Modification of silica gels with small admixtures of titanium ions

Microporous silica gels containing small amounts of titanium ions are synthesized. Addition of Ti ions to the silica gels during the sol-forming step is demonstrated to increase the specific surface area and decrease the volume of sorptive pores. Spectral results indicate that Ti ions uniformly distribute in the silica gel matrix and isomorphously replace Si.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2217–2222, October, 1991.     

Copper Complexes Stabilized by Chitosans: Peculiarities of the Structure,Redox, and Catalytic Properties

Peculiarities of the structure and physicochemical properties of copper–chitosan complexes prepared by different methods were studied by IR, UV-visible, ESR spectroscopy, and electron microscopy. The catalytic activity of redox copper centers stabilized by the chitosan matrix in the reactions of oxidation of o- and p-dihydroxybenzenes in an aqueous medium was determined. Quantitative ESR measurements provide evidence for the localization of virtually all copper ions introduced in the initial heterogeneous chitosan samples with copper contents below 1.5 wt % in the form of isolated Cu²⁺ ions in square planar coordination. The chitosan matrix was shown to strongly bind copper ions under conditions of redox transformations in the catalytic tests or upon prolonged heating in boiling water. Reoxidation of the samples with H₂O₂ results in quantitative restoration of the initial ESR signal of Cu(II). Heterogenized copper–chitosan samples exhibited high activity and stability in the catalytic oxidation of dihydroxybenzenes into quinones, whereas the homogeneous system was characterized by irreversible poisoning due to formation of copper–hydroquinone complexes. Preparation of the binary composite system with a thin heterogeneous copper–chitosan film supported on a macroporous silica allows one to dramatically enhance the specific catalytic activity and the efficiency of the active component. Such an approach may turn out to be useful in the synthesis of supported chitosan catalyst with a low noble metal content.     

Synthesis and some properties of titanium-containing silica gels

Microporous silica gels containing small amounts of titanium ions have been synthesized. Porous structure and surface active sites of silica gels have been studied. It has been found that the titanium ions are distributed uniformly in silica gel matrix, substituting silicon ions isomorphically.     

Metathesis of hex-1-ene in ionic liquids catalyzed by WCl6

Metathesis of hex-1-ene in ionic liquids catalyzed by WCl₆ was studied. The metathesis is preceded by isomerization of hex-1-ene to hex-2-ene, from which the main reaction product, viz., oct-4-ene, is derived. The WCl₆-1-butyl-3-methylimidazolium tetrafluoroborate (BMIM·BF₄) system efficiently catalyzes metathesis of linear olefin, the ionic liquid serving as the reaction medium by forming a stable homogeneous catalytic system with WCl₆. The yields of the metathesis products increase with increasing reaction temperature. The addition of tin-containing promoters leads to a substantial increase in the reaction rate. In the WCl₆-BMIM·BF₄-SnBu₄ system, the selectivity of the formation of oct-4-ene is significantly enhanced.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2094–2097, October, 2004.     

Solvation of Aniline in Mixtures of Water with N,N-Dimethylformamide and Acetonitrile

Thermal effects of aniline solution in water-N,N-dimethylformamide (DMF) and water-acetonitrile mixtures were measured at 25°C. In almost the whole range of compositions of the mixed solvents, the thermal effects are more positive in aqueous acetonitrile than in aqueous DMF. Particular attention was given to binary solvents with a very low content of the organic cosolvent. In the mixture with the mole fraction of DMF of 10^{- 3}, the enthalpy of aniline solution is higher than in water by 5%, and in the mixture with the mole fraction of acetonitrile of 4 × 10^{- 4}, even by 15%. Features of specific solvation of aniline and an aliphatic amine (n-BuNH₂) in the water-DMF mixture were discussed taking into account the acid-base properties of the mixtures. The coefficients of pair interactions aniline-organic solvent in water and aniline-water in the organic solvent were calculated using the McMillan-Mayer theory. These coefficients correlate with the enthalpies of hydration of aprotic solvent molecules.     

Investigation of the state of palladium in the Pd/SO4/ZrO2 system by diffuse-reflectance IR spectroscopy

The Pd/ZrO₂ and Pd/SO₄/ZrO₂ systems were investigated by diffuse-reflectance IR spectroscopy using CO as the probe molecule. For the Pd/ZrO₂ system, the behavior of the metal is characteristic of the weak metal-support interaction. Intense bands attibuted to the bridging CO species indicate the formation of large metal particles in the reduced systems. Modification of the ZrO₂ support with SO₄ ^2? anions leads to an increase in the metal—support interaction and makes the metal more resistant to reduction. On the surface promoted by SO₄ ^2? anions, metal particles with a positive charge (Pd⁺ and Pd^δ+) were observed. The smaller the size of the metal clusters and the higher degree of oxidation of sulfur, the stronger the influence of acidic protons and surface sulfur compounds on the metal.     

Electrochemical modification of steel by platinum nanoparticles

The aim of this study was to synthesize low-concentration catalysts with a highly developed surface based on nanodispersed platinum deposited onto the steel surface electrochemically modified with the use of an ionic liquid. Sintered fibers of austenitic steel without pretreatment (steel 1) and etched with hydrochloric acid to remove surface oxides (steel 2) were used as substrates. 1-Butyl-4-methylimidazolium acetate [BMIM][Ac] ionic liquid was used. Variation of the current intensity and anodic treatment time leads to the formation of different structures at the steel surface. For steel 2, optimal conditions leading to self-organization, namely, formation of hexagonal structures, have been selected. It has been demonstrated that formation of nanostructures at the steel surface can occur without the participation of fluoride ions. Low-concentration (Pt/steel 2) catalysts with a uniform distribution of platinum nanoparticles over the surface were prepared via galvanostatic deposition from an aqueous solution of H₂PtCl₆.