A. E. Ermakov

Effects of Copper(II) Ions and Copper Oxide Nanoparticles on Elodea densa Planch.

Effects of copper ions and copper oxide nanoparticles on lipid peroxidation rate, activities of anti-oxidant enzymes (superoxide dismutase, catalase, and peroxidase), and photosynthesis have been studied in experiments with Elodea densa Planch. The results show that nanoparticles are more actively accumulated by plants. Both copper ions and nanoparticles activate lipid peroxidation (to 120 and 180% of the control level, respectively). Catalase and superoxide dismutase activities in plants treated with nanoparticles increase by a factor of 1.5–2.0. Copper ions suppress photosynthesis at a concentration of 0.5 mg/l, whereas nanoparticles produce such an effect only at 1.0 mg/l. The observed effects of different forms of copper on E. densa are discussed in a comparative aspect.

Kinetics of interaction of Mg-based mechanically activated alloys with hydrogen

Parameters of interaction of hydrogen with magnesium powders and structure of powder magnesium alloys alloyed with different metals and oxides (such as Fe, Ni, Al, Cu, Ti, Pd, NiPd, V2O5, and VH2) prepared by mechanical activation under either argon or hydrogen atmosphere in a vibration mill have been studied. The mechanically activated alloys absorb to 7 wt% hydrogen at 300°C for 20 min. For most of the additions used, the effect of the grain size and type of addition on the rate of hydrogen absorption was found to manifest itself only at the stage of the formation of the MgH2 phase upon mechanical activation in the hydrogen atmosphere; virtually no effect is observed upon subsequent hydrogenation. The temperature of the hydrogen desorption also depends only slightly on the addition kind. The increase in the hydrogenation rate of the Mg-based alloys resulting from the mechanical activation was shown to be due to the formation of a specific structural state of the particle surface, which exhibits a high catalytic activity for the hydrogen sorption. A study of the mechanically activated alloys by proton nuclear magnetic resonance showed a substantial increase in the rate of proton spin-lattice relaxation as compared to that observed for MgH2 produced by direct hydrogenation. This can be due to the interaction of protons with paramagnetic centers formed at the imperfect surface of mechanically activated Mg particles.

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.

Specific features of the electronic structure and optical spectra of nanoparticles with strong electron correlations

Analysis of the experimental optical spectra of CuO nanoparticles with the electronic structure characterized by strong electron correlations has revealed the appearance of unusual states inside the band gap. The intragap states and the specific features of the electronic structure of CuO nanoparticles are discussed in the framework of the generalized tight-binding method previously developed for describing the electronic structure of superconducting cuprates.

Anomalies in the optical properties of nanocrystalline copper oxides CuO and Cu2O near the fundamental absorption edge

A 0.1–0.15-eV displacement of the fundamental absorption edge in the optical absorption spectra of nanocrystalline oxide n-CuO (relative to the position of the fundamental absorption edge in the spectra of CuO single crystals) towards lower energies (red shift) is observed against the background of strong blurring. Nanocrystalline n-Cu2O exhibits a displacement of the fundamental absorption edge towards higher energies (blue shift) by approximately 0.35 eV. The size of crystallites in n-CuO and n-Cu2O ranges from 10 to 90 nm. The blue shift of the fundamental absorption edge of n-Cu2O is typical of classical wide-gap semiconductors and can be explained by size quantization upon a change in the particle size. The anomalous red shift of the fundamental absorption edge of the strongly correlated nanocrystalline oxide n-CuO can be attributed to the highly defective structure of n-CuO, anomalies in the electronic structure of strongly correlated compounds based on 3d metals, and their tendency to electronic phase separation with the formation of metal-like inclusions.

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).