MICHAEL ADDITION OF NITROALKANE TO α,β-UNSATURATED CARBONYL COMPOUNDS ON KF / Al_2O_3/ PEG4000

Michael addition of nitroalkanes to α,β-unsaturated carbonyl compounds occurs in the presence of KF/AI_2O_3/PEG4000 without solvent.Yields are fair to good and work-ups are easy.

SYNTHESIS AND X-RAY POWDER STUDY OF A NEW COMPOUND:Ba_6Ti_7Nb_9O_(42)

A new compound Ba6Ti7Nb9O42 was prepared for the first time by solid state reaction in BaO-TiO2-Nb2O5, ternary system. The X-ray powder diffraction data of the title compound was determined. Ba6Ti7Nb9O42 crystallizes in the hexagonal system -with unit cell parameters a=9.0527(4) A,c=11.790(1) A,and space group P63/mcm(193),z=1. The calculated and measured densities are 5. 293 g/cm3 and 5.285 g/cm3, respectively.

Coexistence of Polaronic States and Superconductivity in Iron-Pnictide Compound Ba_2Ti_2Fe_2As_4O

The electronic structure of iron-pnictide compound superconductor Ba_2Ti_2Fe_2As_4O, which has metallic intermediate Ti_2O layers, is studied using angle-resolved photoemission spectroscopy. The Ti-related bands show a‘peak-dip-hump＇ line shape with two branches of dispersion associated with the polaronic states at temperatures below around 120 K. This change in the spectra occurs along with the resistivity anomaly that was not clearly understood in a previous study. Moreover, an energy gap induced by the superconducting proximity effect opens in the polaronic bands at temperatures below T_c（~21 K）. Our study provides the spectroscopic evidence that superconductivity coexists with polarons in the same bands near the Fermi level, which provides a suitable platform to study interactions between charge, lattice and spin freedoms in a correlated system.

Preparation of porous α-Fe_2O_3-supported Pt and its sensing performance to volatile organic compounds

Porous α-Fe2O3 was synthesized by a simple hydrothermal treatment of FeC13 aqueous solution followed by a calcination process. In the synthesis of porous α-Fe2O3, no templates or pore-directing agents were used. The as-prepared porous α-Fe2O3 was further employed as a support for loading Pt nanoparticles. The gas sensing performance of the obtained porous α-Fe2O3-supported Pt to VOCs was investigated. The sensor presented a high response and fast response-recovery characteristic to several VOCs including acetone, ether, methanol, ethanol, butanol and hexanol. Meanwhile, it exhibited a much higher response than the pure α-Fe2O3 at the operating temperature of 260 ℃. The enhanced sensing properties may be related to the unique porous structure of the α-Fe2O3 support and the promoting effect of active Pt nanoparticles for the sensing reactions.

SYNTHESIS AND STRUCTURE OF TETRANUCLEAR MOLYBDENUM CLUSTER COMPOUND[Mo_4S_4(μ-O_2CC_6H_5)_2(dtp)_4]

The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in the presence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c, Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4; Dc=1.78g/cm^3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]cluster core and t-(dtp)^(-1)ligands are retained and only μ-bridged(dtp)^(-1)ligands are substituted by(C_6H_5CO_2)^(-1)in the substitution reaction,thus producing the new title cluster compound,the structure of which contains two species of bidentate ligand.

Activation of Carcinogenic Non-aminoazo Compounds iu Horseradish Peroxidase/H_2O_2 System

Eriochrome black T and Nitrosulfophenol S were advocated as the chemical models of carcinogenic non-aminoazo compounds. The main products of their oxidative cleavage in horseradish peroxidase/H2O2 system was identified as the benezenediazonium ion, the ultimate carcinogens, which could bind to DNA. The reaction conditions were investigated preliminarily. Some inhibitors and inducers of the reaction were discovered.

IN-SITU HVEM STUDY ON PHASE TRANSITION OF YBa_2Cu_3O_(7-x) SUPERCONDUCTING COMPOUND IN PROCESS OF HEATING

In-situ HVEM observation on phase transition of the YBa_2Cu_3O_(7-x) superconducting compound in pro- cess of heating was carried out,and high temperature X-ray diffraction analysis in air and X-ray diffraction phase analysis for the sample treated in vacuum condition were made.The results showed that the temperature of phase transition is related to oxygen content in the sample and in general,is 100℃ to 120℃ lower in vacu- um condition than in air.At 320℃ to 350℃ twin bands begin to disappear,and some Cu_2O are formed on the surface of the sample and transit from orthorhombic YBa_2Cu_3O_(7-x) to arthorhombic Y_2BaCuO_5 compound. This transition was completed at about 500℃.Above 900℃,this compound consists of the Y_2BaCuO_5, BaCuO_2,Y_2O_3 and some other minor compounds.No phase transition was observed during cooling the sample.

Preparation and Characterization of TiO₂Photocatalytic Thin Film and Its Compounds by Micro-Arc Oxidation Technique

Mesoporous TiO2 ceramic films have been prepared upon the Ti alloy substrate by the micro-arc oxidation (MAO) technology. To enhance the photo-catalytic property of the films, Eu2O3 particles were added into the electrolyte solution of Na2CO3/Na2SiO3. Scanning electron microscope (SEM), energy dispersive (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) are employed to characterize the modified films. Diffuse reflectance spectra (DRS) test, photo-generated current test and photo decomposition test are applied to evaluate the photo-catalytic property of the modified films. The results show that Eu2O3 transformed into one-dimensional (1-D) nano-wires embedded within the composite film, and the film has high photo-catalytic property.

Polarizabilities and Orientational Order Parameter in N-(p-n-Ethoxybenzylidene)- p-n-Alkoxy Anilines, 2O.Om LC Compounds

n.m, n.Om, nO.m and nO.Om compounds play an important role in the fundamental and applied aspects. As a part of our systematic studies of the above homologous series regarding the synthesis, characterization and phase transition studies, here the authors report the polarizabilities and orientational order parameter, S in N-(p-n-ethoxybenzylidene)-p-n-alkoxy anilines, 2O.Om with m = 3 to 10 liquid crystalline compounds except with m = 5 which has been already published. The rest of the compounds exhibit the nematic LC phase except with m = 10 which shows the smectic-C phase along the nematic phase which is originally not detected by Godzwon et al. But the author’s observations with TM and differential scanning calorimeter have shown the existence on SmC phase in addition to nematic phase. Further, SmC is clarified using the histogram technique whose details are given below and are published elsewhere. The orientstonal order parameter, S is estimated using different methods and compared with the value obtained from birefringence, δn = (ne – no) where no field model is used. It is observed in these compounds case as in other LC compounds Vuks isotropic model is favored compared to that of anisotropic model proposed by Neugebauer.

焦化废水中几种含氮杂环有机物在A_1-A_2-O系统中的降解特性研究

在对焦化废水中有机物在A1 A2 O生物膜系统中降解转化规律进行分析的基础上 ,选取焦化废水中 6种主要的含氮杂环化合物 :吡啶、吲哚、喹啉、异喹啉、2 甲基喹啉、8 羟基喹啉 ,与苯酚共同配制成溶液 ,在A1 A2 O生物膜系统中运行 ,结果表明上述几种含氮杂环有机物在A1 A2 O系统中都可得到较完全的去除 .它们在厌氧段的降解速率从大到小依次为 :吲哚>2 甲基喹啉 >8 羟基喹啉 >异喹啉 >喹啉 >吡啶 .在厌氧条件下 ,吲哚和喹啉存在拮抗作用 ,而吡啶对喹啉有协同作用 ;

N2O Decomposition over K-Ce Promoted Co-M-AI Mixed Oxide Catalysts Prepared from Hydrotalcite-like Precursors

A series of mixed oxide catalysts with different composition of Co-M-Al and Co-M-Ce- Al （M=Zn, Ni, Cu） were prepared by co-precipitation method from hydrotalcite-like compounds. The experimental results revealed the catalytic activity of Co-Ni-Al is slightly higher than that of Co-Zn-Al and much higher than that of Co-Cu-Al for direct decomposition of N2O. Moreover, addition of small amounts of Ce02 improved the catalytic activity signif- icantly and made the decomposition temperatures at which the N2O conversion was 50% and 90% （T50 and Tgo） both decreased 80 ℃ than those of Co-M-Al catalysts without CeO2 added. Further, potassium-load also promoted the catalytic activity, and the decomposi- tion temperatures of T50 and T90 both decreased approximately 50 ℃. It is significant for decomposing N2O from industries and reducing carbon emission from atmosphere.

O,O-二甲基硫代磷酰-(2-噻唑硫酮)胺的合成研究

报道了以三氯硫磷为起始原料,合成了含有杀虫和杀菌基因的有机磷化合物——O,O-二甲基硫代磷酰-(2噻唑硫酮)胺。

Insight into catalytic properties of Co3O4-CeO2 binary oxides for propane total oxidation

A series of Co3O4-CeO2 binary oxides with various Co/(Ce+Co)molar ratios were synthesized using a citric acid method,and their catalytic properties toward the total oxidation of propane were examined.The activities of the catalysts decrease in the order CoCeOx-70>CoCeOx-90>Co3O4>CoCeOx-50>CoCeOx-20>CeO2.CoCeOx-70(Co/(Ce+Co)=70% molar ratio)exhibits the highest catalytic activity toward the total oxidation of propane,of which the T90 is 310℃(GHSV=120000 mL h^-1 g^-1],which is 25℃ lower than that of pure Co3 O4.The enhancement of the catalytic performance of CoCeOx-70 is attributed to the strong interaction between CeO2 and Co3O4,the improvement of the low-temperature reducibility,and the increase in the number of active oxygen species.In-situ DRIFTS and reaction kinetics measurement reveal that Ce addition does not change the reaction mechanism,but promotes the adsorption and activation of propane on the catalyst surface.The addition of water vapor and CO2 in reactant gas has a negative effect on the propane conversion,and the catalyst is more sensitive to water vapor than to CO2.In addition,CoCeOx-70 exhibits excellent stability and reusability in water vapor and CO2 atmosphere.

A simple and efficient synthesis of 2-substituted benzothiazoles catalyzed by H_2O_2/HCl

A simple and efficient procedure for the synthesis of substituted benzothiazoles through condensation of 2-aminothiophenol with aromatic aldehydes in the presence of H2O2/HCl system in ethanol at room temperature is described. The target compounds have been characterized by ^1H NMR, ^13C NMR, IR and MS. Short reaction time, easy and quick isolation of the products, and excellent yields are the main advantages of this procedure.

基于Cu-BTC骨架的Cu_(2)O-CuO复合材料的制备及吸其附性能

为了提高材料对放射性碘的吸附性能,在制备立方体和十二面体铜基均苯三甲酸(Cu-BTC)材料的基础上,通过调节煅烧气氛环境,获得更为疏松多孔的氧化亚铜-氧化铜(Cu_(2)O-CuO)复合材料。通过扫描电子显微镜、X射线衍射、红外光谱等手段对材料进行表征,发现所得材料分别为立方体和十二面体的Cu_(2)O-CuO,并依旧保留大部分Cu-BTC结构骨架。对碘离子的吸附实验结果显示,立方体和十二面体的Cu_(2)O-CuO饱和吸附容量分别能够达到49.72、91.91 mg/g。热力学和动力学吸附研究结果表明,2种形貌的Cu_(2)O-CuO均属于以化学吸附为主,符合Langmuir吸附模型的单分子层吸附。制备的Cu_(2)O-CuO能够在吸附时与碘离子生成CuI。吸附剂在弱酸条件吸附性能更强,干扰离子中,弱酸根离子会阻碍材料对碘离子的吸附,而强酸根离子则能一定程度上促进吸附,提升吸附剂吸附性能。

Conversion and reaction kinetics of coke oven gas over a commercial Fe-Mo/Al_2O_3 catalyst

Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst(T-202) were studied in a continuous flow fixed bed reactor under pressures of 1.6-2.8 MPa, space time of 1.32-3.55 s and temperatures of 240-360 °C. Though the COG contains about 0.6 mol/mol H2, hydrogenation of CO and CO2 is not significant on this catalyst. The conversions of unsaturated hydrocarbons depend on their molecular structures. Diolefins and alkynes can be completely hydrogenated even at relatively low temperature and pressure. Olefins, in contrast, can only be progressively hydrogenated with increasing temperature and pressure. The hydrodesulfurization(HDS) of CS2 on this catalyst is easy. Complete conversion of CS2 was observed in the whole range of the conditions used in this work. The original COS in the COG can also be easily converted to a low level. However, its complete HDS is difficult due to the relatively high concentration of CO in the COG and due to the limitation of thermodynamics. H2 S can react with unsaturated hydrocarbons to form ethyl mercaptan and thiophene, which are then progressively hydrodesulfurized with increasing temperature and pressure. Based on the experimental observations, reaction kinetic models for the conversion of ethylene and sulfur-containing compounds were proposed; the values of the parameters in the models were obtained by regression of the experimental data.

Catalytic transfer hydrogenation of levulinate ester intoγ-valerolactone over ternary Cu/ZnO/Al2O3 catalyst

An effective catalytic transfer hydrogenation (CTH) process of bio-based levulinate esters into γ-valerolactone (GVL) was explored over ternary Cu/ZnO/Al2O3 catalyst which was prepared by coprecipitation method and could be sustainably used. As a result, quantitative conversion of ethyl levulinate (EL) and 99.0% yield of GVL were obtained in the CTH process using i-PrOH as hydrogen donor. The Cu/ZnO/Al2O3 catalyst with high-surface-area could be reused at least four times without the loss of catalytic activity. Furthermore, the structure and properties of Cu/ZnO/Al2O3 catalyst was characterized through XRD, BET, SEM, TEM and H2-TPR. Also, the influence of different support oxides and calcination temperatures was investigated.

Effect of anions on preparation of ultrafine α-Al_2O_3 powder

Ultrafine alumina power was obtained by calcining the precursor at 1 200 ℃ for 2 h, which was prepared by homogeneous precipitation method using aluminium salts and urea as raw materials. The effects of anions on the morphology, particle size, surface area and configuration of the precursors were studied. The results show that the reactions of urea with aluminium nitrate and aluminium chloride result in agglomerates gels with bad filtering performance, the morphology is fibrillar. Aluminium sulphate-urea reactions result in the direct formation of amorphous powders with good filtering performance, of which morphology are regular spherical particles with larger granularity and smaller surface area. The reaction of mutual compound of aluminium sulphate and aluminium nitrate with molar ratio of 40:60 with urea can produce precursor with good filtering performance, spherical morphology, and uniform granularity distribution in the particle size range of 2-3 μm.

Influence of coexisting substances on the photodegradation behaviors of 17α-ethinylestradiol (EE_2) in the UV/H_2O_2 process

The batch photodegradation reactor was used to investigate the influence of the common coexisting substances in wastewater,such as H+,anions (HCO3-,Cl-and NO3-) and organic compounds (methanol and bisphenol A),on the photodegradation behaviors of EE2 in the UV/H2O2 process.The results indicated that the addition of coexisting substances can influence the photodegradation behaviors of EE2 and it also follows the first-order kinetics.The acidic (pH 2-4) and alkaline (pH 10-12) medium benefit the photodegradation of EE2,but the photodegradation rate constant of EE2 keeps almost constant in the pH value of 4-10.The addition of anions,such as HCO3-,Cl-and NO3-,can inhibit the photodegradation of EE2,and the rate constant has a negative linear relationship with the concentration of the anions.However,the reduction degrees vary with the anions kinds,and the inhibition effect of the three anions is in the order of HCO3->NO3->Cl-.Addition of 5 mg/L methanol and bisphenol A can reduce the photodegradation rate constant of EE2by 84.31% and 72%,respectively.By comparison,the retardant effect of methanol is much more evident.In the studied concentrations range,the photodegradation rate constant of EE2 is the unary quadratic function of the organic compounds concentrations.

O，O—二（2—乙基已基）二硫代磷酸合成过程的^（31）PNMR谱研究

报道了不同反应条件下所制得Ｏ，Ｏ—二（２—乙基己基）—二硫代磷酸的３１ＰＮＭＲ谱．研究了其合成产物组成分的变化及其反应机理．