4 pigment particles with high reflectivity by polymeric-aerosol pyrolysis

Spherical cobalt blue particles with good reflectivity characteristics were synthesized by spray pyrolysis. Two different spray solutions were prepared to investigate the differences in the morphology and the reflectivity properties of cobalt blue particles. One was an aqueous solution, and the other was a polycation solution that was obtained by chemically modifying the aqueous solution with NH4OH. The cobalt blue particles prepared with the aqueous solution had an irregular morphology after heat treatment at 1000°C for 2 h. On the contrary, spherical and dense particles were obtained from the polycation solution. The spherical and dense cobalt blue particles showed remarkable improvement in reflectivity compared with that of irregular morphology particles as well as the commercial.     

Reduction of friction of steel covered with oxide scale in hot forging

The hot ring compression test of chrome steel covered with an oxide scale film is carried out to examine the effects of the oxide scale film on the hot forging characteristics through experiment and finite element analysis. The nominal coefficient of shear friction of the scale is estimated from the plastic deformation behavior of the chrome steel covered with oxide scale film. The estimated coefficient of shear friction of the oxide scale is found to be lower than that of the chrome steel. The plastic deformations and temperature changes of the chrome steel workpiece and the oxide scale layer are calculated using finite element analysis method to investigate the mechanism underlying the reduction in the friction during the hot forging of chrome steel covered with an oxide scale film. Low friction and thermal conductivity values of the oxide scale lead to low forging load in the hot forging of chrome steel covered with an oxide scale film.     

Synthesis of spherical COA12O4 pigment particles with high reflectivity by polymeric-aerosol pyrolysis

Spherical cobalt blue particles with good reflectivity characteristics were synthesized by spray pyrolysis. Two different spray solutions were prepared to investigate the differences in the morphology and the reflectivity properties of cobalt blue particles. One was an aqueous solution, and the other was a polycation solution that was obtained by chemically modifying the aqueous solution with NH4OH. The cobalt blue particles prepared with the aqueous solution had an irregular morphology after heat treatment at 1000℃ for 2 h. On the contrary, spherical and dense particles were obtained from the polycation solution. The spherical and dense cobalt blue particles showed remarkable improvement in reflectivity compared with that of irregular morphology particles as well as the commercial.     

Synthesis,morphology, microstructure and magnetic properties of hematite submicron particles

We report on hydrothermal synthesis, plate-like morphology, microstructure and magnetic properties of hematite (α-Fe₂O₃) plate-like particles. The sample is obtained immediately after the hydrothermal process without using any template and without further heat treatment. The so-obtained sample is characterized by X-ray powder diffraction (XRPD), energy-dispersive X-ray spectroscopy (EDX), field-emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and superconducting quantum interference device (SQUID) magnetometer. XRPD confirms the formation of a single-phase hematite sample whereas EDX reveals that iron and oxygen are the only components of the sample. SEM, FE-SEM, TEM and HRTEM show that the sample is composed of plate-like particles. The width of the particles is ～500 nm whereas thickness is ～100 nm (aspect ratio 5:1). The HRTEM images exhibit well defined lattice fringes of α-Fe₂O₃ particles that confirm their high crystallinity. Moreover, the HRTEM analysis indicates the plate-like particles preferring crystal growth along [0 1 2] direction. Magnetic measurements display significant hysteretic behavior at room temperature with coercivity H_C = 1140 Oe, remanent magnetization M_r = 0.125 emu/g and saturation magnetization M_S = 2.15 emu/g as well as the Morin transition at T_M ～ 250 K. The magnetic properties are discussed with respect to morphology and microstructure of the particles. The results and comparison with urchin-like, rods, spherical, hexagonal, star-like, dendrites, platelets, irregular, nanoplatelets, nanocolumns and nanospheres hematites reveal that the plate-like particles possess good magnetic properties. One may conjecture that the shape anisotropy plays an important role in the magnetic properties of the sample.     

Synthesis and characterization of cuprous oxide dendrites: New simplified green hydrothermal route

Cuprous oxide (Cu₂O) dendrites were prepared by simple hydrothermal route at two different temperatures using starch as reducing and stabilizing agent. Scanning Electron Microscopy (SEM) revealed the alterations in morphology with reaction temperature and time. The spherical nanoparticles obtained at lower reaction temperature self-assembled into distinct dendritic nanostructures at high temperature. The mechanism of formation of dendrite over the polysaccharide template has been discussed. Transmission Electron Microscopy (TEM) revealed that the crystalline size of these dendrites in one dimension is about 50 nm. The nanoparticles were characterized by UV-vis and photoluminescence (PL) spectroscopy, X-ray diffraction (XRD), FT-IR and Thermal Gravimetry Analyzer (TGA). Impedance analysis of the nanostructures showed conductivity to be a function of temperature.