Template-assisted syntheses of two novel porous zirconium methylphosphonates

Two porous zirconium methylphosphonates (designated as ZMPmi and ZMPme respectively) were synthesized by using dibutyl methylphosphonate (DBMP) as a template. Two efficient post-synthetic treatments were developed to remove the incorporated template without destroying the hybrid structures. The materials were characterized by SEM, EPMA, TG, DTA, FTIR, and NMR. Specific surface area and porosity were evaluated by BET, alpha(s)-plots and DFT methods based on N-2 adsorption-desorption isotherms. The specific surface areas of ZMPmi and ZMPme are determined to be 279 and 403 m(2) g(-1) and the maxima of pore size distributions are at 0.7 and 1.3 nm respectively. (c) 2005 Elsevier Inc. All rights reserved.

Hydrothermal synthesis and characterization of microporous crystals of trivalent metal-containing zirconium phosphates

Two organically templated trivalent metal-containing crystalline zirconium phosphate materials FeZrPO-8 and AlZrPO-8 have been prepared hydrothermally by using fluoride as a mineralizer, and 1,6-diaminohexane (DAH) as templates. The powder XRD patterns indicate that the as-synthesized products are new materials. Substitutions of Al3+ or Fe3+ into Zr4+ sites were confirmed by a combination of powder X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) studies. The thermal behavior of the title compounds have been investigated using TG-DTA and X-ray thermodiffractometry, which indicated that the inorganic framework of the compounds are thermally stable up to similar to400 degreesC. (C) 2004 Elsevier B.V. All rights reserved.

Preparation of palladium membrane over porous stainless steel tube modified with zirconium oxide

A palladium membrane has been prepared by electroless plating on the surface of a porous stainless steel tube. Since the large surface pores of the tube are obstacle for preparation of a defect-free palladium film on the surface, zirconium oxide particles were deposited inside the pores. The mean thickness of the resulting Pd membrane on the modified tube was ca. 10 mum. It is suggested that the permeability of hydrogen is partly governed by gas diffusion in the pores. (C) 2004 Elsevier B.V. All rights reserved.

Dimerization of 1-butene via zirconium-based Ziegler-Natta catalyst

A zirconium-based Ziegler-Natta catalytic system has been tested in the dimerization of 1-butene. It was found that the concentration of Et2AlCl, Ph3P and PhONa as well as the reaction temperature had great influences on the activity and selectivity of the catalyst. Under the optimum reaction conditions, the conversion of 1-butene is 91.9%, and the selectivity of dimers is 76.7%. Basic ligands such as Ph3P and PhONa can inhibit isomerization of 1-butene to 2-butene effectively. In addition, the metal hydride mechanism was also suggested and some indirect evidence was obtained in favor of this mechanism.

Thermal barrier coating of lanthanum-zirconium-cerium composite oxide made by electron beam-physical vapor deposition

Lanthanum-zirconium-cerium composite oxide (La-2(Zr0.7Ce0.3)(2)O-7, LZ7C3) as a candidate material for thermal barrier coatings (TBCs) was prepared by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, thermophysical properties, surface and cross-sectional morphologies and cyclic oxidation behavior of the LZ7C3 coating were studied. The results indicated that LZ7C3 has a high phase stability between 298 K and 1573 K, and its linear thermal expansion coefficient (TEC) is similar to that of zirconia containing 8 wt% yttria (8YSZ). The thermal conductivity of LZ7C3 is 0.87 W m(-1) K-1 at 1273 K, which is almost 60% lower than that of 8YSZ. The deviation of coating composition from the ingot can be overcome by the addition of excess CeO2 and ZrO2 during ingot preparation or by adjusting the process parameters.

Synthesis of Titanate-Based Nanotubes for One-Dimensionally Confined Electrical Properties

Structural tailoring for dimensionally confined electrical properties is fundamentally important for nanodevices and the relevant technologies. Titanate-based nanotubes were taken as a prototype one-dimensional material to study. First, Na0.96H1.04Ti3O7 center dot 3.42H(2)O nanotubes were prepared by a simple hydrothermal condition, which converted into Na0.036H1.964Ti3O7 center dot 3.52H(2)O nanotubes by a subsequent acidic rinsing. Systematic sample characterization using combined techniques of X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy, electron paramagnetic resonance, Fourier transform infrared spectroscopy, elemental analyses, and alternative current impedance indicated that both nanotubes possessed a scrolled trititanate-type structure with the (200) crystal face predominant on the tube surface. With increasing temperature, both nanotubes underwent a continuous dehydration process, which however imposed different impacts oil the structures and electrical properties, depending on the types of the nanotubes

Self-immobilized titanium and zirconium catalysts with phenoxy-imine ligands for ethylene polymerization. X-ray crystal structure of bis(N-(3-tert-butylsalicylidene)-4 '-allyloxyanilinato) zirconium(IV) dichloride

Four self-immobilized FI catalysts with allyl substituted phenoxy-imine ligands [{4-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2) MCl2] (1: M = Ti: 2: M = Zr), [{3-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2)MCl2] (3: M = Zr), [{4-(CH2=CHCH2-2,6-(iso-C3H7)(2))C6H5N=CH-C6H3(3,5-(NO2)(2))O}(2)MCl2] (4: M = Zr) have been synthesized and characterized. The molecular structure of 2 has been determined by X-ray crystallographic analysis. The results of ethylene polymerization showed that the self-immobilized titanium (IV) and zirconium (IV) catalysts 1-3 kept high activity for ethylene polymerization and 4 showed no activity. SEM showed the immobilization effect could greatly improve the morphology of polymer particles to afford micron-granula polyolefin as supported catalysts.

Syntheses and characterization of half-sandwich zirconium complexes with dichalcogenolate o-carborane ligands

Metallocene complex (Cp2ZrCl2)-Zr-tt (Cp-tt = eta(5)-1,3-(Bu2C5H3)-Bu-t) (1) has been prepared from the reaction of LiCptt with ZrCl4 in good yield. Reactions of 1 with dilithium dichalcogenolate o-carboranes afforded new type of half-sandwich compounds with dichalcogenolate o-carboranyl ligands [Li(THF)(4)][(CpZr)-Zr-tt(E2C2B10H10)(2)] (E = S, 2a; E = Se, 2b) in which only one cyclopentadienyl ring ligand existed. Complexes 1 and 2a were structurally characterized by X-ray analyses. In complex 2a, the Zr(IV) ion is eta(5)-bound to one 1,3-di-tert-cyclopentadienyl ring and a-bound to four mu(2)-sulfur atoms of two dithio-carboranes. The zirconium atom and four sulfur atoms form a distorted pyramid. The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur atoms and the fulcrum at the zirconium atom.

Enhanced thermal stability of zinc-based titanate (dielectric) ceramics prepared by the modified sol-gel route

A multi-component substitution of Co and Ni was incorporated into ZnTiO3 to form pure hexagonal Zn1-x(Co1/2Ni1/2)xTiO(3) (x = 0,0.8,0.9,1.0) dielectric ceramic powders by a modified sol-gel route, following heat treatments at 600 degrees C for 3 h and at 800 degrees C for 6 h. Differential scanning calorimetry measurements revealed that the order of increasing thermal stability of solid solution compound Zn1-x(Co1/2Ni1/2)(x)TiO3 was ZnTiO3 (945 degrees C), Zn0.1Ni0.9TiO3 (1346 degrees C), Zn-0.1(Co1/2Ni1/2)(0.9)TiO3 (1390 degrees C), and Zn0.1Co0.9TiO3 (> 1400 degrees C). Both the dielectric constant and loss tangent reached a maximum at x = 0.8 and then decreased with solubility, x, and measurement frequency.

Titanium and zirconium complexes with aminoiminophosphorane ligands

A series of titanium and zirconium complexes based on aminoiminophosphorane ligands [Ph2P(Nt-Bu)(NR)](2)MCl2 (4, M = Ti, R = Ph; 5, M = Zr, R = Ph; 6, M = Ti, R = SiMe3; 7, M = Zr, R = SiMe3) have been synthesized by the reaction of the ligands with TiCl4 and ZrCl4. The structure of complex 4 has been determined by X-ray crystallography. The observed very weak interaction between Ti and P suggests partial pi-electron delocalization through both Ti and P. The complexes 4-7 are inactive for ethylene polymerization in the presence of modified methylaluminoxane (MMAO) or i-Bu3Al-Ph3CB(C6F5)(4) under atmospheric pressure, and is probably the result of low monomer ethylene concentration and steric congestion around the central metal.

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalted alpha-zirconium phosphate micro particles

Methylene blue-intercalated a-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V (vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1 x 10(-6)-4 x 10(-3) mol L-1 and 1.5 x 10(-7) mol L-1, respectively.

Carbon ceramic electrodes modified with sub-micron particles of new methylene blue (NMB) intercalated alpha-zirconium phosphate

New methylene blue-intercalated a-zirconium phosphate (NMBZrP) was synthesized in the presence of n-butylamine and characterized by powder XRD, FTIR, TEM and elemental analysis. Sub-micron particles of NMBZrP in deionized water were apt to deposit onto the surface of graphite powder to yield graphite powder-supported NMBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing new methylene blue. Cyclic voltammetric studies revealed that peak currents of the NMBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled. at high scan rates. In addition, NMBZrP immobilized in a carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution in the pH range from 0.52 to 3.95.