A. A. Mysik

Specific features of luminescence properties of nanostructured aluminum oxide

Aluminum oxide nanopowders are prepared by the gas phase method and characterized according to the particle sizes and the phase composition. Samples of the nanostructured ceramic material are produced by pressing and annealing in air. The photoluminescence and cathodoluminescence spectra of the Al2O3 nanostructured ceramic material and α-Al2O3 anion-defect single crystals are investigated under comparable conditions. The luminescence bands of centers formed by oxygen vacancies are revealed in the spectra of two types of samples. The nanostructured ceramic material is characterized by the appearance of a new luminescence band at 3.4 eV and a decrease in the luminescence decay time. The inference is made that the characteristic features of the luminescence of the nanostructured ceramic material can be associated with the presence of non-equilibrium phases and the specific features of relaxation processes.

Synthesis, structure, and magnetic properties of iron and nickel nanoparticles encapsulated into carbon

Nanocomposites based on iron and nickel particles encapsulated into carbon (Fe@C and Ni@C), with an average size of the metal core in the range from 5 to 20 nm and a carbon shell thickness of approximately 2 nm, have been prepared by the gas-phase synthesis method in a mixture of argon and butane. It has been found using X-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy that iron nanocomposites prepared in butane, apart from the carbon shell, contain the following phases: iron carbide (cementite), α-Fe, and γ-Fe. The phase composition of the Fe@C nanocomposite correlates with the magnetization of approximately 100 emu/g at room temperature. The replacement of butane by methane as a carbon source leads to another state of nanoparticles: no carbon coating is formed, and upon subsequent contact with air, the Fe3O4 oxide shell is formed on the surface of nanoparticles. Nickel-based nanocomposites prepared in butane, apart from pure nickel in the metal core, contain the supersaturated metastable solid solution Ni(C) and carbon coating. The Ni(C) solid solution can decompose both during the synthesis and upon the subsequent annealing. The completeness and degree of decomposition depend on the synthesis regime and the size of nickel nanoparticles: the smaller is the size of nanoparticles, the higher is the degree of decomposition into pure nickel and carbon. The magnetization of the Ni@C nanocomposites is determined by several contributions, for example, the contribution of the magnetic solid solution Ni(C) and the contribution of the nonmagnetic carbon coating; moreover, some contribution to the magnetization can be caused by the superparamagnetic behavior of nanoparticles.

The hydrodechlorination of chlorobenzene in the vapor phase in the presence of metal-carbon nanocomposites based on nickel, palladium, and iron

Metal-carbon nanocomposites based on nickel, palladium, and iron and bimetallic palladium-nickel-carbon nanocomposites were for the first time used as catalysts of hydrodechlorination of chlorobenzene in the vapor phase in the atmosphere of hydrogen. Nickel and Pd-Ni nanoparticles completely coated by a carbon layer not only were stable to oxidation and agglomeration but also exhibited considerable activity in hydrodechlorination of chlorobenzene at temperatures much lower than those at which dechlorination on carbon carriers occurred. The dependence of catalytic properties (activity, selectivity, and stability) on temperature and nanocomposite composition was studied. Depending on the nature of the metal, the composition of bimetallic particles and temperature the selectivity could be changed, and the reaction could be directed toward the formation of benzene or cyclohexane. Carbon coating was stable under reaction conditions at least up to 350°C and did not hinder hydrodechlorination. Substrate adsorption likely occurred on the outside carbon surface of composite particles. The activity and structure of Ni@C composite remained almost unchanged after triple cycling over the temperature range from 50 to 350°C in a flow system.

A voltammetric sensor on the basis of bismuth nanoparticles prepared by the method of gas condensation

A procedure is developed for the immobilization of bismuth nanoparticles prepared by the method of gas condensation on inert supports manufactured by the screen printing method using carbon-containing inks. The electrochemical behavior of the immobilized bismuth nanoparticles is investigated, and the conditions of their electrochemical activation are found. The composition of the modifying suspension “bismuth nanoparticles-liquid” is optimized. The elaborated thick-film carbon-containing electrode modified by bismuth nanoparticles is shown to be similar in its analytical parameters to the commercially available thick-film carbon-containing electrode premodified by calomel, and substantially exceeds carbon-containing electrodes with electrolytically deposited bismuth films in its properties. The limits of detection for heavy metals by stripping voltammetry are as follows (μg/L): 0.38 for Zn(II), 0.40 for Cd(II), and 0.55 for Pb(II) at the preconcentration time 180 s.

The synthesis, structure, and properties of carbon-containing nanocomposites based on nickel, palladium, and iron

Nickel, iron, palladium, and bimetallic nickel-palladium nanoparticles encapsulated in carbon were synthesized by contactless levitation fusion of metals in a magnetic field in a flow of an inert gas containing a hydrocarbon. The products were characterized by X-ray diffraction, differential thermal analysis, thermogravimetry, high-resolution transmission electron microscopy, and adsorption. A layered carbon shell preventing agglomeration and oxidation formed on the surface of nickel- and iron-containing particles. The size of particles depended on preparation conditions and could be of 5–15 nm.

Catalytic effect of nanosized metal oxides in the Biginelli reaction

The effect of nanosized metal oxides on the regio- and stereoselectivity of the multicomponent Biginelli reaction and the reaction mechanism under conditions of heterogeneous catalysis were studied. It was found that the considerable activation of reagents occurred on the surface of metal nanooxides. The Biginelli reaction occurred by two mechanisms: a carbocationic mechanism took place along with the generally accepted mechanism (through the N-acyliminium ion). Nanosized metal oxides in the presence of chiral inductors increased the regio- and stereoselectivity of the Biginelli reaction.

Heat release in magnetic nanoparticles in AC magnetic fields

Using the method of gas-phase synthesis, nanocrystalline powders on the basis of iron oxides (defect magnetite Fe3O4), with an average size of 16, 21, 30, and 44 nm, and nanocomposites on the basis of iron and cobalt encapsulated into carbon, with an average size less than 10 nm have been prepared. The nano-particles placed into a buffer solution were subjected to the action of an ac (rotating and axial) magnetic field. The rotating field ensures higher values of heat release as compared to the axial field in media with a comparatively low viscosity. The greatest values of heat liberation in the axial field at frequencies to 100 kHz are observed for the iron-oxide particles with an average size on the order of 16 nm (up to 20 W/g). For the nano-composite on the basis of Fe@C and Co@C, the specific heat losses in rotating fields are greater than for the axial field (10 and 26 W/g, respectively).

Magnetism and optical properties of nanocrystalline Cu2O and TiO2 powders

The optical spectra of Cu2O and TiO2 nanopowders have been studied, which contain information about structural defects and are of interest in the search for optimum regimes providing the synthesis of ferromagnetic nanocrystals with Curie temperatures above room temperature.

Surface magnetism of nanocrystalline copper monoxide

The effect of the surface on the magnetic susceptibility of nanopowders of the CuO semiconducting antiferromagnet was studied. Single-phase nanopowders with nanoparticles 15, 45, and 60 nm in size were prepared through copper vapor condensation in an argon environment, with subsequent oxidation of the copper. The temperature dependences of the magnetic susceptibility of the nanopowders differ qualitatively from the χ (T) relations for bulk samples. In the region 80≤T≤600 K, the magnetic susceptibility of nanopowders is inversely proportional to temperature and is described by the sum of contributions due to the bulk part of CuO and to the Cu2+ paramagnetic ions localized in surface layers. The paramagnetic contribution to the total susceptibility is shown to increase with decreasing particle size and sample density. A comparison of the χ (T) relations is made for nanopowders and for a dense CuO nanoceramic with grain size 5≤d≤100 nm prepared using the shock wave technique.

Application of NMR relaxometry for determining the concentration of nanopowder magnetite in aqueous media

The use of the effect of a decrease in the transverse relaxation time T2 of the NMR signal of water protons in the presence of magnetic particles has been suggested for the quantitative estimation of the concentration of magnetite (Fe3O4) nanopowder in water. A calibration dependence of the relaxivity T2−1 on the iron concentration has been obtained for model suspensions of magnetite nanoparticles with sizes of approximately 20 nm in the concentration range of 0.15–70 mg/L. For comparison, the concentration dependences of T2−1 for aqueous solutions of Fe(NO3)3 · 9H2O and FeSO4 · 7H2O and paramagnetic salts Ni(NO3)2 · 9H2O, Cr(NO3)3 · 9H2O, and CuSO4 · 5H2O have been studied to show that they correlate with their paramagnetic susceptibilities.