Polyaniline/12-phosphotungstic acid/V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanocomposite and its platinum analog as oxygen reduction electrocatalysts

A guest-host nanocomposite based on electroconducting polyaniline doped with 12-phosphotungstic acid and V₂O₅ as well as its bifunctional analog containing not more than 5 mass% nanosized platinum were obtained. A study was carried out on the structure of these nanocomposites, their redox characteristics, and electrocatalytic activity in the reduction of oxygen. These nanocomposites were found to display catalytic properties in the electrochemical reduction of oxygen, while the presence of even a slight amount of nanosized platinum in the bifunctional composite leads to a significant increase in its electrocatalytic activity. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 307–314, September–October, 2007.     

Spectral and electrochemical properties of polyaniline-V2O5 composites of the intercalation type

We propose a new approach to obtaining composites of the intercalation type based on polyaniline and V₂O₅. We have determined the characteristics of these composites using x-ray diffraction, IR spectroscopy, and EPR. We show that the compounds obtained exhibit stable redox properties in aqueous and aprotic electrolytes.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 6, pp. 361–364, November–December, 1995.We would like to express our thanks to V. G. II'in for help in carrying out the x-ray phase investigations. This work was made possible with the partial support of the International Science Foundation (grant N U6B000).     

The interaction of 2, 6-di-tert-butyl-4-butoxyphenoxyl and diphenylnitrogen radicals with molecules containing N-H and O-H bonds

It has been shown by the EPR method that the thermal decomposition of bis-(1, 3, 5-tri-tert-butyl-cyclohexadien-2, 5-one)-peroxide (I) into 2, 6-di-tert-butyl-4-butoxyphenoxyl radicals (II) in xylene solution at 80–100 C follows first order kinetics. The transfer of hydrogen from the molecule of diphenylamine (DPA) and 2, 6-di-tert-butyl-4-methylphenol (ionol) to the radicals of (II) formed by the decomposition of (I) has been established and investigated.The diphenylnitrogen (DPN) radicals formed by the thermal dissociation of tetraphenylhydrazine (TPH) in organic solvents at 100 C split a hydrogen atom from the hydroxyl group of sterically hindered phenols, leading to the formation of the corresponding phenoxyl radicals.     

Green Chemistry and Modern Technology

The basic principles, approaches, and early achievements of green chemistry are considered. The definition of green chemistry as a branch of chemistry that studies the laws of passing of chemical reactions and the properties of substances participating in such reactions, with the aim of acquiring basic knowledge that provides a basis for designing chemical technologies that eliminate (sharply curtail) the use and production of materials that pose a risk to the environment.     

Research on polyfunctional oxides

N,N-Diethylcarbamoyl-4,5-epoxy-2-hexenoic acid reacts with ketones in the presence of anhydrous FeCl₃ to give 2,2,4-trialkyl-5-[2-N,N-diethylcarbamoyl(vinylene)]-1,3-dioxolane. 2,2,4-Trimethyl-5-(1-propenyl-3-hydroxy)-1,3-dioxolane is formed in the reduction of 2,2,4-trimethyl-5-[2-carbethoxy(vinylene)]-1,3-dioxolane withlithium aluminum hydride.     

ESR spectra and the behavior of substituted indophenoxyl radicals

ESR spectra and structure are compared for radicals formed from substituted indophenols by oxidation (substituents CH₃, i-C₃H₇, t-C₄H₉, t-C₅H₁₁, cyclohexyl). The unpaired electron interacts with the nitrogen and with the hydrogen in the ortho and meta positions of both benzene rings. A kinetic equation of first order with respect to the indophenol applies to the reaction of the latter with benzoyl peroxide. The loss of indophenoxyl radicals in benzene obeys an equation of second order in the radical concentration. The rate constants for radicals with various substituents indicate the radical stability, which falls greatly in going from ones with ortho-t-alkyl substituents to ones with less highly branched groups.     

Investigation of the electrochemical production and doping of soluble electrically conducting poly(3-methyl-4-phenylthiophene)

The electrochemical production and doping of soluble, as well as the physicochemical properties of a soluble electrically conducting polymer based on 3-methyl-4-phenylthiophene were studied.Translated from Teoreticheskaya i Éxperimental'naya Khimiya, Vol. 29, No. 2, pp. 143–148, March–April, 1993.The authors would like to express gratitude to the State Committee of the Ukraine on questions of science and technology for financial support for this work within the framework of the State Scientific and Technical Program 7.1. Materials for Electronic Technology, as well as to V. P. Kandilenko and V. Ya. Chernov for aid in recording the fluorescence spectra of the P3M4PT films.     

Electrochemical functionalization of organic compounds by “small” molecules

The author's results and published data on the electrochemical insertion of small molecules (CO₂, SO₂, CS₂, NO) into organic substrates are reviewed. Special attention is paid to the cathodic carboxylation of halogen-containing aliphatic and aromatic compounds, polymers, and olefins, the sulfonylation and dithiocarboxylation of Freons, and anodic nitrosation of amines. The probable mechanisms of such processes and the effects of the nature of the reagents and the electrolysis conditions on the composition and yields of the final reaction products are examined.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 2, pp. 97–114, March–April, 1992.