Preparation of Pt-Ru-Ni ternary nanoparticles by microemulsion and electrocatalytic activity for methanol oxidation

Ternary platinum-ruthenium-nickel nanoparticles are prepared by water-in-oil reverse microemulsions of water/Triton X-100/propanol-2/cyclohexane. Nanoparticles formed in the microemulsions are characterized by transmission electron microscopy (TEM), electron diffraction (ED), X-ray diffractometry (XRD), energy dispersive X-ray analysis (EDX). These resulting materials showed a homogenous alloy structure, the mono-dispersion and an average diameter of 2.6 ± 0.3 nm with a narrow particle size distribution. The composition and particle size of ternary Pt-Ru-Ni nanoparticles can be controlled by adjusting the initial metal salt solution and preparation conditions. Pt-Ru-Ni ternary metallic nanoparticles showed an enhanced catalytic activity towards methanol oxidation compared to Pt-Ru bimetallic nanoparticles.     

A novel magnetic nanocomposite involving anatase titania coating on silica-modified cobalt ferrite via lower temperature hydrolysis of a water-soluble titania precursor

A high surface area magnetic nanocomposite titania/silica/cobalt ferrite photocatalyst was synthesized via controlled hydrolysis and condensation of water-soluble titanium bis-ammonium lactato dihydroxide at relatively lower temperature (<97 °C) and characterized by XRD, FTIR, HRTEM, BET, XPS and magnetism analysis. The results reveal that as-prepared photocatalyst possesses a core/shell structure involving ferrite particles sequentially coated with coherent silica layer and anatase nanocrystallites via a heterogeneous nucleation and growth mechanism. The photodegradation of the photocatalyst for methyl orange is comparative to Degussa P25 and higher than the heated samples, being tentatively attributed to the proper microstructure and isolation/immobilization functions by silica intermediate phase as well as the surface-bond hydroxyl groups.     

Synthesis, thermal stability, and photocatalytic activity of nanocrystalline titanium carbide

Titanium carbide (TiC) was prepared via one simple route by the reaction of metallic magnesium powders with titanium dioxide (TiO₂) and potassium acetate (CH₃COOK) in an autoclave at 600 °C and 8 h. Phase structure and morphology were characterized by X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). The results indicated that the product was cubic TiC, which consisted of particles with an average size of about 100 nm in diameter. The product was also studied by the thermogravimetric analysis (TGA) and its photocatalysis. It had good thermal stability and oxidation resistance below 350 °C in air. In addition, we discovered that the cubic TiC powders exhibited photocatalytic activity in degradation of Rhodamine-B (RhB) under 500 W mercury lamp light irradiation.     

Route to transition metal carbide nanoparticles through cyanamide and metal oxides

We have designed an efficient route to the synthesis of transition metal carbide nanoparticles starting from an organic reagent cyanamide and transition metal oxides. Four technologically important metal carbide nanoparticles such as tungsten carbide, niobium carbide, tantalum carbide and vanadium carbide were synthesized successfully at moderate temperatures. It is found that cyanamide is an efficient carburization reagent and that the metal oxides are completely transmitted into the corresponding carbide nanoparticles. A possible mechanism is proposed to explain the results of the reaction between cyanamide and the metal oxides.     

Low-temperature hydrothermal synthesis of phase-pure rutile titania nanocrystals: Time temperature tuning of morphology and photocatalytic activity

In this paper, a simple and efficient methodology for the low-temperature synthesis of phase-pure nanocrystalline rutile TiO₂ with tuned morphology is reported. Control on morphology has been achieved by simple variation of the hydrothermal process, starting with titanium-tetrachloride without using mineralizers, additives or templating agents. The X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns showed no other phases of TiO₂ establishing the formation of phase-pure rutile titania in the entire temperature range of synthesis (40-150 °C) and most noticeably even at a considerably low temperature (40 °C). Fourier transform infrared (FT-IR) spectra strongly indicated the presence of hydroxyl group or surface adsorbed water and the thermogravimetry and differential thermo-gravimetry (TG-DTG) showed no phase change up to 1000 °C. A combination of reaction parameters (temperature, time) with a thorough transmission electron microscopy (TEM) study demonstrated the formation of phase-pure rutile titania nanocrystals as nano-rods, bunched nano-spindles or spherical nanoparticles depending on the hydrothermal reaction conditions. The photocatalytic activity of the synthesized nanocrystals has been successfully evaluated on the photodegradation of methyl orange (MO), a well-known pollutant azo-dye, as a model reaction.     

Preparation of VO2 nanowires and their electric characterization

Large-scale VO₂ nanowires have been synthesized by two-step method. First, we have been obtained (NH₄)_0.5V₂O₅ nanowire precursors by hydrothermal treatment of ammonium metavanadate solution at 170 °C. Secondly, the precursors have been sealed in quartz tube in vacuum and annealed to form VO₂ nanowires at 570 °C. Scanning electron microscope and transmission electron microscope analysis show that the nanowires have self-assembling nanostructure with the diameter of about 80-200 nm, length up to125 μm. Electrical transport measurements show that it is semiconductor with conduction activate energy of 0.128 eV. A metal-semiconductor transition can be observed around 341 K.     

Preparation and characterization of organic-inorganic poly(ethylene glycol)/WS2 nanocomposite

Layered nanocomposite PEG/WS₂, intercalating oligomeric poly(ethylene glycol) (PEG6000) into the tungsten disulfide host galleries, was synthesized using the exfoliation-adsorption technique. X-ray diffraction revealed that the intercalated oligomer within the host galleries is in a double-layer arrangement with an interlayer expansion of about 8.8 Å. The optimum conditions were explored to prepare the single-phase product with a composition of Li_0.12(PEG)_1.51WS₂. Thermal analyses suggested that the resulting material shows good thermal stability, with the decomposition of the interacted oligomeric chains within the disulfide galleries occurring at around 258 °C. Despite high conductivity of the host material, those of the PEG/WS₂ nanocomposite were found to be high in the order of 1 × 10⁻² S cm⁻¹ at ambient temperature, resulted from the host guest-host charge transfers.     

Preparation of polymer/LDH nanocomposite by UV-initiated photopolymerization of acrylate through photoinitiator-modified LDH precursor

The exfoliated polymer/layered double hydroxide (LDH) nanocomposite by UV-initiated photopolymerization of acrylate systems through an Irgacure 2959-modified LDH precursor (LDH-2959) as a photoinitiator complex was prepared. The LDH-2959 was obtained by the esterification of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959) with thioglycolic acid, following by the addition reaction with 3-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560), finally intercalation into the sodium dodecyl sulfate-modified LDH. For comparison, the intercalated polymer/LDH nanocomposite was obtained with additive Irgacure 2959 addition. From the X-ray diffraction (XRD) measurements and HR-TEM observations, the LDH lost the ordered stacking-structure and well dispersed in the polymer matrix at 5 wt% LDH-2959 loading. The glass transition temperature of UV-cured exfoliated nanocomposites increased to 64 °C from 55 °C of pure polymer without LDH addition. The tensile strength was improved from 10.1 MPa to 25.2 MPa, as well the Persoz hardness enhanced greatly, while the elongation at break remained an acceptable level.     

Microwave synthesis and electrochemical characterization of mesoporous carbon@Bi2O3 composites

An efficient and quick microwave method has been employed to prepare worm-like mesoporous carbon@Bi₂O₃ composites for the first time. As-prepared products have been characterized by X-ray diffraction, N₂ adsorption-desorption, scanning electron microscopy, transmission electron microscopy and inductive coupled plasma atomic emission spectroscopy. The electrochemical measurement shows the worm-like mesoporous carbon@Bi₂O₃ composites exhibits excellent capacitance performance and the maximum specific capacitance reaches 386 F g⁻¹, three times more than the pure worm-like mesoporous carbon.     

Preparation of superhydrophobic boehmite and anatase nanocomposite coating films

Developing a surface with water-repelling and self-cleaning ability has attracted much interest in nano-technology. We prepared superhydrophobic films in this study using a mixture of small anatase particles and large boehmite particles. Additionally, a N₂ automated adsorption apparatus, atomic force microscopy and contact angle meter were employed to examine the effects of the added boehmite and anatase to the boehmite ratio on the roughness, micropore ratio and contact angle of the hydrophobic films.As boehmite addition increased from 0 to 8 wt.%, the average roughness increased up to 30 nm, which resulted in the water contact angles increasing from 105° to 155°. The hardness of the films increased from 6B to 2H. The addition of a proper amount of small anatase particles into the large boehmite particles could lead to increasing the micropore ratio in the films, which would enhance the contact angle.     

One-step through-mask electrodeposition of a porous structure composed of manganese oxide nanosheets with electrocatalytic activity for oxygen reduction

Potentiostatic electrolysis of a mixed aqueous solution of Bu₄NBr and MnSO₄ at +1.0 V (vs. Ag/AgCl) on Pt electrode led to the oxidation of Br⁻ and Mn²⁺ ions. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and X-ray diffraction (XRD) revealed that this anodic process was followed by the deposition of insulating crystals of bromide salt of Bu₄N⁺ and the subsequent formation of layered manganese oxide in the interstitial spaces of the bromide grains already grown. Dissolution of the bromide crystals in water left a well-dispersed porous texture composed of manganese oxide nanosheets. The resulting MnO_x-modified electrode exhibited a larger catalytic current for the reduction of oxygen in alkaline solution, compared to the bare Pt electrode.     

Influence of morphology and surface characteristics on the photocatalytic activity of rutile titania nanocrystals

This article presents the synthesis of phase-pure rutile titania with different morphologies via hydrothermal method at significantly low temperatures (40-150 °C) without any additives and their application as efficient photocatalyst for environmental remediation. Phase and morphology has been determined with X-ray diffraction (XRD) and transmission electron microscopy (TEM). Ultra violet diffuse reflectance spectroscopy (UV-DRS) shows the optical band-gap in the range of ∼2.8-3.1 eV and Brunauer-Emmett-Teller specific surface area is found to be between 70 and 140 m²/g depending on the synthesis conditions. Raman spectroscopic analyses of the samples provide valuable insights into the structural and stoichiometric details. Photodegradation of the pollutant azo-dye, methyl orange (MO) in presence and absence of oxygen was performed to study the photocatalytic efficiency of the synthesized materials. Complete photodegradation of the dye is confirmed with high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) study. Dependence of dye photodegradation rate on morphology, specific surface area, surface nonstoichiometry and acidity were investigated in detail. Catalyst performance was compared from the rate constants obtained for each reaction using non-linear least square fitting (NLSF) to the experimental data in a concentration ratio (C₀/C_t) versus time (t) plot which shows extraordinarily high activity for all samples compared to commercial reference. Among them the catalyst synthesized at 40 °C for 16 h showed best activity. Kinetic study of the reaction matches well with simulated fit to experimental data and confirms to be pseudo-first order reaction.     

Preparation of hexagonal-MoO3 and electrochemical properties of lithium intercalation into the oxide

Metastable hexagonal molybdenum trioxide has been synthesized by chemical precipitation and hydrothermal treatment at low temperature. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize the product, which has a unique hexagonal prism-like morphology. Excellent electrochemical performances were exhibited: the first reversible discharge specific capacity can reach 402 mAh g⁻¹ versus Li metal at 0.1 mA cm⁻² (voltage range 1.2-4.0 V).     

Preparation of Sm-doped ceria (SDC) nanowires and tubes by gas–liquid co-precipitation at room temperature

Sm-doped cerium dioxide (SDC) with fcc structure was formed using a gas–liquid chemical co-precipitation process at room temperature. Morphology and structure of the as-prepared samples were characterized using TG, XRD, TEM, HRTEM and SAED techniques. Under our specific experimental conditions, two kinds of 1D nano-structures SDC have been mainly obtained. SDC nanowires are 0.3–1.2 μm in lengths and 5–20 nm in diameters. SDC nanotubes have outer diameters in 10–40 nm with lengths up to 2 μm. The as-prepared SDC shows very strong UV absorption ability and the maximum absorption peak redshifts compared with that of SDC nanoparticles.     

The use of a dynamic hydrogen electrode as an electrochemical tool to evaluate plasma activated carbon as electrocatalyst support for direct methanol fuel cell

The objectives of this study were to functionalize the carbon black surface by chemically introducing oxygenated groups using plasma technology. This should enable a better interaction of the carbon support with the metallic catalyst nanoparticles, hindering posterior support particle agglomeration and preventing loss of active surface. PtRu/C nanoparticles were anchored on the carbon supports by the impregnation method and direct reduction with hydrazine. Physical characterization of the materials was carried out using energy dispersive X-ray analysis and transmission electron microscopy. The screen printing technique was used to produce membrane electrode assemblies for single cell tests in methanol/air (DMFC). Tests were carried out using the dynamic hydrogen electrode as an electrochemical tool to evaluate the anode and cathode behavior separately.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Preparation, characterization, and luminescence of host (Y zeolite)-guest (FeS, CoS, NiS) nanocomposite materials

The host-guest nanocomposites (Y zeolite)-sulfides (FeS, CoS, NiS) were successfully prepared by a hydrothermal method and characterized by powder XRD, chemical analysis, adsorption technique, infrared spectroscopy and X-ray photoelectron spectroscopy. The Y zeolite-NiS host-guest nanocomposite material was found to exhibit luminescence. This paper suggests that the luminescence mechanism of Y-NiS resulted from the excitons in the confinement areas and from the defects in the materials. The material Y-NiS may be used as luminescent materials.     

Preparation and electrochemical properties of multiwalled carbon nanotubes-nickel oxide porous composite for supercapacitors

Porous nickel oxide/multiwalled carbon nanotubes (NiO/MWNTs) composite material was synthesized using sodium dodecyl phenyl sulfate as a soft template and urea as hydrolysis-controlling agent. Scanning electron microscopy (SEM) results show that the as-prepared nickel oxide nanoflakes aggregate to form a submicron ball shape with a porous structure, and the MWNTs with entangled and cross-linked morphology are well dispersed in the porous nickel oxide. The composite shows an excellent cycle performance at a high current of 2 A g⁻¹ and keeps a capacitance retention of about 89% over 200 charge/discharge cycles. A specific capacitance approximate to 206 F g⁻¹ has been achieved with NiO/MWNTs (10 wt.%) in 2 M KOH electrolyte. The electrical conductivity and the active sites for redox reaction of nickel oxide are significantly improved due to the connection of nickel nanoflakes by the long entangled MWNTs.     

Photochemical performance and electrochemical capacitance of titania nanocomplexes

Titania nanocomplexes, comprising the disordered nanoribbons or nanowires on the top surface and highly ordered nanotube array on the underlaying layer, has been fabricated by longitudinally splitting off nanotubes in a controlled anodization process. Anatase titania nanocomplexes show higher photovoltage and photocurrent responses and photocatalysis activity than titania nanotube array due to the enhanced light harvesting caused by nanoribbons and nanowires. Furthermore, titania nanowire-nanotube demonstrates a higher photoelectrical performance than nanoribbon-nanotube due to its thicker space charge layer caused by long nanotubes and more effective surface area contributed by nanowires. Cyclic charge-discharge measurements show that titania nanotube array exhibits a much higher electric double layer capacitance than titania nanocomplexes because the surface nanoribbons or nanowires inhibit the free diffusion and transportation of electrolyte ions into the underlaying nanotubes. Therefore, titania nanocomplexes can act as a photoactive material for photocatalysis applications and titania nanotube array can act as an electrode substrate for electrochemical supercapacitor applications.     

Formation and stability of anatase phase of phosphate incorporated and carbon doped titania nanotubes

Phase transformation analysis of the phosphate containing and carbon doped titania nanotubes, prepared by a simple anodization method, reveals complete transformation from amorphous to anatase phase in air between 360 and 400 °C. Activation energies for formation of anatase phase are evaluated and compared for the two types of titania nanotubes. A detailed analysis of the phase transformation characteristics and stability of the anatase phase is reported.