


Vol 12, No 5-6 (2017)
- Year: 2017
- Articles: 13
- URL: https://journals.rcsi.science/2635-1676/issue/view/13627
Article
In situ IR spectroscopy study of ethanol steam reforming in the presence of Pt–Ru/DND nanocatalysts
Abstract
Ethanol steam reforming (ESR) over a Pt–Ru(0.3%) catalyst supported on detonation nanodiamonds (DNDs) and on DNDs containing no noble metals has been studied. It has been shown that the two catalysts provide the formation of the same products; however, their yield and distribution significantly change after supporting Pt–Ru on DND. The adsorbed species that formed during ESR over DND and the Pt–Ru(2.5%)/DND model catalyst have been studied by in situ high-temperature diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). It has been shown that the ability of pure DND to mediate the ESR process is provided by the carbonyl and carboxyl groups on the DND surface; this feature is the main difference of the Pt–Ru/DND catalytic nanocomposite from catalysts in which Pt and Ru are supported on various oxides. On the basis of a comparison of the results obtained during ESR in a catalytic reactor and in a DRIFTS cell, a mechanism of the process over DND-supported catalysts has been proposed.



On the possibilities of recognizing the architecture of binary Pt–M nanoparticles
Abstract
The identification of subtle structural effects in bimetallic nanoparticles via conventional methods is discussed using the example of PtCu/C nanostructured electrocatalysts. The divergence factors between experimental X-ray diffraction profiles and patterns simulated in the single-phase approximation for pure (or solid solution) and bi-phase metals in a suspected core–shell structure are found to be different. The catalysts containing the core–shell nanoparticles may be chosen from some materials with nanoparticles of different architectures based on X-ray diffraction and cyclic voltammetry data if the nanoparticles consist of a relatively massive Cu core and a thick Pt shell.



MF-4SC hybrid membranes doped with carbon nanotubes functionalized with proton-acceptor groups
Abstract
Carbon nanotubes functionalized with proton acceptor groups are obtained for their use as dopants for hybrid materials based on an MF-4SC perfluorinated sulfonated membrane. Ion conductivity at high and low relative humidity, diffusion permeability of hydrochloric acid and methanol permeability, interdiffusion of H+/Na+ ions and mechanical properties of the final hybrid materials are studied as well. Introducing a small amount of dopant (0.5 wt %) is shown to favor an increase in ion conductivity at both high and low humidity, along with a decrease in methanol permeability, compared to the analogous initial membrane. In the specimens with 1–3 wt % of dopant, cation transport selectivity is higher than in the initial MF-4SC membrane. Furthermore, the mechanical properties of hybrid materials are found to not deteriorate, at least.



Amorphization model of nanostructured composite solid electrolytes
Abstract
In the last decades, extensive research has been undertaken to find solid electrolytes that might increase the power and safety of promising electrochemical devices such as lithium batteries, supercapacitors, and solid oxide fuel cells. It is mainly based on the screening of advanced functional suprastructures and developing special synthesis procedures to obtain nanosized materials, allowing one to increase ionic conductivity. That’s why special attention is paid to composite solid electrolytes. In this work we use the accumulated knowledge on the physical chemistry of metals and alloys to describe the amorphization effects. It is known that amorphization at the interphase boundaries (interfaces) and grain boundaries noticeably increases (sometimes by orders of magnitude) the ionic transfer rate and, therefore, affects the functional properties of nanostructured composite solid electrolytes. In the theoretical model proposed, we have attempted to elucidate the reasons, inducing the amorphization effects which are observed upon the crystallization of inorganic eutectics and composite formation. We have especially used the approximation of rigid discs, considered, unit-cell volumes. In the context of the theory, describing the amorphization as an excess molar volume arising upon the crystallization of metals and alloys, we have established that the degree of amorphization depends not only on the synthesis conditions, but also on the incommensurability of crystal unit cells in the components. The findings can be useful in the elaboration of novel inorganic materials for various applications.



Investigation into the dependence of time characteristics of ignition and combustion of iron nanopowders on air on the duration of passivation after synthesis
Abstract
A method of estimating the extent of passivation of iron nanopowders based on color high-speed filming is suggested. It is established that the number of primary centers of combustion and the time of their emergence depend on the passivation time: the more the passivation time is, the lower the number of primary centers of combustion is. This allows using the dependence for estimating both the extent of passivation and the minimum time of complete passivation. A method for calculating the time of complete passivation for the sample of arbitrary thickness is suggested.



Radiation and catalytic properties of the n-ZrO2–n-Al2O3 systems in the process of hydrogen production from water
Abstract
The influence of the interaction between n-ZrO2 and n-Al2O3 on their radiation and catalytic activities in the process of hydrogen production from water is investigated. It is established that, as a result of the interaction between n-ZrO2 and n-Al2O3, the new phase n-ZrO2–n-Al2O3 is formed, which leads to the reduction of radiation and catalytic activity in comparison with separate components and the additive sum of their activities. Regularities of dependences of radiation and catalytic activity from the maintenance of components of the n-ZrO2–n-Al2O3 system are received in the process of hydrogen production. Mechanisms of processes of energy transfer and transmission in the studied nanodimensional systems are offered.



Direct plasmadynamic synthesis and preparation of superdispersed Ti–Si–N compositions
Abstract
The preparation of nanodisperse titanium nitride and titanium carbide compositions by the direct plasmadynamic synthesis in the Ti–Si–N system is described in this paper. The use of the method of direct plasmadynamic synthesis allows one to achieve good mixing of the product and to create ceramic materials without areal defects produced by local agglomerations.



Effect of synthesis conditions on the photocatalytic activity of titanium dioxide nanomaterials
Abstract
The photocatalytic activity of nanosized titanium dioxide powders synthesized by thermal treatment of the precursor phases precipitated from aqueous solutions on the degradation of methylene blue in a solution under the action of UV radiation has been studied. The dependence of the photocatalytic activity on pH of the medium used to precipitate precursor phases in combination with temperatures and duration of their thermal treatment has been found. The selected synthesis conditions allowed to obtain titanium dioxide materials that appear to be at least two times more active than the commercial catalyst Degussa P25. It is found that the materials based on anatase modification of titanium dioxide obtained from the phases precipitated at pH 7–9 and calcined at 600°C for 1–2 h show the highest photocatalytic activity. It is shown that under UV radiation 25 min is enough for almost complete destruction of methylene blue dye in the solution with an initial concentration of 20 mg/L.



Generation of laser radiation by nanostructured solid active elements based on nanoporous aluminum oxide films activated with rhodamine 6G
Abstract
The generation of laser radiation by a solid active element based on a nanoporous aluminum oxide film activated with rhodamine 6G has been obtained for the first time in the geometry to reflection. The lasing is characterized by high-quality radiation with the absence of a spontaneous component. It is found that the application of silicone oil as the immersion substance reduces the generation threshold more than two times. The optimal concentration of rhodamine 6G molecules in the impregnation solution for mirror films of nanoporous aluminum oxide is determined, at which the dye fluorescence intensity has the maximum value. The generation by a nanoporous aluminum oxide film activated with rhodamine 6G in the continuous mode has been obtained for the first time.



Localized plasmon resonance
Abstract
A new analytical solution of the Helmholtz equation in spherical coordinates for an infinite homogeneous space, as well as the solution of the boundary problem for a piecewise-homogeneous medium (space divided into homogeneous domains with various dielectric permittivities of the spherical symmetry borders) has been obtained. The application of the derived formulas to spherical nanoparticles of metal makes it possible to record a mathematical relation to the localized plasmon resonance, which connects the resonance parameters of such a system and the electromagnetic waves. The equation of plasmon resonance confirms the known experimental result of significant amplification of an electromagnetic field at the localized plasmon resonance. The condition of the optical resonance obtained in the work is applicable to layered spheres with an arbitrary number of layers of any size and material.



Alternative correlative microscopy in the studies of cell nucleus subcompartments
Abstract
A new method combining atomic force (AFM) and confocal laser scanning microscopy (CLSM) and permitting not only to obtain information about the surface topography of nanostructures in the cell nucleus, but to simultaneously identify their molecular composition by using fluorescent dyes and treatment with specific enzymes, is proposed. The content of the vegetative nuclei of the ciliate Paramecium caudatum stained with DAPI for revealing DNA and fluorescently labeled phalloidin specifically binding fibrillar actin was been sequentially studied using CLSM and AFM and by successive analysis with AFM after RNAse and Proteinase K treatments. The proposed method allows one to characterize the surface topography of chromatin and RNP-complexes and reveal nanostructures containing nuclear actin which cannot be visualized using CLSM only.



Biokinetic study of selenium nanoparticles and salt forms in living organisms
Abstract
An experimental study of absorption, distribution, metabolism, and excretion from the body of radioisotope-labeled nanoparticles (NPs) of elemental Se in comparison with the traditional form of this trace element (sodium selenite) has been performed, being administered in the gastrointestinal tract of rats that were normally supplied with Se or experiencing its nutritional deficiency. Nuclear activation analysis is used for the detection of Se in the biological tissue, which is based on the measurement of a gamma-emitting label [75Se34] that is introduced in the Se NPs or its salt by thermal neutron irradiation in a nuclear reactor. It is shown that Se NPs administered into the gastrointestinal tract have bioavailability comparable to the salt form of this element. According to some experimental data, the metabolic assimilation of both forms of Se is greater in animals that suffer from a deficiency in this element when compared to those that are normally supplied with it. There are some differences in the kinetics of accumulation of Se NPs and its salts in the blood and liver, which can be explained by the presence of limiting steps in the absorption and biotransformation of Se-containing NPs. The retention of Se that is administered in the form of NPs or salts to Se-deficient animals differs significantly. These results demonstrate the capacity of the Se NPs to be a source of Se in a new generation of biologically active food supplements.



Mathematical simulation of the biokinetics of selenium nanoparticles and salt forms in living organisms
Abstract
A mathematical simulation of the absorption, distribution, metabolism, and excretion from the body of radioisotope-labeled nanoparticles (NPs) of elemental selenium (Se) in comparison with the traditional form of the trace elements (sodium selenite) has been performed, with them being administered in the gastrointestinal tract of rats that are normally supplied with Se or experience its nutritional deficiency. A compartmental mathematical model that describes the biokinetics of the mentioned Se forms at different levels of its supply is constructed. The quantitative parameters of the model are set using the experimental data from a biokinetic study on rats who, via their gastrointestinal tract, received [75Se]-labeled sodium selenite or Se NPs which were obtained by laser ablation and had an average diameter of 97 ± 5 nm. The proposed model, despite the number of necessary simplifications, satisfactorily explains the difference between the experimental data for both Se-supplied and Se-deficient groups of animals. Thus, in the case of Se deficiency, its assimilation by organs occurs more actively than when it is supplied normally. Se in the form of NPs is preferable to its salt form due to the slower formation of HSe- anion and excretable Se forms, which are potentially highly toxic. This conclusion is consistent with the hypothesis that Se NPs may be the basis for the development of a new generation of dietary sources of selenium.


