Mechanochemical Synthesis of Layered Double Hydroxides as a Promising Method for the Preparation of Adsorbents and Catalysts

Kinetics and Catalysis - The results of studies in the field of synthesis and characterization of layered double hydroxides (LDHs) obtained using solid-phase reactions are summarized. The effect of...     

Studies of the compositions of Pd(II) hydrolysis products

The characterization of the clusters formed on alkaline hydrolysis of [PdCl₄]^2– was performed using¹⁷O,²³Na,³⁵Cl,¹³³Cs NMR and UV spectroscopy. The chemical composition of the clusters was found to be [Pd(OH)₂] _n ·nNaCl. No mononuclear oxo- or hydroxocomplexes were detected. The spatial structure of the clusters is stabilized by alkali metal cations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 675–679, April, 1993.     

Preparation of colloidal solutions of noble metals stabilized by polyoxometalates and supported catalysts based on these solutions

Conditions for the preparation of stable aqueous monometallic and bimetallic colloidal solutions (sols) of noble metals (Ru, Rh, Pd, Pt, Ir, Ag, and Au) in the presence of polyoxometalates containing W, Mo, V, and Nb were found. The stability of sols against coagulation at room temperature was studied. The metal/C samples prepared by metal adsorption from sols were studied by powder X-ray diffraction analysis and transmission electron microscopy. The following factors of importance for the preparation of a stable sol are discussed: (1) the formation of a sol of a metal polyhydroxo complex stabilized by a polyoxometalate (preliminary stage) and (2) the formation of polyoxometalate-metal clusters in the course of reduction of polyhydroxo complexes.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 921–929.Original Russian Text Copyright © 2004 by Maksimova, Chuvilin, Moroz, Likholobov, Matveev.     

Structure of polynuclear palladium(ii) hydroxocomplexes formed upon alkaline hydrolysis of palladium(ii) chloride complexes

The structure of polynuclear Pd^II hydroxocomplexes (PHC) formed as a result of alkaline hydrolysis of Pd^II chloride complexes was studied by EXAFS, SAXS, and TEM methods. It is established that in aqueous solutions a hydroxocomplex particle is a filament curled into a ball containing about 100 Pd atoms. The filament consists of planar coordination squares of PdO₄ units linkedvia one or two oxygen bridges of different geometry. Aging of samples results in an increase in the number of single bridging ligands and a decrease in the diameter of particles. Interatomic distances around palladium atoms were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimlcheskaya, No. 10, pp. 1901–1905, October, 1995.     

WO3/MO2 (M = Zr, Sn, Ti) heterogeneous acid catalysts: Synthesis, study, and use in cumene hydroperoxide decomposition

Thirty (5–40)% WO₃/MO₂ (M = Zr, Ti, Sn), heterogeneous acidic catalysts have been synthesized by two methods, specifically, via homogeneous acid solutions and from solutions brought to pH 9 with ammonia, both followed by calcination at 600–900°C. The catalysts have been characterized by IR spectroscopy and scanning electron microscopy, and their aqueous washings have been analyzed. Their acidity has been determined by the thermal analysis of samples containing adsorbed pyridine, and in terms of the proton affinity scale. Catalytic activities have been compared for cumene hydroperoxide (CHP) decomposition at 40°C in cumene and acetone. For all M, the catalysts are one type and contain W in strongly and weakly bound states, the latter being a polyoxometalate that can be washed off. Both tungstate phases are active in acid catalysis. Brønsted acid sites with a broad strength distribution have been found. The strongest of them are heteropolyacid protons. The catalysts 30% WO₃/SnO₂ and 20% WO₃/ZrO₂ (in acetone) and 10–20% WO₃/TiO₂ (in cumene) are the most active in CHP decomposition, and their activity is not related to their total acidity. Phases containing W⁶⁺ that form during the high-temperature synthesis are responsible for the high acidity, and additional protons that may appear owing to W⁶⁺ reduction can play only a minor role.     

Low-temperature hydrodechlorination of 2,3-dichlorodibenzo-p-dioxin and chlorobenzene with hydrides catalyzed by transition metal compounds

Hydrodechlorination of chlorobcnzene by chemically bound hydrogen in the presence of transition metal compounds was studied. Alkali and alkaline earth metal hydrides (NaH, MgH₂, LiAlH₄, NaH(LiAlH₄)/12) were used as the sources of the chemically bound hydrogen. The effect of the natures of the hydride and of the transition metal on the activity was studied under comparable conditions. The Pd/C-NaH(LiAlH₄1/2 catalytic system was found to be the most active. This system made it possible to perform the quantitative dechlorination of 2,3-dichlorodibenzo-p-dioxin at 70 °C.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1391–1394, June, 1996.     

Adsorption of H3PW12O40 by porous carbon materials

Adsorption of H₃PW₁₂O₄₀ from water and organic oxygen-containing solvents (AcOH, Me₂CO, MeOH) by carbon mesoporous materials, viz., Sibunit and catalytic filamentous carbons (CFC), was studied. The amount of irreversibly sorbed heteropolyacid is 50—100 mg g^–1 of support and decreases in the series of solvents: H₂O > Me₂CO > AcOH > MeOH. The adsorption capacity of CFC depends on the specific surface, total pore volume, and microstructure of the CFC fiber.     

Propylene oxidation by palladium nitro and nitrato complexes: in situ NMR and IR studies

The mechanism of the propylene oxidation by Pd(NO_n)Cl_2 − m(CH₃CN)₂ complexes (n = 2, 3; m = 0, 1, 2) in chloroform solutions has been studied by ¹H NMR and IR spectroscopy. The main reaction products are acetone and 2-nitropropylene, with their ratio depending on the equilibrium existing in the reaction solutions between palladium complexes containing NO_n ligands bonded to a palladium atom via either an oxygen or a nitrogen atom. Reactivities of the oxygen bonded nitrato and nitrito complexes are significantly higher than that of the nitrogen bonded nitro complex. Various new organopalladium intermediates have been observed and monitored in situ. A reversible insertion of the coordinated propylene into the Pd-O or Pd-N bonds results in nitrato-, nitrito- and nitropalladation intermediates, which then decompose via a β-hydrogen elimination. Two isomers of the nitritopalladation intermediate have been detected, i.e., a palladium metallacycle and an open ring complex, with the latter being much more reactive towards the β-hydrogen elimination than the former. The decomposition of the nitrato- and nitritopalladation intermediates results in the organometallic precursor of acetone, i.e., an acetonylpalladium complex, and then in acetone itself. On the other hand, the nitropalladation intermediate originates 2-nitropropylene. In the presence of dioxygen, which re-oxidizes the nitrosyl groups, the acetone formation becomes a catalytic reaction with respect to both palladium and nitrogen.     

Institute of Hydrocarbon Processing,Siberian Branch,Russian Academy of Sciences advances of science and practice in solving problems of chemical hydrocarbon processing

The paper provides information about the Institute of Hydrocarbon Processing which was founded in 2003 and is the yangest chemical institute of the Siberian Branch of the Russian Academy of Sciences (IHP SB RAS). Advances of the Institute both in basic applied research, as well as perspective lines of research on hydrocarbon processing technologies and synthesis of carbon materials are demonstrated.     

Influence of carbon support pretreatment on properties of Pd/C catalysts

Preoxidation of the surface of carbon support was found to increase the dispersity of palladium and activity of Pd/C catalysts obtained by reduction of supported Pd(OAc)₂, in hydrogenation of olefins. Probable reasons for this effect are discussed.

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, Pd/C , Pd(OAc), . .