Alternating copolymerization of carbon dioxide and propylene oxide by single-component cobalt salen complexes with various axial group

A series of single-component cobalt salen complexes, N,N'-bis(salicylidene)-1,2phenylenediamino cobaltIII X(X = Cl (1a), Br (1b), NO3 (1c), CF3COO (1d), BF4 (le), and N3 (If)) (SalphCoX), were prepared for alternating copolymerization of carbon dioxide and propylene oxide(PO) under mild condition. The axial anion X group of the SalenphCoX played important role in tailoring the catalytic activity, polymeric/cyclic carbonate selectivity, as well as stereochemistry of carbonate unit sequence in the polymer chain. SalenphCoX with an electron-withdrawing axial X group (complex 1c) was an ideal catalyst for the copolymerization of CO2 and PO to selectively produce polycarbonate with similar to 99% carbonate linkage and over 81% head-to-tail structure.

(R,R)-DPEN-modified Ru/gamma-Al2O3 - An efficient heterogeneous catalyst for enantioselective hydrogenation of acetophenone

An efficient enantioselective catalyst of 5 wt.% Ru/-gamma-Al2O3 modified with R,R-1,2-diphenylethylene-diamine ((R,R)-DPEN) for the hydrogenation of a non-activated aromatic ketone of acetophenone has been investigated, a relatively high enantiomeric excess (ee) of 60.5% was obtained at both the conversion and selectivity larger than 99%, it was about three times higher than the ee values reported up to now for acetophenone hydrogenation with the supported transition metal catalysts modified by chiral reagents. The influences of some reaction parameters such as phosphine ligand, substrate/catalyst/modifier molar ratios, base, solvent, pressure and reaction temperature have been discussed. The chiral modifier of (R,R)-DPEN was very important in controlling the enantioselectivity through adsorption competing with other substrates on the surface of active metal species. The phosphine ligand and base were also important and indispensable in the present reaction.

Mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and a catalyst in catalytic degradation of polyethylene

The possibility of mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and catalyst for polyethylene (PE) catalytic degradation was investigated. Here, HMCM- 41 and AIMCM-41, and mesoporous silicoaluminophosphate molecular sieves (SAPO1 and SAPO2) were synthesized and used as acid solid. Much more gases were produced during catalytic degradation in PE/acid solid mixtures via in situ polymerization than those via physical mixing. The particle size distribution results exhibited that the particle size of SAPO1 in the PE/SAPO1 mixture via in situ polymerization was about 1/14 times of that of the original SAPO1 or SAPO1-supported metallocene catalyst. This work shows a novel technology for chemical recycling of polyolefin.

A novel route to polyethylene-polystyrene blends through the fragmentation of porous polystyrene beads supported metallocene in ethylene polymerization

Polyethylene-polystyrene blends were synthesized by in situ ethylene polymerization with polystyrene porous beads supported metallocene; the influence of fragmenting support beads on the morphology and the mechanical performance of the blends was investigated.

The synthesis and catalytic activity of poly(bis(imino)pyridyl) iron(II) metallodendrimer

The first and second generation carbosilane dendrimers with silicon hydride terminated were synthesized, and then reacted with bis(imino)pyridyl containing allyl [4-CH2==CHCH2-2,6-(Pr2C6H3N)-Pr-i==CMe(C5H3N)MeC==N(2,6-'Pr2C6H3)], in the presence of H2PtCl6 as a hydrosilylation catalyst, to afford the first and second generation carbosilane supported ligands. Complexation reactions with FeCl(2)(.)4H(2)O give rise to iron-containing carbosilane dendrimers with FeCl2 moieties bound on the periphery. The metallodendrimers were used as catalyst precursors, activated with modified methylaluminoxane, for the polymerization of ethylene. In the case of low Al/Fe molar ratio, the metallodendrimers display much higher catalytic activity towards ethylene polymerization and produce much higher molecule weight polyethylenes than the corresponding single-nuclear complex under the same conditions.

Structure and catalytic properties of magnesia-supported copper salts of molybdovanadophosphoric acid

The structure and stability of magnesia-supported copper salts of molybdovanadophosphoric acid (Cu2PMo11VO40) were characterized by different techniques. The catalyst was prepared in ethanol by impregnation because this solvent does not hurt texture of the water-sensitive MgO and Cu2PMo11VO40. The Keggin-type structure compound may be degraded partially to form oligomerized polyoxometalate when supported on MgO. However, the oligomers can rebuild as the Keggin structure again after thermal treatment in air or during the reaction. Meanwhile, the V atoms migrate out of the Keggin structure to form a lacunary structure, as observed by Fourier transform IR spectroscopy. Moreover, the presence of Cu2+ as a countercation showed an affirmative influence on the migration of V atoms, and the active sites derived from the lacunary species generated after release of V from the Keggin anion. The electron paramagnetic resonance data imply that V5+ autoreduces to V4+ in the fresh catalyst, and during the catalytic reaction a large number of V4+ ions are produced, which enhance the formation of O2- vacancies around the metal atoms. These oxygen vacancies may also improve the reoxidation function of the catalyst. This behavior is correlated to higher catalytic properties of this catalyst. The oxidative dehydrogenation of hexanol to hexanal was studied over this catalyst.

Electrooxidation of methanol on carbon nanotubes supported Pt-Fe alloy electrode

The synthesis and characterization of catalysts based on bimetallic materials, Pt-Fe supported on multi-walled carbon nanotubes (MWNTs) for methanol electrooxidation is reported here. The catalyst was prepared by a spray-cooling process and characterized by TEM, EDS, ICP and XRD. The electrocatalytic properties of the Pt-Fe/MWNTs electrode for methanol oxidation have been investigated by cyclic voltammetry and chronoamperometry. It presented higher electrocatalytic activity and stability than a comparative Pt/ MWNTs catalyst. This may be attributed to the addition of Fe which leads to the small average particle size and high utilization of Pt in the Pt-Fe/MWNTs catalyst. The results imply that the Pt Fe/MWNTs composite has good potential applications in fuel cells.

Developments and applications of supported liquid phase catalysts

Supported liquid phase catalyst (SLPC) is one of effectively heterogenized homogeneous catalysts using organometallic complexes as active components, which are dissolved in a small quantity of liquid phase dispersed in the form of isle or film on the surface of supports. The SLPC has successfully been applied for several chemical transformations and this article will review recent results with respect to the preparation and catalytic performance, the applicability to continuous flow operations, and the capability of multifunctional catalysis.

Room temperature preparation of carbon supported Pt-Ru catalysts

A carbon supported Pt-Ru (Pt-Ru/C-T) catalyst can be prepared by a chemical reduction method in an aqueous solution with tetrahydrofuran (THF) at room temperature. The Pt-Ru particles possess high alloying, small average size and a low relative crystallinity. The electrocatalytic activity of the prepared Pt-Ru/C catalyst for methanol oxidation is much higher than that of commercial Pt-Ru/C (Pt-Ru/C-E) catalysts which have a similar average size and relative crystallinity, but the alloying extent is much lower than that in our Pt-Ru/C-T catalyst. The results illustrate that the alloying extent of Pt and Ru in the Pt-Ru/C catalyst plays an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for methanol oxidation.

Surface-appropriate lipophobicity - Application in isobutene oligomerization over Teflon-modified silica-supported 12-silicotungstic acid

A series of silica-supported 12-silicotungstic acid catalysts (H4SiW12O40, abbreviated as HSiW), modified with various loadings of Teflon (HSiW/SiO2-Teflon), were prepared by an impregnation method. The surface properties of the catalysts were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), BET, infrared (IR) spectroscopy, NH3-TPD and the Drop Shape Analysis (DSA). SEM results combined with energy-dispersive X-ray (EDX) measurements of HSiW/SiO2-Teflon revealed that F-compound (Teflon) is effectively coated on the catalyst surface. The contact angles for water and oil of 50 wt% HSiW/SiO2 and HSiW/SiO2-Teflon indicate that HSiW/SiO2-Teflon catalyst enhances not only the surface hydrophobicity but also the surface lipophobicity by means of the addition of Teflon. Silica-supported 12-silicotungstic acid modified with Teflon exhibits higher C-8(=) selectivity and longer lifetime than that of silica-supported 12-silicotungstic acid in isobutene oligomerization. Thus, surface-appropriate lipophobicity of catalysts may be effective for decreasing the interaction between coke precursors and the catalyst surface and for removing deposited coke more easily.

PEG-supported dipyridyl ligand for palladium-catalyzed Suzuki and Suzuki-type reactions in PEG and aqueous media

An air- and water-stable PEG-supported bidentate nitrogen ligand is prepared and its applications in the palladium-catalyzed Suzuki reaction of aryl halides with arylboronic acids in PEG and Suzuki-type reaction of aryl halides with sodium tetraphenylborate in aqueous media are reported. The homogeneous catalyst system is environmentally friendly and offers the advantages of high activity, reusability and easy separation.

Preparation of functionalized montmorillonites and their application in supported zirconocene catalysts for ethylene polymerization

Ethylene polymerization was carried out with zirconocene catalysts supported on montmorillonite (or functionalized montmorillonite). The functionalized montmorillonite was from simple ion exchange of [CH3O2CCH2NH3](+) (MeGlyH(+)) ions with interlamellar cations of layered montmorillonites. The functionalized montmorillonlites [high-purity montmorillonite (MMT)-MeGlyH(+)] had larger interlayer spacing (12.69 Angstrom) than montmorillonites without treatment (9.65 Angstrom). The zirconocene catalyst system [Cp2ZrCl2/methylaluminoxane (MAO)/MMT-MeGlyH(+)] had much higher Zr loading and higher activities than those of' other zirconocene catalyst systems (Cp2ZrCl2/MMT, Cp2ZrCl2/MMT-MeGlyH(+), Cp2ZrCl2/MAO/MMT, [CP2ZrCl](+)[BF4]/MMT, [Cp2ZrCl][BF4](-)/MMT-MeGlyH(+), [CP2ZrCl](+)[BF4](-)/MAO/MMT-MeGlyH(+), and [Cp2ZrCl](+)[BF4](-)/MAO/MMT). The polyethylenes with good bulk density were obtained from the catalyst systems, particularly (CP2ZrCl2/MAO/MMT-MeGlyH(1)). MeGlyH(+) and MAO seemed to play important roles for preparation of the supported zirconocenes and polymerization of ethylene. The difference in Zr loading and catalytic activity among the supported zirconocene catalysts is discussed.

C-13 NMR study of ethylene/propylene/octene-1 terpolymers synthesized with TiCl4/MgCl2/i-Bu3Al as the catalyst

The theory of chemical shift effect of substituent was applied to the assignment of the C-13 NMR spectra of the ethylene/propylene and ethylene/octene-1 copolymers. Using the parameters derived above and the DEFT technique, we then entirely assigned the C-13 NMR spectra of the ethylene/propylene/octene(-1) terpolymers synthesized in the presence of the same heterogeneous supported Ziegler-Natta catalyst, TiCl4/MgCl2/i-Bu3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene-1 terpolymers.

Renewable manganous hexacyanoferrate-modified graphite organosilicate composite electrode and its electrocatalytic oxidation of L-cysteine

Manganous hexacyanoferrate (MnHCF) supported on graphite powder was dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite, which was used as electrode material to construct a renewable three-dimensional MnHCF-modifed electrode. MnHCF acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. Cyclic voltammetry was exploited to investigate the dependence of electrochemical behavior on supporting electrolytes containing various cations. The chemically modified electrode can electrocatalytically oxidize L-cysteine, and exhibits a distinct advantage of polishing in the event of surface fouling, as well as simple preparation, good chemical and mechanical stability, and good repeatability of surface renewal.

A novel catalyst for clean production of diphenols - Ferric trisacetylacetonate MCM-41

Ferric trisacetylacetonate has been deposited within the zeolite MCM-41 and the product characterized by XRD and IR. In water at pH 7 it catalyzes the oxidation of phenol by H2O2, giving 58% conversion in 1 h at 50 degrees C: products are catechol (66%), hydroquinone (27%) and benzoquinone (7%). Other oxidants and solvents are much less effective. UV-VIS spectra suggest a radical substitution mechanism, and a pollution-free process for phenol hydroxylation is now possible.