Studies on the Electrochemical Characteristics of K2FeO4 Electrode

Discharge performance of K2FeO4 electrode under different conditions was studied by the constant electric current discharge method. The electrochemical characteristics of K2FeO4 electrode were investigated for the first time by means of cyclic voltammetry. The results show that the K2FeO4 electrode made at moderate pressure (20MPa) and discharged at lower current has better discharge performance. It is also found that K2FeO4 electrode is significantly rechargeable.     

Selective Acetylation of Alcohols and Amines with Ethyl Acetate in the Presence of H<Subscript>6</Subscript>[PMo<Subscript>9</Subscript>V<Subscript>3</Subscript>O<Subscript>40</Subscript>] as the Catalyst

Summary. Acetylation of various alcohols and benzyl amine was tested in the presence of H₆[PMo₉V₃O₄₀], a mixed addenda heteropolyacid, in ethyl acetate under reflux condition. Phenols and anilines are not affected under the reaction conditions. Selective transestrification of alcohols can be achieved in the presence of phenol and aniline derivatives using this method.     

二甲醚反应化学的研究进展

随着GTL(Gas-to-Liquid)技术的发展,从煤炭或天然气经由合成气制备甲醇的反应过程已转向合成二甲醚的反应过程,最近的研究表明由合成气直接生产二甲醚能突破甲醇合成的热力学限制,实现单程的完全转化[1],其中煤基合成气一步法合成二甲醚较甲醇更具技术和经济优势.从物理性质看,     

Hierarchical Structure‐Within‐Structure Morphologies in A2‐star‐(B‐alt‐C) Molecules

We employ dissipative particle dynamics (DPD) to examine the self‐assembly behavior of A₂‐star‐(B‐alt‐C) molecules. We successfully observe various types of hierarchical structure‐within‐structures, such as A‐formed spheres in the matrix formed by B and C alternating layers, hexagonally packed A‐formed cylinders in the matrix with B and C segregated layers, B and C alternating layers‐within‐lamellae, coaxial B and C alternating domains within hexagonally packed BC‐formed cylinders in the A‐matrix, and co‐centric BC‐alternating domains within BC‐formed spheres in the A‐matrix, by increasing the A composition. Generally speaking, the small length‐scale B and C segregated domains are in parallel to the large length‐scale structures. This hierarchical periodicity along the same axis as well as the various characteristic structures, that the A₂‐star‐(B‐alt‐C) copolymers display, are quite different from those in A‐block‐(B‐graft‐C) coil‐comb copolymers. Moreover, it is interesting to find that when the copolymer chain length increases, though the hierarchical structure type is maintained, the number of small length‐scale lamellae that can form within the large length‐scale structure increases. These hierarchical structures under various compositions are reported theoretically for the first time in the copolymer systems consisting of the alternating blocks, and are in good agreement with the most recent experimental work by Matsushita and co‐workers (Macromolecules 2007 , 40, 4023).     

The Preparation and Characterization of Highly Dispersed PdO over Alumina for Low‐temperature Combustion of Methane

PdO/Al₂O₃ catalysts prepared by glow discharge plasma treatment followed by thermal calcination show a much higher dispersion and a better catalytic activity for methane combustion at relatively low temperatures. The dispersion of palladium active species by such plasma prepared catalysts is 29.7%, 5.4 times higher than that of conventional catalysts. XPS analysis indicates that a surface enrichment of Pd active species (PdO) has been achieved after plasma treatment. The surface atomic composition of PdO of plasma prepared catalysts reaches 10.5%. XRD characterization also confirms a wellcrystallized PdO phase present on the plasma prepared catalyst. The lightoff temperature of the plasma prepared catalyst is 370°C, 50°C lower than that obtained from the conventional catalyst.     

Efficient dehalogenation of polyhalomethanes and production of strong acids in aqueous environments: water-catalyzed O--H-insertion and HI-elimination reactions of isodiiodomethane (CH2I-I) with water

A combined experimental and theoretical study of the ultraviolet photolysis of CH2I2 in water is reported. Ultraviolet photolysis of low concentrations of CH2I2 in water was experimentally observed to lead to almost complete conversion into CH2(OH)2 and 2HI products. Picosecond time-resolved resonance Raman spectroscopy experiments in mixed water/acetonitrile solvents (25%-75% water) showed that appreciable amounts of isodiiodomethane (CH2I-I) were formed within several picoseconds and the decay of the CH2I-I species became substantially shorter with increasing water concentration, suggesting that CH2I-I may be reacting with water. Ab initio calculations demonstrate the CH2I-I species is able to react readily with water via a water-catalyzed O--H-insertion and HI-elimination reaction followed by its CH2I(OH) product undergoing a further water-catalyzed HI-elimination reaction to make a H2C=O product. These HI-elimination reactions produce the two HI leaving groups observed experimentally and the H2C=O product further reacts with water to produce the other final CH2(OH)2 product observed in the photochemistry experiments. These results suggest that CH2I-I is the species that reacts with water to produce the CH2(OH)2 and 2HI products seen in the photochemistry experiments. The present study demonstrates that ultraviolet photolysis of CH2I2 at low concentration leads to efficient dehalogenation and release of multiple strong acid (HI) leaving groups. Some possible ramifications for the decomposition of polyhalomethanes and halomethanols in aqueous environments as well as the photochemistry of polyhalomethanes in the natural environment are briefly discussed.     

金属酞菁化合物在TiO2表面的分散研究

Dispersion of copper(Ⅱ) phthalocyanine (CuPc), copper(Ⅱ) phthalocyaninesulfonate (CuPcS) and cobalt(Ⅱ)phthalocyaninetetrasulfonate (CoPcTS) on the surface of titanium dioxide was investigated by XRD, XPS, FT-IR and UV-Vis techniques. Results show that interaction between CuPc and TiO2 was very weak and CuPc was difficult to disperse on the surface of the support. While partly sulfurized CuPcS could be dispersed on the surface of support through sulfo-groups and its dispersion capacity was determined to be 0.085 g CuPcS/g TiO2. Completely sulfurlzed CoPcTS could also be dispersed on the surface of TiO2 as a monolayer and its dispersion capacity was 0.12 g CoPcTS/g TiO2. Interactions of the sulfo-groups as well as the electrons of CoPcTS with the surface of TiO2 could be evidenced by FT-IR characterization. Therefore, it was suggested that CoPcTS molecules be adsorbed on the surface of TiO2 in a flat-lying mode while CuPcS in a slanting one. UV-Vis spectra show that the dispersed CuPcS and CoPcTS molecules exist in both forms of monomers and dimers.     

Determination of imazalil by on-line coupled capillary isotachophoresis with capillary zone electrophoresis

A simple, rapid and reproducible capillary isotachophoretic on-line coupled with capillary zone electrophoresis (CITP-CZE) method for the determination of IMz in food packaging extracts and its residues in apples is described. A good separation of the IMZ from other sample constituents was achieved within 15 minutes without any sample clean up. Method characteristics (linearity, accuracy, intra-assay and detection limit) were determined. Less amount of time involved, sufficient sensitivity and low running cost are the important attributes of CITP-CZE method.     

Kinetic Determination of Microquantities of Rutin by Perturbation of the Bray-Liebhafsky Oscillatory Reaction in an Open System

A kinetic method is described for the microquantitative (microconcentration/microvolume) determination of rutin based on potentiometric monitoring of the concentration perturbations of the Bray-Liebhafsky (BL) oscillatory reaction being in a non-equilibrium stationary state close to a bifurcation point. The experiments are carried out in an open reactor. The response of the matrix system to perturbations by different concentrations of rutin ethanolic solutions is followed by a Pt-electrode. In the concentration range between 7.8×10^–8moldm^–3 and 9.1×10^–6mol dm^–3, we found a linear dependence of the maximal potential shift, E_m, on the logarithm of the rutin concentrations. The unknown concentrations can be determined from the calibration curve up to an accuracy of ±5%. The detection limit is 3.6×10^–8mol dm^–3. The amount of required sample can be as small as 10µL.