Catalyst-free chemical vapor deposition is used to form thin (1-2 nm) carbon layers on the surface of alumina nanofibers resulting in carbon-alumina nanocomposites. Thermal analysis, X-ray fluorescent microanalysis, Raman spectroscopy, and electrical resistance measurements of these composites show that increasing of synthesis time not only increases the amount of carbon on alumina surface, but also the ordering and density of the carbon layers. Nitrogen adsorption data reveal the decrease of total pore volume with increasing the synthesis time. The obtained composite material could be employed for the preparation of ion-selective membranes with switchable ion transport, electroconductive ceramics, and electrochemical sensors.

The effect of an external electric field on the ionic conductivity and selective properties of ceramic membranes based on alumina nanofibers coated with a conductive carbon layer has been studied. It has been shown that the membranes are ideally polarizable in the polarizing voltage range of −500 to +500 mV and, therefore, can be used for implementing switchable ionic selectivity. Experiments have revealed that the membrane resistance decreases with a change in the applied potential from 0 to ±500 mV. It has been shown that the membrane selectivity can be switched from anion to cation by varying the external potential. The surface charge density of the membranes has been determined in terms of the Teorell–Meyer–Sievers model according to the experimental measurements of the membrane potential.

We report a new mechanism for the generation of membrane potential in polarizable nanoporous membranes separating electrolytes with different concentrations. The electric field generated by diffusion of ions with different mobilities induces a non–uniform surface charge, which results in charge separation inside the nanopore. The corresponding Donnan potentials appear at the pore entrance and exit leading to a dramatic enhancement of membrane potential in comparison with an uncharged non–polarizable membrane. At high concentration contrast, the interaction between electric field and uncompensated charge at a low concentration side results in the development of electrokinetic vortices. The theoretical predictions are based on the Space–Charge model, which is extended to nanopores with polarizable conductive surface for the first time. This model is validated against full Navier–Stokes, Nernst–Planck, and Poisson equations, which are solved in a high aspect ratio nanopore connecting two reservoirs. The experimental measurements of membrane potential of dielectric and conductive membranes in KCl and NaCl aqueous solutions confirm the theoretical results. The membranes are prepared from Nafen nanofibers with ∼10nm in diameter and modified by depositing a conductive carbon layer. It is shown theoretically that the membrane potential enhancement becomes greater with decreasing the electrolyte concentration and pore radius. A high sensitivity of membrane potential to the ratio of ion diffusion coefficients is demonstrated. The described phenomenon may find applications in precise determination of ion mobilities, electrochemical and bio–sensing, as well as design of nanofluidic and bioelectronic devices.

A novel type of ion-selective membranes based on Nafen TM alumina nanofibers coated with carbon is proposed. The membranes are produced by filtration of a Nafen nanofiber suspension through a porous support followed by drying and sintering. A thin carbon layer (up to 2 nm) is deposited on the nanofibers by chemical vapor deposition (CVD). Its formation is confirmed by the results of Raman spectroscopy and visually observed in TEM images. According to low temperature nitrogen adsorption experiments, the formation of carbon layer leads to decreasing pore size (the maximum of pore size distribution shifts from 28 to 16 nm) and the corresponding decrease of porosity (from 75 to 62%) and specific surface area (from 146 to 107 m 2 g –1 ). The measurement of membrane potential in an electrochemical cell has shown that the deposition of carbon on the membrane results in high ionic selectivity. In an aqueous KCl solution, the membranes display high anion selectivity with anion and cation transference numbers of 0.94 and 0.06, respectively. The fixed-charge density of membrane has been determined by fitting the experimental data using the Teorell–Meyer–Sievers model. It has been found that the membrane fixed-charge density increases with increasing electrolyte concentration. Possible applications of the membranes produced include nanofiltration, ultrafiltration, and separation of charged species in mixtures. The formation of a conductive carbon layer on the pore surface can be employed for fabricating membranes with switchable ion-transport selectivity.

The authors propose a novel type of ion-selective membranes, which combine the advantages of ceramic nanofibrous media with good electrical conductivity. The membranes are produced from Nafen alumina nanofibers (diameter around 10nm) by filtration of nanofiber suspension through a porous support followed by drying and sintering. Electrical conductivity is achieved by depositing a thin carbon layer on the nanofibers by chemical vapor deposition (CVD). Raman and FTIR spectroscopy, X-ray fluorescence analysis, and TEM are used to confirm the carbon structure formation. The deposition of carbon leads to decreasing porosity (from 75 to 62%) and specific surface area (from 146 to 107m(2) g(-1)) of membranes, while the pore size distribution maximum shifts from 28 to 16nm. Measurements of membrane potential in an electrochemical cell show that the carbon coated membranes acquire high ionic selectivity (transference numbers 0.94 for anion and 0.06 for cation in aqueous KCl). Fitting the membrane potential data by the Teorell-Meyer-Sievers model shows that the fixed membrane charge increases proportionally with increasing electrolyte concentration. The carbon coated membranes are ideally polarizable for applied voltages from -0.5 to +0.8V. The potential applications of produced membranes include nano- and ultrafiltration, separation of charged species, and switchable ion-transport selectivity.

It was shown that methane decomposition on metal–carbon nanocomposites with transition metal (Co, Fe, and Ni) nanoparticles distributed in the bulk of the amorphous carbon matrix leads to carbon deposition with the formation of a graphite-like shell around a metal core. The resulting “core-shell” structures have a diameter of 10–40 nm and contain up to 50 graphene layers with an interlayer distance of 0.34–0.35 nm. For the synthesis of the initial metal–carbon nanocomposites, a method that we proposed earlier was used, which involves low-temperature formation of carbon structures from carbon-chain chloropolymers based on their dehydrochlorination with the formation of polyvinylenes as reactive carbon precursors.

When a charged membrane separates two salt solutions of different concentrations, a potential difference appears due to interfacial Donnan equilibrium and the diffusion junction. Here, we report a new mechanism for the generation of a membrane potential in polarizable conductive membranes via an induced surface charge. It results from an electric field generated by the diffusion of ions with different mobilities. For uncharged membranes, this effect strongly enhances the diffusion potential and makes it highly sensitive to the ion mobilities ratio, electrolyte concentration, and pore size. Theoretical predictions on the basis of the space charge model extended to polarizable nanopores fully agree with experimental measurements in KCl and NaCl aqueous solutions.

Carbon–carbon nanocomposite (CCNC) was synthesized by introducing a dispersion of reduced graphite oxide (RGO) into the reaction medium upon the synthesis of polymer with a conjugated bond system (polyvinylene), which is a product of alkaline dehydrochlorination of polyvinylchloride, followed by carbonization of the resulting adduct–RGO-polyvinylene. After activation of CCNC in the CO2 environment (900°С) a high-porosity material (the specific BET surface is more than 1700 m2/g) with a developed volume of micro- and mesopores was obtained. According to electrochemical investigations, this material possesses a large capacity (100–200 F/g) and high performance, and, therefore, it can be applied in supercapacitor traction systems and for load leveling in electric power lines.

Experimental and Modelling Study of Ionic Selectivity in Carbon Coated Alumina Nanofiber Membranes Ilya I. Ryzhkov*, Denis V. Lebedev, Vera S. Solodovnichenko, Alexey V. Shiverskiy, Michael M. Simunin, Vladimir A. Parfenov Institute of Computational Modelling SB RAS, Akademgorodok 50–44, Krasnoyarsk, Russia Molecular electronics department KSC SB RAS, Akademgorodok 50–44, Krasnoyarsk, Russia National Research University of Electronic Technology – MIET, Shokin square 1, Zelenograd, Moscow, Russia Institute of Chemistry and Chemical Technology SB RAS, Akademgorodok 50–24, Krasnoyarsk, Russia rii@icm.krasn.ru

The applicability of a porous carbon material obtained as a result of the “chemical” dehydrochlorination of chlorinated polyvinyl chloride as a support for palladium hydrogenation catalysts was demonstrated. The efficiency of the catalyst was evaluated in the liquid-phase reactions of nitrobenzene hydrogenation and chlorobenzene hydrodechlorination. Although the specific activity of the catalyst was lower by a factor of 3–4 than that of the samples based on Sibunit and carbon nanotubes, the complete conversion of the initial compounds with the selective formation of end products under mild conditions was achieved at a relatively low palladium content (1.5%).

A method for carbon materials synthesis based on polyvinyl chloride has been proposed. Method includes polymer dehydrochlorination by alkali with carbon-rich conjugated structures (polyvinylenes) formation and its subsequent carbonization at relatively low temperatures. Raman and 13C NMR spectroscopy and transmission electron microscopy show that thermal treatment of the resulting polyvinylenes up to 400 °C leads to the formation of amorphous carbon material with chlorine contain less than 0.5 wt.%. These results can be used to develop dioxin-free technology of utilization of polyvinyl chloride and its wastes.

This work shows the possibility in principle of forming hydrocarbon structures in polyvinyl chloride films free of admixtures and polyvinyl chloride films modified with 5-mass % ferrocene via a radiation chemical transformation in the atmosphere with the use of an electron accelerator with a plasma cathode operating in the pulsed-periodic mode maximal electron energy no higher than 160 keV, pulse length of 40 μs, and current density of 5 mA/cm 2 . According to the results of semiquantitative X-ray microanalysis, an irradiated polyvinyl chloride film free of admixtures contains 92 of carbon, 6 of oxygen, and 2 mass % of chlorine; the irradiated polyvinyl chloride is an amorphous carbon material. A possible mechanism of the phenomenon is discussed.

Mechanochemical activation of PVC in a high-energy centrifugal-planetary mill was shown to increase its reactivity in dehydrochlorination under the action of bases. Thus modified PVC is capable of low-temperature carbonization and can form a carbon material even at the temperatures below 400°C.

A method for the synthesis of core-shell structures during methane decomposition in a cobalt-carbon composite with metal particles uniformly dispersed in its bulk is proposed. These composites are obtained by the low-temperature formation of carbon structures based on reactive conjugated polymers obtained by the dehydrochlorination of chlorine-containing carbon-chain polymers. Eelectron microscopy studies show the formation of structures containing 10–50 graphene layers closely packed around a metal core with an interlayer distance of 0.34–0.35 nm.