N. A. Maiorova

Tolerant-to-methanol cathodic electrocatalysts based on organometallic clusters

A new approach to the fabrication of catalytic systems based on hetero-and homometal-chalcogenide clusters of Pt-M-X type (M: Fe, Mn; X: S, Se, Te), which provides the reproducibility of catalyst composition and uniform distribution of catalyst over the carbon support, is proposed. Thus obtained catalysts are characterized using the XRD, TEM, and EDAX methods. The electrocatalytic activity of these systems in the oxygen reduction reaction, the role of the nature of chalcogenide atom and the atom of the second metal, which is the platinum partner, and the electrochemical behavior of nonplatinum chalcogenide systems are studied.

Nanostructured catalysts for cathodes of oxygen-hydrogen fuel cells

Bimetallic catalysts platinum-cobalt, platinum-chromium, and platinum-tungsten, deposited onto highly dispersed carbon black from complex cluster-type compounds of corresponding metals with a 1: 1 atomic ratio of metals are developed. The catalysts are characterized by methods of x-ray diffraction analysis and energy dispersive analysis of x-rays. The procedure involving use of a thin-film rotating disk electrode is employed to probe kinetic parameters of the oxygen reduction reaction on the catalysts developed. The investigated binary catalysts exhibit specific electrochemical characteristics that are not inferior and, in some cases, are superior to the characteristics intrinsic to the commercial platinum catalyst E-TEK, when tested in the composition of a gas-diffusion electrode under conditions that are close to real conditions in which cathodes of oxygen-hydrogen fuel cells operate.

Thin-film rotating disk electrode as a tool for comparing the activity of catalysts in the hydrogen oxidation reaction

A thin-film disperse rotating disk electrode is used to study the hydrogen oxidation reaction on platinum catalysts E-TEK with different purification degrees and on disperse palladium catalysts obtained from colloid solutions of organometallic complex precursors with subsequent thermal decomposition in an inert atmosphere or in hydrogen at diverse temperatures. Kinetic currents of the hydrogen oxidation reaction on these catalysts are determined at a potential of 0.025 V. The obtained values of currents may be utilized for performing a comparative estimation of the activity of various catalysts and the degree of their purification from the precursors or accidental impurities.

Electrochemical frontiers in global environment and energy (survey of materials of the 62nd annual meeting of the international society of electrochemistry)

The state of the art and the main trends in the development of modern theoretical and applied electrochemistry are surveyed based on results of the 62nd Annual Meeting of the International Society of Electrochemistry.

Effect of the functionalizing of carbon nanotubes on the electrodeposited catalysts’ structure and catalytic properties

The structure and hydrophilic-hydrophobic properties of functionalized single-wall carbon nanotubes are studied by the standard porosimetry method. It is shown that the functionalized nanotubes have highly hydrophilic surface; at that the summary surface area measured “by octane” decreased, as a result of the functionalizing, due to the blocking of the nanotubes’ inner channels by the functional groups located at the nanotubes’ ends. The nanotubes’ capacitive properties are studied; their charging-discharging curves appeared being highly reversible, unlike those of other carbonaceous materials. Catalytic properties of the functionalized nanotubes are studied, with particular tendency toward their using as a carrier of platinum catalysts for the methanol oxidation and oxygen electroreduction reactions. When minor amounts (5–10 µg cm−2) of platinum or platinum-ruthenium alloy are deposited onto the nanotubes’ hydrophilic surface, uniform layer of the catalyst is formed, with specific surface area up to 150–300 m2 g−1; high current of the methanol oxidation or oxygen electroreduction is observed at these catalysts. When the catalyst deposit mass increased, its specific surface area decreased, as well as the specific current of the reactions occurring thereon. When the current is related to the electrochemically active unit surface, the catalytic activity is nearly the same both for different catalyst mass deposited onto the nanotubes and the same catalyst mass at different carbonaceous carriers.

Development of methanol–air fuel cells with membrane materials based on new sulfonated polyheteroarylenes

New proton-conducting membranes were synthesized from sulfonated polynaphthoyleneimide (SPNI) and polytriazole (SPTA), which are of interest for use in portable methanol fuel cells. The membrane electrode assembly (MEA) based on SPNI and SPTA showed power and voltage-current characteristics comparable to those of MEA based on Nafion®-117. The direct and reverse polarization curves coincided almost completely in shape, indicating that the obtained characteristics are stable. At a voltage of 0.3 V and a temperature of 40°С, the current density and power density reached 68 mA cm–2 and 20.5 mW cm–2, respectively.

Photoelectrocatalytical Kolbe synthesis on thin film electrode of n-TiO2

The possibility of the photoelectrochemical reaction of acetate and trifluoroacetate oxidation to yield the corresponding hydrocarbons and perfluorocarbons on UV illumination of a film of nanosized titania n-TiO2 is demonstrated by the methods of cyclic voltammetry and preparative photoelectrolysis. Thus, the use of solar energy makes it possible to synthesize the Kolbe reaction products at substantially lower potentials on electrodes-catalysts containing no platinum.

Electrochemical oxidation of perfluorovaleric and perfluoro-2-propoxypropionic acids on different electrodes in the presence of unsaturated acceptors

The composition of the products of the additive Kolbe electrosynthesis involving perfluorovaleric and perfluoro-2-propoxypropionic acids and conducted in the presence of butadiene and their current efficiencies are determined by competitive adsorption of the corresponding carboxylates and butadiene at the anode. The perfluoro-2-propoxypropionate anion was the most effective adsorbate in this series. The perfluorovalerate anion was largely displaced by butadiene from the anode. This drastically decreased the current efficiency and led to an anomalously high content of higher telomer homologs among the products of additive electrosynthesis.

Catalytic phenomena during the methanol oxidation at platinum electrodes in contact with solid polymer electrolytes

The methanol electrooxidation at platinum-gauze electrodes contacting a solid polymer electrolyte is studied in water and sulfuric-acid solutions by voltammetry in a broad potential range and by measuring steady-state currents and electrode coverages with chemisorbed species at low anodic potentials. The specific rate of the methanol oxidation in these systems is higher than that of similar platinum electrodes in liquid electrolytes. The catalytic action depends on the measurements conditions and the electrode potential. Reasons for catalytic effects at different potentials are discussed.

The Photoelectrochemical Activity of Titanium Dioxide Nanosized Films in the Visible Spectral Region

From solutions of organic precursors, nanosized films of titanium dioxide with photoelectrochemical activity in the visible region are obtained. A possibility of photoelectrochemical oxidation of a number of organic compounds under illumination with monochromatic light at a wavelength of 464 nm is demonstrated, which may be due to a decrease in the n-TiO2 band-gap energy to 2.7 eV.