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.     

Structural Peculiarities of Anomalous Electrolytic Palladium Deposits Prepared under Hydride Formation Conditions

The peculiarities of bulk and surface structures of electrolytic palladium deposits formed under hydride formation conditions are studied by x-ray diffraction (XRD) and x-ray photoelectron spectroscopy techniques. For anomalous deposits with high hydrogen capacities, the evolution of the XRD behavior is traced as a function of thermal treatment. The material is shown to comprise two cubic phases with different lattice parameters.     

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.     

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), . .

     

Gas-phase hydroformylation of propylene on Ru/SiO2 catalysts

Ru/SiO₂ catalysts prepared by reduction of supported RuCl₃·xH₂O are active in gas-phase hydroformylation of propylene at low pressure (ca. 0.3 MPa) of H₂+CO+C₃H₆ mixtured and show unexpectedly high selectivity towards unbranched oxo-products. Data concerning the effect of electronic state and dispersity of Ru on their catalytic behavior have been obtained.

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Ru/SiO₂, RuCl₃·xH₂O, (0,3 ) - . .

     

Electron microtomography: A new method for studying the spatial structure of catalysts

The spatial arrangement of active component (Pt) particles on the surface of a support (Sibunit globule) has been studied by bright-field electron tomography. A tomographic attachment for a standard specimen holder and tomographic grids have been designed. The tomographic procedure has been refined, and adequate tilt series alignment and tomographic reconstruction algorithms have been chosen. The 3D distribution of the active component in the catalyst grain has been studied: particles hidden in micropores have been directly observed, and the size of the pores connecting internal cavities with the exterior has been estimated.     

Electrochemical method for producing radionuclide Lu-177 with high specific activity

A modified method for the isolation of radionuclide ¹⁷⁷Lu obtained from a Yb-176 target irradiated with thermal neutrons is proposed. The method consists of the combination of two electrochemical processes— cementation of ytterbium acetate–chloride solution to sodium amalgam and subsequent electrolysis of the ytterbium solution in a separate electrolytic cell without adjusting the solution. The electrochemical setup consisting of two cells gives the purification factor of ¹⁷⁷Lu from ytterbium at a level of 10⁵–10⁶, which allows using ¹⁷⁷Lu of such quality for labeling bioorganic molecules.     

Flexible polyvinyl chloride neutron guides for transporting ultracold and very cold neutrons

The transmission of ultracold neutrons (UCNs) through flexible polyvinyl chloride (PVC) tubes with lengths of up to 3 m and an internal diameter of 6–8 mm has been studied. High UCN transmission is found even for arbitrarily bent tubes (single bend, double bend, triple bend, figure eight, etc.). The transmission can be improved significantly by coating the inner surface of the tube with a thin layer of liquid fluorine polymer. The prospects of these neutron guides in fundamental and applied research are discussed.