Synthesis and characterization of polyethylene/clay-silica nanocomposites: A montmorillonite/silica-hybrid-supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT-Si) supported catalyst, was developed. MT-Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT-Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay-silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system.

Silica coated noble metal nanoparticle hydrosols as supported catalyst precursors

Synthesis of well-defined nanoparticles has been intensively pursued not only for their fundamental scientific interest, but also for many technological applications. One important development of the nanomaterial is in the area of chemical catalysis. We have now developed a new aqueous-based method for the synthesis of silica encapsulated noble metal nanoparticles in controlled dimensions. Thus, colloid stable silica encapsulated similar to 5 nm platinum nanoparticle is synthesized by a multi-step method. The thickness of the silica coating could be controlled using a different amount of silica precursor. These particles supported on a high surface area alumina are also demonstrated to display a superior hydrogenation activity and stability against metal sintering after thermal activation.

Ethylene polymerization with porous polystyrene spheres supported Cp2ZrCl2 catalyst

A catalyst with porous polystyrene beads supported Cp2ZrCl2 was prepared and tested for ethylene polymerization with methylaluminoxane as a cocatalyst. By comparison, the porous supported catalyst maintained higher activity and produced polyethylene with better morphology than its corresponding solid supported catalyst. The differences between activities of the catalysts and morphologies of the products were reasonably explained by the fragmentation processes of support as frequently observed with the inorganic supported Ziegler-Natta catalysts. Investigation into the distribution of polystyrene in the polyethylene revealed the fact that the porous polystyrene supported catalyst had undergone fragmentation during polymerization.

Preparation of poly (styrene-co-4-vinyl pyridine) /silica nanoscale hybrids supported cyclopentadienyltitanium trichloride (CpTiCl3) catalyst and styrene polymerization

To obtain a novel support with practical value for metallocene catalyst (eta -C5H5)TiCl3 (CpTiCl3), poly (styrene-co-4-vinylpyridine) /SiO2 nanoscale hybrid material (SrP/SiO2) was firstly produced as support. After pretreatment by methylaluminoxane (MAO), the hybrid materials reacted with CpTiCl3. The results from SAXS, SEM and TEM indicated the morphology and structure of organic/inorganic hybrid materials, and the size of inorganic particle in hybrid was nanoscale. The results from IR and XPS showed that there were two possible cationic active species in the hybrid-supported catalyst, the polymerization results of styrene proved this possibility.

Preparation and application of a novel core-shell-particle-supported zirconocene catalyst

The use of functional groups bearing silica/poly(styrene-co-4-vinylpyridine) core-shell particles as a support for a zirconocene catalyst in ethylene polymerization was studied. Several factors affecting the behavior of the supported catalyst and the properties of the resulting polymer, such as time, temperature, Al/N (molar ratio), and Al/Zr (molar ratio), were examined. The conditions of the supported catalyst preparation were more important than those of the ethylene polymerization. The state of the supported catalyst itself played a decisive role in both the catalytic behavior of the supported catalyst and the properties of polyethylene (PE). IR and X-ray photoelectron spectroscopy were used to follow the formation of the supports. The formation of cationic active species is hypothesized, and the performance of the core-shell-particle-supported zirconocene catalyst is discussed as well. The bulk density of the PE formed was higher than that of the polymer obtained from homogeneous and polymer-supported Cp2ZrCl2/methylaluminoxane catalyst systems. (C) 2001 John Wiley & Sons, Inc.

Physical and electrochemical evaluation of ATO supported IrO2 catalyst for proton exchange membrane water electrolyser

Antimony doped tin oxide (ATO) was studied as a support material for IrO₂ in proton exchange membrane water electrolyser (PEMWE). Adams fusion method was used to prepare the IrO₂-ATO catalysts. The physical and electrochemical characterisation of the catalysts were carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder conductivity, cyclic voltammetry (CV) and membrane electrode assembly (MEA) polarisation. The BET surface area and electronic conductivity of the supported catalysts were found to be predominantly arisen from the IrO₂. Supported catalyst showed higher active surface area than the pristine IrO₂ in CV analysis with 85% H₃PO₄ as electrolyte. The MEA performance using Nafion®−115 membrane at 80 °C and atmospheric pressure showed a better performance for IrO₂ loading ≥60 wt.% than the pristine IrO₂ with a normalised current density of 1625 mA cm⁻² @1.8 V for the 60% IrO₂-ATO compared to 1341 mA cm⁻² for the pristine IrO₂ under the same condition. The higher performance of the supported catalysts was mainly attributed to better dispersion of active IrO₂ on electrochemically inactive ATO support material, forming smaller IrO₂ crystallites. A 40 wt.% reduction in the IrO₂ was achieved by utilising the support material.

The design and synthesis of a true, heterogeneous, asymmetric catalyst

This work describes the design and synthesis of a true, heterogeneous, asymmetric catalyst. The catalyst consists of a thin film that resides on a high-surface- area hydrophilic solid and is composed of a chiral, hydrophilic organometallic complex dissolved in ethylene glycol. Reactions of prochiral organic reactants take place predominantly at the ethylene glycol-bulk organic interface.

The synthesis of this new heterogeneous catalyst is accomplished in a series of designed steps. A novel, water-soluble, tetrasulfonated 2,2'-bis (diphenylphosphino)-1,1'-binaphthyl (BINAP-4S0_3Na) is synthesized by direct sulfonation of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP). The rhodium (I) complex of BINAP-4SO_3Na is prepared and is shown to be the first homogeneous catalyst to perform asymmetric reductions of prochiral 2-acetamidoacrylic acids in neat water with enantioselectivities as high as those obtained in non-aqueous solvents. The ruthenium (II) complex, [Ru(BINAP-4SO_3Na)(benzene)Cl]Cl is also synthesized and exhibits a broader substrate specificity as well as higher enantioselectivities for the homogeneous asymmetric reduction of prochiral 2-acylamino acid precursors in water. Aquation of the ruthenium-chloro bond in water is found to be detrimental to the enantioselectivity with some substrates. Replacement of water by ethylene glycol results in the same high e.e's as those found in neat methanol. The ruthenium complex is impregnated onto a controlled pore-size glass CPG-240 by the incipient wetness technique. Anhydrous ethylene glycol is used as the immobilizing agent in this heterogeneous catalyst, and a non-polar 1:1 mixture of chloroform and cyclohexane is employed as the organic phase.

Asymmetric reduction of 2-(6'-methoxy-2'-naphthyl)acrylic acid to the non-steroidal anti-inflammatory agent, naproxen, is accomplished with this heterogeneous catalyst at a third of the rate observed in homogeneous solution with an e.e. of 96% at a reaction temperature of 3°C and 1,400 psig of hydrogen. No leaching of the ruthenium complex into the bulk organic phase is found at a detection limit of 32 ppb. Recycling of the catalyst is possible without any loss in enantioselectivity. Long-term stability of this new heterogeneous catalyst is proven by a self-assembly test. That is, under the reaction conditions, the individual components of the present catalytic system self-assemble into the supported-catalyst configuration.

The strategies outlined here for the design and synthesis of this new heterogeneous catalyst are general, and can hopefully be applied to the development of other heterogeneous, asymmetric catalysts.

Performance improvement in direct methanol fuel cell cathode using high mesoporous area catalyst support

Black Pearls 2000 (designated as BP- 2000) and Vulcan XC-72 (designated as XC-72) carbon blacks were chosen as supports to prepare 40 wt % (the targeted value) Pt/C catalysts by a modified polyol process. The carbon blacks were characterized by N-2 adsorption and Fourier tranform infrared spectroscopy. The prepared catalysts were characterized by inductively coupled plasma atomic emission spectroscopy, transmission electron microscopy, scanning electron microscopy (SEM), in situ cyclic voltammetry, and current-voltage curves. On BP- 2000, Pt nanoparticles were larger in size and more unevenly distributed than on XC-72. It was observed by SEM that the corresponding catalyst layer on BP- 2000 was thicker than that of XC-72 based catalyst at almost the identical catalyst loading. And the BP- 2000 supported catalyst gave a better single cell performance at high current densities. These results suggest that the performance improvement is due to the enhanced oxygen diffusion and water removal capability when BP- 2000 is used as cathode catalyst support. (C) 2004 The Electrochemical Society.

Immobilization of dipyridyl complex to magnetic nanoparticle via click chemistry as a recyclable catalyst for Suzuki cross-coupling reactions

A magnetic nanoparticle (MNP)-supported di(2-pyridyl)methanol palladium dichloride complex was prepared via click chemistry. The MNP-supported catalyst was evaluated in Suzuki coupling reaction in term of activity and recyclability in DMF. It was found to be highly efficient for Suzuki coupling reaction using aryl bromides as substrates and could be easily separated by an external magnet and reused in five consecutive runs without obvious loss of activity.

Zirconocene catalyst well spaced inside modified montmorillonite for ethylene polymerization: role of pretreatment and modification of montmorillonite in tailoring polymer properties

Zirconocene catalyst was heterogenized inside an organosilane-modified montmorillonite (MMT) pretreated by calcination and acidization, for supported catalyst systems with well-spaced alpha-olefin polymerization active centers. The varied pretreatment and modification conditions of montmorillonite are efficient for supported zirconocene catalysts in control of polyethylene microstructures, in particular, molecular weight distribution. In contrast to other supported catalyst systems, Cp2ZrCl2/modified montmorillonite(MMT-7)-supported catalysts with a distinct interlayer structure catalyzed ethylene homopolymerization and copolymerization with I-octene activated by methylaluminoxane (MAO), resulting in polymers with a bimodal molecular weight distribution (MWD).

Liquid-phase hydrogenation of furfural to tetrahydrofurfuryl alcohol catalyzed by polymer resin supported palladium catalysts

Three kinds of polymer resin supported Pd catalysts were prepared by mixing PdCl2, with alkaline styrene anion exchange resins[D392 -NH2, D382, -NHCH3, D301R, -NH(CH3)(2)], strongly alkaline styrene anion exchanged resin [201 X 7DVB, -NH+ (CH3)(3)] and alkaline epoxy exchange resin (701, -NH2), and hydrogenating in liquid phase at 1.013 X 10(5) Pa. The hydrogenation of furfural was studied under the reaction conditions such as solvent, temperature. Pd content in the supported catalyst and the amount of the catalyst. The yield of hydrogenation reaction of furfural markedly increased to 100% and the selectivity to tetrahydrofurfuryl alcohol increased to over 98% by polymer (alkaline styrene anion exchange resins D392, -NH2, D382, -NHCH3) supported palladium catalysts comparing with the yield over 70% and selectivity over 97% by palladium catalyst, in 50% alcohol-50% water or pure water solution at 1.013 X 10(5) Pa. The relationship between hydrogenation and the structures of functional group in the supporting resin was examined by XPS method.

Preparation of polymer-supported zirconocene catalysts and olefin polymerization

A novel polymer-supported metallocene catalyst with crosslinked poly(styrene-co-acrylamide) (PSAm) as the support has been prepared and characterized. The probability of long sequences of acrylamide (Am) in PSAm is still low even at an Am amount of 32.8 mol %, implying the relatively homogeneous distribution of Am. The infrared spectra of PSAm and the supported catalyst substantiate that an amide group in PSAm coordinates with methylaluminoxane through both oxygen and nitrogen atoms. Ethylene/alpha-octene copolymerization showed that the catalytic activity is not markedly affected by adding alpha-octene. C-13 NMR analysis of the ethylene/alpha-octene copolymer indicated that the composition distribution of the copolymer is uniform. (C) 1999 John Wiley & Sons, Inc.