New technology for selective catalytic oxidation of ammonia to nitrogen

The selective catalytic oxidation (SCO) of ammonia to N₂ was studied by using a series of noble metal-V₂O₅-WO₃ catalysts supported on titania-silica (TS) prepared by coprecipitation method. In the V₂O₅-WO₃ catalyst system, the use of TS as a support was very effective to enhance catalytic activity compared with TiO₂ or SiO₂ alone. The addition of a slight amount of Pd and Ir to V₂O₅-WO₃/TS catalyst caused also remarkable enhancement of the catalytic activity without decreasing the selectivity to N₂. The present catalysts provide remarkably high catalytic performance for SCO of ammonia to N₂ under the practical reaction conditions for an industrial application.     

Effects of electrolytes on the configuration change of cobalt(II)-halide complexes in chloroform/water reverse micelle systems.

The effects of various salts and HClO4 on the configuration change of cobalt(II)-halide complexes in CHCl3/CTAC or CTAB/H2O reverse micelle systems were examined at 25 degrees C by means of spectrophotometry, where CTAC and CTAB represent cetyltrimethylammonium chloride and bromide, respectively. The formation of the [CoCl4]> or [CoBr4]2- species of the tetrahedral configuration from [Co(H2O)6]2+ of the octahedral configuration in the reverse micelles was greatly promoted not only by a decrease in the W value (W = [H2O]/[surfactant]), but also, at a constant W value (e.g., W = 2.0), by the addition of relatively low concentrations of salts or the acid (e.g., 4.0 mol dm(-3) in the aqueous phase or 4.0 x 10(-2) mol dm(-3) in the whole reverse micelle system). The effects of perchlorate salts increased as Na+ < or = Li+ approximately H+ < Sr2+ < Ca2+ < Mg2+. Non-metallic salts, various tetraalkylammonium (R4N+) salts at lower concentrations, gave minor effects. The enhanced effects of metal salts on the configuration change of the cobalt(II)-halide complexes were interpreted by a further distortion of the hydrogen-bonded structure of the water in a "water pool" in the presence of salts of even relatively low concentrations. A conformation change with increasing temperature was also attributed to a further distortion of the water structure. An almost completed formation of [CoBr4]2- as well as [CoCl4]2- was attained in the reverse micelles at a low W value of 0.69 containing LiClO4 or HClO4. A partial transfer of the [CoX4]2- species from a "water pool" into the CHCl3 phase by the addition of the metal salts may be suspected. An examination of cobalt(II)-bromide complexes in dichloromethane/CTAB/H2O at W = 1.3 - 5.55 justified all the arguments concerning the chloroform systems. The Raman spectra of D2O containing concentrated LiBr and LiClO4 have supplied conclusive evidence that the hydrogen-bonded structure of the bulk water is completely distorted by extremely concentrated salts.     

Solvent effect on protein binding by polymer brush grafted onto porous membranes

An epoxy-group-containing polymer chain was grafted onto the hollow-fiber form of a porous polyethylene membrane by the immersion of the electron beam-irradiated trunk polymer in glycidyl methacrylate diluted with methanol and 1-butanol. The epoxy group density ranged from 8.5 to 13.4 mol per kg of the trunk polymer. Subsequently, the epoxy groups produced were converted into sulfonic acid and diethylamino groups. The density of -SOH and -N(C2H5), groups was 0.40 and 2.2 mol per kg of the product. respectively. The polymer brush, defined as a polymer chain extending from the surface of a pore toward the interior of the pore, was evaluated from the determination of an equilibrium binding capacity of hen egg lysozyme (HEL) and bovine serum albumin (BSA). The polymer brush prepared in 1-butanol was found to be longer than that prepared in methanol from the determinations of liquid permeability and protein adsorptivity. The proteins were bound to the polymer brush prepared in 1-butanol, followed by the functionalization, at higher degrees of multilayer binding: about 30 for HEL and 6 for BSA.     

Synthesis of Ultrafine SiC Powders from Carbon-Silica Hybridized Precursors with Carbothermic Reduction

Inorganic-organic hybrid gels were prepared by simultaneous condensation of the liquid mixture of ethyl silicate, ethyl borate and water soluble phenol resin with low molecular weight. The liquid mixtures were changed into lightly colored transparent gels after a catalyst addition and stirring. The obtained gels were crushed, dried and fired in controlled conditions to yield the inorganic precursors. Since the tailored inorganic precursors mainly consisted of SiO2 and carbon, silicon carbide was formed with the heat treatments in an Ar atmosphere beyond 1773 K with carbothermic reduction. The properties and morphology of the formed silicon carbide powders in terms of the starting precursor compositions and the conditions of the carbothermic reduction were investigated with SEM, XRD and TG-DTA analysis.     

Syntheses, crystal structures and properties of novel zinc(II) complexes obtained by reactions of zinc(II) malonate with flexible multidentate ligands

Complex [Zn₂(bimb)₂(mal)₂(H₂O)₂]·4H₂O (1) (mal=⁻OCOCH₂COO⁻) was obtained by reaction of bidentate ligand 4,4′-bis(imidazole-1-ylmethyl)biphenyl (bimb) with zinc(II) salt of malonate, while the reaction of the same metal salt with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) gives another novel complex [Zn₂(titmb)₂(mal)][mal]·12H₂O (2). The structures of these complexes were determined by X-ray crystallography. The results revealed that 1 is a cyclic dinuclear complex in which the malonate groups act as terminators and prevent further aggregation, while 2 is a 2D honeycomb network in which each independent 2D sheet contains two sub-layers bridged by the malonate groups and complex 2 also contains free malonate as a counteranion connected to the 2D layer by C-H?O hydrogen bonds. The entirely different structure and topology of complexes 1 and 2, on the one hand, indicates that the nature of organic ligands affected the structures of assemblies greatly, and on the other, reveals the versatility of the malonate which can act as a bridging and/or blocking ligand.     

Effects of metal salts on polymerization. Part VII. Radical polymerization and spectra of vinylpyridine in the presence of cobaltous chloride

The radical polymerizability of vinylpyridines in the presence of cobaltous chloride was studied in DMF solution, and the results were correlated with the spectroscopic data obtained for methanol solution. In general, the behavior of vinylpyridine complexed with cobaltous chloride is qualitatively the same as that of zinc complexes reported previously. The rates of polymerization were enhanced by the addition of cobaltous chloride when 4-vinylpyridine(4-VP) or 2-methyl-5-vinylpyridine(MVP) was the monomer, whereas the polymerization of 2-vinylpyridine(2-VP) was retarded by cobaltous chloride. The monomer reactivity of all the vinylpyridines was also enhanced by complex formation as studied by copolymerization with styrene. The enhancement of reactivity of 4-VP complexed with cobaltous chloride is somewhat smaller than that of the corresponding zinc complex.     

Collision-energy-resolved Penning ionization electron spectroscopy of p-benzoquinone: study of electronic structure and anisotropic interaction with He(*)(2 (3)S) metastable atoms

Collision energy dependence of partial ionization cross sections (CEDPICS) of p-benzoquinone with He(*)(2 (3)S) metastable atoms indicates that interaction potentials between p-benzoquinone and He(*)(2 (3)S) are highly anisotropic in the studied collision energy range (100-250 meV). Attractive interactions were found around the C==O groups for in-plane and out-of-plane directions, while repulsive interactions were found around CH bonds and the benzenoid ring. Assignment of the first four ionic states of p-benzoquinone and an analogous methyl-substituted compound was examined with CEDPICS and anisotropic distributions of the corresponding two nonbonding oxygen orbitals (n(O) (+),n(O) (-)) and two pi(CC) orbitals (pi(CC) (+),pi(CC) (-)). An extra band that shows negative CEDPICS was observed at ca. 7.2 eV in Penning ionization electron spectrum.     

Effects of the intramolecular NH...S hydrogen bond in mononuclear platinum(II) and palladium(II) complexes with 2,2'-bipyridine and benzenethiol derivatives

A series of complexes, [M(bpy)(SAr)2] (M = platinum(II) or palladium(II), bpy = 2,2'-bipyridine, SAr = 2- or 4-(acylamino)benzenethiolate, or 2-(alkylcarbamoyl)benzenethiolate), were synthesized and characterized on the basis of 1H NMR, IR, and electrochemical properties. The structures of [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) and [Pt(bpy)(S-2-t-BuNHCOC6H4)2] (3) were determined by X-ray analysis. The complexes have intramolecular NH...S hydrogen bonds between the amide NH group and the sulfur atom. A weak NH...S hydrogen bond in these complexes and [Pd(bpy)(S-2-Ph3CCONHC6H4)2] (4) is detected from the 1H NMR spectra and the IR spectra in chloroform and in the solid state. [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) exhibits a remarkably high-energy-shifted lowest-energy band in UV-visible spectra and has a positively shifted oxidation potential. The blue-shift of 42 nm and the positive shift of +0.24 V, as compared to those of [Pt(bpy)(SC6H5)2), are due to the effect of the NH...S hydrogen bond.