Kinetics of low-temperature initiation of H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/H<Subscript>2</Subscript>O mixture combustion upon the excitation of molecular vibrations in H<Subscript>2</Subscript>O molecules by laser radiation

The initiation of H₂/O₂/H₂O mixture combustion when asymmetric vibrations in H₂O molecules are excited by a resonant IR laser radiation is considered. It is shown that the vibrational excitation of the molecules gives rise to new efficient channels for the formation of chemically active O and H atoms and OH radicals. As a result, the chain mechanism of combustion in the mixtures is enhanced and, as a consequence, the induction time is cut and the ignition temperature is lowered. Even at a minor radiant energy flux delivered to the gas (E_in≈2.5 J/cm²), the ignition temperature of the stoichiometric H₂/O₂ mixture containing only 5% of H₂O may become as low as 300 K.     

H<Subscript>2</Subscript>O<Subscript>2</Subscript>-molecular beam epitaxy of high quality ZnO

We have studied the growth and characterization of ZnO epilayers on (0001)-sapphire by H₂O₂-molecular beam epitaxy (MBE). A high temperature (HT) MgO buffer followed by a low-temperature ZnO buffer was introduced in order to accommodate the lattice mismatch between ZnO and sapphire. The surface morphology of the samples was studied using atomic force microscopy (AFM), and scanning electron microscopy (SEM). The crystalline quality of the layers was investigated by employing high resolution X-ray diffractometry (HRXRD) and high resolution transmission electron microscopy (HRTEM). The electrical properties of the grown ZnO layers were studied by Hall-effect measurements in a standard van der Pauw configuration. The measured surface roughness for the best layers is as low as 0.26 nm rms. HRXRD measurements of the obtained ZnO layers show excellent quality of the single crystalline ZnO heteroepitaxially grown on (0001)-sapphirewith a HT MgO buffer layers. The influence of the growth conditions on the crystalline quality is discussed. The FWHM of the HRXRD (0002) rocking curves measured for the 2-inch ZnO-on-sapphire is as low as 27 arcsec with a very high lateral homogeneity across the whole 2-inch ZnO epilayers. The results indicate that H₂O₂-MBE is a suitable technique to fabricate ZnO epilayers of very high quality. PACS 61.10.Nz; 68.37.Lp; 81.05.Dz; 81.15.Hi     

Synthesis of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles with tunable magnetism by the modified hydrothermal method

Cobalt ferrite (CoFe₂O₄) nanoparticles were synthesized by using the hydrothermal route with the addition of trisodium citrate dihydrate (Na₃CA·2H₂O). The formation of CoFe₂O₄ nanoparticles with size ranging from 13 to 19 nm was confirmed by X-ray diffraction, energy dispersive X-ray analysis, and Fourier transform infrared spectroscopy; the clear-cut sharp of the nanoparticles was observed by transmission electron microscopy. By these characterization methods, the evolution of lattice constant and morphologies of the nanoparticles with the addition of Na₃CA·2H₂O is observed. Furthermore, the magnetic hysteresis loops measured at room temperature indicate that the magnetic properties of the products also show clear relationship with the masses of Na₃CA·2H₂O. For example, coercivity and high-field paramagnetic susceptibility increase with the increasing masses of Na₃CA·2H₂O, whereas the saturation magnetization and the effective magnetic anisotropy constant have the maximum values as the mass of Na₃CA·2H₂O is 1 g. This change of magnetic properties is related with the expanded lattice and the varied size and shape because of the addition of Na₃CA·2H₂O.     

Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

Kinetics of the plasmon optical response of Au nanoparticles/TiO<Subscript>2</Subscript> catalyst under O<Subscript>2</Subscript> and H<Subscript>2</Subscript> followed by differential diffuse reflectance spectroscopy

The changes in the optical properties of Au/TiO₂ powder catalyst, prepared by the deposition-precipitation method, are measured in the visible range by use of a home-made diffuse differential reflectance spectrometer, when the ambient atmosphere is switched between H₂ and O₂. Two main features are observed: (i) a short wavelength one, located between 400 and 600 nm, is shown to be related to the modifications of the plasmon resonance of the 3-dimensional metallic gold particles with mean size around 4 nm, induced by the exposure to oxygen or by its removal; (ii) a second feature, observed at long wavelengths between 600 and 1100 nm, is extremely sensitive to the exposure to oxygen. This optical feature could be due to the presence in the catalyst, either of Au⁰ clusters of several tens atoms, which are expected to display molecular-like transitions in this optical range, or to specific sites of the Au particles (edge atoms or peripheral atoms at the interface with the TiO₂ support), which could be highly reactive to oxygen.     

Oxidation of hydrogen sulfide and corrosion of stainless steel in gas mixtures containing H<Subscript>2</Subscript>S,O<Subscript>2</Subscript>, H<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript>

The composition of volatile and solid products of oxidation of hydrogen sulfide and stainless steel in gas mixtures containing H₂S, O₂, H₂O, and CO₂ has been determined using mass spectrometry, x-ray diffraction analysis, and scanning electron microscopy. It has been shown that holding an H₂S–O₂ mixture at 301 K results in prevailing formation of elemental sulfur and iron sulfides in the form of porous hygroscopic crust on the reactor wall surface. Formation of gas-phase sulfur causes self-acceleration of the oxidation of hydrogen sulfide; the resulting water triggers corrosion of the reactor wall. Heating of the resulting sulfur-sulfide crust in O₂ medium is accompanied by formation of SO₂ and heat release at T > 508 K. After heating of the H₂S–CO₂ mixture to 615 K, H₂ and COS were found in the volatile reactants; no noticeable corrosion of the reactor wall has been detected. It has been established that addition of O₂ to the H₂S–CO₂ mixture and its heating to 673 K leads to formation of ferrous sulfates. The mechanisms of the observed processes are discussed.     

Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.     

Characteristic features of optical absorption for Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> and NiO nanoparticles

The technical approach to determination of the structural and optical parameters of oxides with reduced dimensionality based on optical absorption measurements is described by example of gadolinium and nickel oxides. It was established that the temperature behavior of fundamental absorption edge for oxide nanoparticles is similar with the bulk materials with crystal structure. At the same time, the energy characteristics (band gap and effective phonon energies) for low-dimensional oxides are found to be significantly different from their bulk counterparts. The presented methodological method to obtain of qualitative and quantitative correlations of structural and optical characteristics provides novel reliable knowledge of nanoscaled 3d and 4f–metal oxide materials that is useful for development of their practical applications.     

Facile one-pot synthesis of cellulose nanocrystal-supported hollow CuFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles as efficient catalyst for 4-nitrophenol reduction

A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe₂O₄ nanoparticles (H-CuFe₂O₄ NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe₂O₄ NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe₂O₄ NPs with uniform size of 300 nm. The catalytic activity of H-CuFe₂O₄/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe₂O₄/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe₂O₄/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s^?1 g^?1, which was higher than H-CuFe₂O₄ NPs (0.50 s^?1 g^?1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe₂O₄ NPs. In addition, the H-CuFe₂O₄/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe₂O₄/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.

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One-step synthesis of colloidal Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> and γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles at room temperature

A facile room-temperature synthesis has been developed to prepare colloidal Mn₃O₄ and γ-Fe₂O₃ nanoparticles (5 to 25 nm) by an ultrasonic-assisted method in the absence of any additional nucleation and surfactant. The morphology of the as-prepared samples was observed by transmission electron microscopy. High-resolution transmission electron microscopy observations revealed that the as-synthesized nanoparticles were single crystals. The magnetic properties of the samples were investigated with a superconducting quantum interference device magnetometer. The possible formation process has been proposed.     

CeO<Subscript>2</Subscript> and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> modified Ni-YSZ anode for solid oxide fuel cell

Ni sintering at high temperature (～ 800 °C) operation drastically degrades the performance of Ni-yttria-stabilized zirconia (YSZ) anode in solid oxide fuel cell (SOFC). Mixed ionic and electronic conductive oxides such as CeO₂ and Nb₂O₅ enhance the dispersion of Ni, CeO₂ enhances the redox behavior and promotes charge transfer reactions, and Nb₂O₅ increases the triple phase boundary. In the present work, anode-supported SOFC is fabricated and tested in H₂ fuel at 800 °C. YSZ and lanthanum strontium manganite (LSM)-YSZ are used as the electrolyte and composite cathode with NiO-YSZ, CeO₂-NiO-YSZ, and Nb₂O₅-NiO-YSZ as an anode. The peak power density obtained for the cell with 10% CeO₂–30% NiO-YSZ anode at the 5 and 25 h of operation is 330 and 290 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). The peak power density obtained for the cell with 10% Nb₂O₅–30% NiO-YSZ anode at the 5 and 25 h of operation is 301 and 285 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). Physical characterization has been carried to study morphology, elemental analysis, particle size, and phase formation of the fabricated anode before and after cell operation to correlate the cell performance.     

NMR study of the paramagnetic state of low-dimensional magnets LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript>

A comprehensive NMR study of the magnetic properties of single crystal LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) is carried out in the paramagnetic region of the compounds for various orientations of single crystals in an external magnetic field. The values of the electric-field gradient (EFG) tensor, as well as the dipole and transferred hyperfine magnetic fields for ^63,65Cu, ⁷Li, and ²³Na nuclei are determined. The results are compared with the data obtained in previous NMR studies of the magnetically ordered state of LCO/NCO cuprates.     

A novel graphene-chitosan-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite modified sensor for sensitive and selective electrochemical determination of a monoamine neurotransmitter epinephrine

A novel sensitive electrochemical sensor has been developed by modification of glassy carbon electrode (GCE) with graphene (GRP), chitosan (CHIT), and bismuth oxide (Bi₂O₃) nanoparticles. The morphological characteristics of nanocomposite (GRP-CHIT-Bi₂O₃ or GCB) were studied by scanning electron microscope and atomic force microscopy. The electrochemical behavior of epinephrine at nanocomposite modified GCE (GCB/GCE) was investigated in pH 7.4 phosphate buffer solution using cyclic voltammetry and square wave voltammetry. GCB/GCE showed an enhancement in the current response as compared to bare GCE. Electrochemical impedance spectra showed a reduction of charge transfer resistance and higher electrocatalytic behavior of the sensor. The electrooxidation process of epinephrine at the modified sensor was found to be diffusion controlled. GCB/GCE showed a linear response to epinephrine in the range 100 to 500 nM. The limit of detection and limit of quantification were found to be 3.56 and 11.85 nM, respectively, which is lower than many other sensors reported for epinephrine in literature. The modified sensor showed high sensitivity (1.3 nA/nM) and selectivity for epinephrine. The method was employed for quantification of epinephrine in pharmaceutical formulation and human blood serum samples.     

Incommensurate helical magnetic order in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> quasi-one-dimensional compounds

The results of the measurements of the ^{6, 7}Li and ²³Na nuclear magnetic resonance (NMR) and ^{63, 65}Cu nuclear quadrupole resonance in LiCu₂O₂ and NaCu₂O₂ quasi-one-dimensional compounds with a spin chains in the paramagnetic and magnetically ordered states are presented. The shape of the NMR line below T _c = 24 and 13 K for LiCu₂O₂ and NaCu₂O₂, respectively, is characteristic of the incommensurate static modulation of the local magnetic field matching with the incommensurate spiral modulation of the magnetic moments. The differences in the shape of the NMR spectra of ²³Na and ⁷Li are discussed in terms of the features of the crystal structure of LiCu₂O₂ and NaCu₂O₂.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

Conductivity and spectroscopic studies of Li<Subscript>2</Subscript>O-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

Lithium vanadium-borate glasses with the composition of 0.3Li₂O–(0.7-x)B₂O₃–xV₂O₅ (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V₂O₅ concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO₄] structural units occur at V₂O₅ concentration of 45 mol%. It is established that the concentration of V⁴⁺ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li₂O-0.275B₂O₃-0.475V₂O₅ shows the highest electrical conductivity that has the value of 7.4?×?10^?5 S cm^?1 at room temperature.     

Fluorimetry Studies of Oscillating Chemilumnescence in the Luminol= H<Subscript>2</Subscript>O<Subscript>2</Subscript>= KSCN= CuSO<Subscript>4</Subscript>= TMAOH System

Oscillating chemical reactions are complex systems, involving a large number of chemical species. In oscillating chemical reaction, some species, usually a reaction intermediate, exhibit fluctuation in its concentration. In this report, visible oscillating chemiluminescence produced by the addition of luminol (3-aminophthalhydrazide) to the oscillating system of H₂O₂=KSCN=CuSO₄=TMAOH was investigated using spectrofluorimetry method. The effects of ingredient concentration of the oscillating system and complexing agents like citric acid and cysteine on the behavior of the oscillating system were investigated. Moreover, the influence of nonaqueous solvents such as ethanol and ethylene glycol has been studied.