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.

Crystallographic and electrochemical characteristics of melt-spun Ti–Zr–Ni–Y alloys

Ti45Zr30Ni25Yx (x = 1, 3, 5 and 7) alloys were prepared by melt-spinning at wheel velocity of 20 m s(-1). The effect of additive Y on phase structure and electrochemical performance of melt-spun alloys was investigated. Ti45Zr30Ni25Yx melt-spun alloys were composed of I-phase and amorphous phase. T

Structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30-LaNi5 hydrogen storage alloys

The structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30+x% LaNi5 (x=0, 1, 5 and 10) hydrogen storage alloys have been investigated systematically. XRD shows that the matrix phase structure of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure is not changed after adding LaNi5 alloy. However, the amount of the secondary phase increases with increasing LaNi5 content. Field emission scanning electron microscopy-energy dispersive spectroscopy (FESEM-EDS) shows that the C14 Laves phase contains more Zr and the white lard phase has a composition close to (Zr, Ti)(V, Cr, Ni, La)(2).

Crystallographic and electrochemical characteristics of Ti-Zr-Ni-Pd quasicrystalline alloys

Ti45Zr35Ni20-xPdx (x = 0, 1, 3, 5 and 7, at%) alloys were prepared by melt-spinning. The phase structure and electrochemical hydrogen storage performances of melt-spun alloys were investigated. The melt-spun alloys were icosahedral quasicrystalline phase, and the quasi-lattice constant increased with increasing x value. The maximum discharge capacity of alloy electrodes increased from 79 mAh/g (x = 0) to 148 mAh/g (x = 7). High-rate dis-chargeability and cycling stability were also enhanced with the increase of Pd content. The improvement in the electrochemical hydrogen storage characteristics may be ascribed to better electrochemical activity and oxidation resistance of Pd than that of Ni.

Effect of La-Mg-based alloy addition on structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy

Effect of La-Mg-based alloy (AB(5)) addition on Structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy has been investigated systematically. XRD shows that the matrix phase structure is not changed after adding AB(5) alloy, however, the amount of the secondary phase increases with increasing AB(5) alloy content. The electrochemical measurements show that the plateau pressure Ti0.10Zr0.15V0.35Cr0.10Ni0.30 + x% La0.85Mg0.25Ni4.5Co0.35Al0.15 (X = 0, 1, 5, 10, 20) hydrogen storage alloys increase with increasing x, and the width of the pressure plateau first increases when x increases from 0 to 5 and then decreases as x increases further, and the maximum discharge capacity changes in the same trend.

Effect of AB(5) alloy on Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy

The structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30 + x% LaNi4Al0.4Mn0.3Co0.3 (x = 0, 1, 5) hydrogen storage alloys have been investigated systematically. XRD shows that though the main phase of the matrix alloy remains unchanged after LaNi4Al0.4Mn0.3Co0.3 alloy is added, a new specimen is formed. The amount of the new specimen increases with increasing x. SEM-EDS analysis indicates that the V-based solid solution phase is mainly composed of V, Cr and Ni; C14 Laves phase is mainly composed of Ni, Zr and V; the new specimen containing La is mainly composed of Zr, V and Ni. The electrochemical measurements suggest that the activation performance, the low temperature discharge ability, the high rate discharge ability and the cyclic stability of composite alloy electrodes increase greatly with the growth of x.

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-Cu alloys

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction, and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases, and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals, amorphous, and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy, respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeabifity and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni, which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation, as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy, which could work as the electro-catalyst and the micro-current collector.

Effect of La/Ce ratio on the structure and electrochemical characteristics of La0.7-xCexMg0.3Ni2.8Co0.5 (x=0. 1-0.5) hydrogen storage alloys

The effect of La/Ce ratio on the structure and electrochemical characteristics of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1, 0.2, 0.3, 0.4, 0.5) alloys has been studied systematically. The result of the Rietveld analyses shows that, except for small amount of impurity phases including LaNi and LaNi2, all these alloys mainly consist of two phases: the La(La, Mg)(2)Ni-9 phase with the rhombohedral PuNi3-type structure and the LaNi5 phase with the hexagonal CaCU5-type structure. The abundance of the La(La, Mg)(2)Ni-9 phase decreases with increasing cerium content whereas the LaNi5 phase increases with increasing Ce content, moreover, both the a and cell volumes of the two phases decrease with the increase of Ce content. The maximum discharge capacity decreases from 367.5 mAh g(-1) (x = 0.1) to 68.3 mAh g(-1) (x = 0.5) but the cycling life gradually improve. As the discharge current density is 1200 mA g(-1), the HRD increases from 55.4% (x = 0.1) to 67.5% (x = 0.3) and then decreases to 52.1% (x = 0.5). The cell volume reduction with increasing x is detrimental to hydrogen diffusion D and accordingly decreases the low temperature dischargeability of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1-0.5) alloy electrodes.

Crystallographic and electrochemical properties of ball-milled quasicrystalline Ti45Zr35Ni17Cu3 alloy with 20 mass% Ni

Icosahedral quasicrystalline Ti45Zr35Ni17Cu3 alloy powder was ball-milled with 20 mass% Ni, and the effect of the ball-milling time (t) on crystallographic and electrochemical characteristics were investigated. The amounts of icosahedral quasicrystalline and Ni phases decreased when ball-milling time increased from 30 to 180 min. The powder consisted of amorphous and (Ni and Ti) phases after 360 min of ball-milling. The maximum discharge capacity of the powder electrodes first increased from 89 (t = 0 min) to 192 mAh g(-1) (t = 180 min), and then decreased to 138 mAh g(-1) (t = 360 min). The high-rate dischargeability and the discharge capacity after 15 cycles increased with increasing ball-milling time.

Sol-gel derived iridium composite glucose biosensor

Iridium powder is introduced into sol-gel process for the first time to fabricate a novel type of sol-gel derived metal composite electrode. The iridium ceramic electrode shows excellent electrocatalytic action for both oxidation and reduction of hydrogen peroxide. The glucose biosensor based on sol-gel derived iridium composite electrode was fabricated. The biosensor shows highly selectivity towards glucose because of the strong catalytic action of iridium composite matrix for enzyme-liberated hydrogen peroxide at low operating potential, at which common interferences cannot be sensed. The novel type of biosensor can be renewed by simply mechanical polishing with favorable reproducibility and long-term stability.

Sol-gel derived iridium composite glucose biosensor

Iridium powder is introduced into sol-gel process for the first time to fabricate a novel type of sol-gel derived metal composite electrode. The iridium ceramic electrode shows excellent electrocatalytic action for both oxidation and reduction of hydrogen peroxide. The glucose biosensor based on sol-gel derived iridium composite electrode was fabricated. The biosensor shows highly selectivity towards glucose because of the strong catalytic action of iridium composite matrix for enzyme-liberated hydrogen peroxide at low operating potential, at which common interferences cannot be sensed. The novel type of biosensor can be renewed by simply mechanical polishing with favorable reproducibility and long-term stability.

Lithography-independent and large scale fabrication of a metal electrode nanogap

A lithography-independent and wafer scale method to fabricate a metal nanogap structure is demon-strated. Polysilicon was first dry etched using photoresist (PR) as the etch mask patterned by photolithography.Then, by depositing conformal SiO_2 on the polysilicon pattern, etching back SiO_2 anisotropically in the perpendic-ular direction and removing the polysilicon with KOH, a sacrificial SiO_2 spacer was obtained. Finally, after metal evaporation and lifting-off of the SiO_2 spacer, an 82 nm metal-gap structure was achieved. The size of the nanogap is not determined by the photolithography, but by the thickness of the SiO_2. The method reported in this paper is compatible with modern semiconductor technology and can be used in mass production.

Rare-earth-metal mixed hydride/aryloxide complexes bearing mono(cyclopentadienyl) ligands. Synthesis, CO2 fixation, and catalysis on copolymerization of CO2 with cyclohexene oxide

Hydrogenolysis of mono(cyclopentadienyl)-ligated rare-earth-metal bis(alkyl) complexes Cp'Ln-(CH2SiMe3)2(THF) (Ln = Y (1a), Dy (1b), Lu (1c); Cp' = C5Me4SiMe3) with PhSiH3 afforded the mixed hydride/alkyl complexes [Cp'Ln(mu-H)(CH2SiMe3)(THF)](2) (Ln = Y (2a), Dy (2b), Lu (2c)). The overall structure of complexes 2a-c is a C-2-symmetric dimer containing a planar symmetric Ln(2)H(2) core at the center of the molecule. Deprotonation of ArOH (Ar = C6H2-Bu-t(2)-2,6-Me-4) by the metal alkyl group of 2a-c led to formation of the mixed hydride/aryloxide derivatives [Cp'Ln(mu-H)(OAr)](2) (Ln = Y (3a), Dy (3b), Lu (3c)), which adopt the dimeric structure through hydride bridges with trans-accommodated terminal aryloxide groups.

Surface-enhanced resonance Raman spectroscopy and spectroscopy study of redox-induced conformational equilibrium of cytochrome c adsorbed on DNA-modified metal electrode

The redox-induced conformational equilibrium of cytochrome c (cyt c) adsorbed on DNA-modified metal electrode and the interaction mechanism of DNA with cyt c have been studied by electrochemical, spectroscopic and spectroelectrochemical techniques. The results indicate that the external electric field induces potential-dependent coordination equilibrium of the adsorbed cyt c between its oxidized state (with native six-coordinate low-spin and non-native five-coordinate high-spin heme configuration) and its reduced state (with native six-coordinate low-spin heme configuration) on DNA-modified metal electrode. The strong interactions between DNA and cyt c induce the self-aggregation of cyt c adsorbed on DNA. The orientational distribution of cyt c adsorbed on DNA-modified metal electrode is potential-dependent, which results in the deviation from an ideal Nernstian behavior of the adsorbed cyt c at high electrode potentials. The electric-field-induced increase in the activation barrier of proton-transfer steps attributed to the rearrangement of the hydrogen bond network and the self-aggregation of cyt c upon adsorption on DNA-modified electrode strongly decrease the interfacial electron transfer rate.

Assembly of the transition metal substituted polyoxometalates ZnW11M(H2O)O-39(n-) (M = Mn, Cu, Fe, Co, Cr, Ni, Zn) on 4-aminobenzoic acid modified glassy carbon electrode and their electrochemical study

Through layer-by-layer assembly, a series of undecatungstozincates monosubstituted by first-row transition metals, ZnW11M(H2O)O-39(n-) (M=Cr, Mn, Fe, Co, Ni, Cu. or Zn) were first successfully immobilized on a 4-aminobenzoic acid modified glassy carbon electrode surface. The electrochemical behaviors of these polyoxometalates were investigated. They exhibit some special properties in the films different from those in homogeneous aqueous solution. The Cu-centered reaction mechanism in the ZnW11Cu multilayer film was described. The electrocatalytic behaviors of these multilayer film electrodes to the reduction of H2O2 and BrO3- were comparatively studied.