Efficient oxidation of ethylbenzene catalyzed by cobalt zeolitic imidazolate framework ZIF-67 and NHPI

Efficient catalytic oxidation of ethylbenzene to acetophenone was realized using the catalytic system of cobalt zeolitic imidazolate framework ZIF-67/N-hydroxyphthalimide （NHPI） under mild conditions. 95.2% conversion of ethylbenzene with 90.3% selectivity to acetophenone could be obtained at 373 K under 0.3 MPa 02 for 9 h. The results show that there exists synergetic effect between ZIF-67 and NHPI. 1-Phenylethyl hydroperoxide （PEHP） was generated via a radical process involving the hydrogen abstraction from ethylbenzene by phthalimide N-oxyl, and subsequently effectively decomposed to acetophenone by ZIF-67.     

Oxygen permeation and phase structure properties of partially A-site substituted BaCo_(0.7)Fe_(0.225)Ta_(0.075)O_(3-δ) perovskites

Ba0.9R0.1Co0.7Fe0.225Ta0.075O3-δ(BRCFT, R = Ca, La or Sr) membranes were synthesized by a solid-state reaction. Metal cation Ca2+,La3+or Sr2+doping on A-site partially substituted Ba2+in BaCo0.7Fe0.225Ta0.075O3-δoxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, H2-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2+, La3+or Sr2+, whose ionic radii are smaller than that of Ba2+, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experiments showed that BRCFT with A-site fully occupied by Ba2+exhibited good oxygen permeation flux under He flow, reaching about 2.3mL min-1 cm-2at 900 ℃ with 1 mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation(Ba2+La3+Sr2+Ca2+).     

Interconnected sandwich structure carbon/Si-SiO2/carbon nanospheres composite as high performance anode material for lithium-ion batteries

In the present work,an interconnected sandwich carbon/Si-SiO2/carbon nanospheres composite was prepared by template method and carbon thermal vapor deposition（TVD）.The carbon conductive layer can not only efficiently improve the electronic conductivity of Si-based anode,but also play a key role in alleviating the negative effect from huge volume expansion over discharge/charge of Si-based anode.The resulting material delivered a reversible capacity of 1094 mAh/g,and exhibited excellent cycling stability.It kept a reversible capacity of 1050 mAh/g over 200 cycles with a capacity retention of 96%.     

CH4 reforming with CO2 for syngas production over La2O3 promoted Ni catalysts supported on mesoporous nanostructured γ-A12O3

Nanostructured -y-A12O3 with high surface area and mesoporous structure was synthesized by sol-gel method and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by XRD, N2 adsorption-desorption, TPR, TPO, TPH, NH3-TPD and SEM techniques. The BET analysis showed a high surface area of 204 m2.g-1 and a narrow pore-size distribution centered at a diameter of 5.5 nm for catalyst support. The BET results revealed that addition of lanthanum oxide to aluminum oxide decreased the specific surface area. In addition, TPR results showed that addition of lanthanum oxide increased the reducibility of nickel catalyst. The catalytic evaluation results showed an increase in methane conversion with increasing lanthanum oxide to 3 mol% and further increase in lanthanum content decreased the catalytic activity. TPO analysis revealed that the coke deposition decreased with increasing lanthanum oxide to 3 mol%. SEM and TPH analyses confirmed the formation of whisker type carbon over the spent catalysts. Addition of steam and Oxide to drv reformin feed increased the methane conversion and led to carbon free ooeration in combined orocesses.     

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks （MOFs） have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I（also named Cu-BTC or MOF-199） was chemically reduced by doping it with alkali metals （Li, Na and K） and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction （XRD）, thermo-gravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li＋, Na＋ and K＋, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.     

青川黑木耳吸水机理研究

黑木耳具有优良的吸水性能。通过IR和SEM研究了黑木耳的化学组成和微观结构,研究了其在不同温度、不同溶液环境下的吸胀曲线,并研究了其保水和重复吸水能力。结果表明,黑木耳富含羟基、羧基、酰胺基等吸水基团,木耳胶质主要为疏松多孔结构,腹侧角质层较为致密,含少量微孔,背侧含有丰富的纤维绒毛,绒毛直径约为5微米。吸水性能测试结果表明,木耳具有良好的吸水能力,最大吸水倍率为23倍,且具有优良的保水及复水能力。     

圆二色法研究铜离子存在下葛根素对牛血清白蛋白二级结构的影响

采用圆二色光谱法(CD)研究了Cu2+存在下葛根素(PUE)对牛血清白蛋白(BSA)二级结构的影响。结果表明,在pH 7.4的条件下,BSA的各种二级结构分别为56.3%α-螺旋,26.1%β-折叠,17.6%转角和无规则卷曲。葛根素和Cu2+-葛根素都能诱导BSA二级结构发生改变。葛根素使BSA的α-螺旋含量增加,β-折叠含量减少,这表明葛根素与BSA的相互作用,可使蛋白质分子的疏水作用增强,导致BSA的肽链结构收缩。Cu2+-葛根素使BSA的α-螺旋含量大幅度降低,β-折叠含量略有增加,这表明Cu2+-葛根素与BSA的相互作用以配位作用为主,使得BSA的肽链结构伸展,蛋白质的构象发生变化。     

有机蒙脱土改性脲醛树脂胶黏剂的制备及结构表征

采用"碱-酸-碱"合成工艺,在各阶段将OMMT(有机蒙脱土)投入反应体系,制备有机蒙脱土改性脲醛树脂胶黏剂,测试胶黏剂的各项性能,用XRD(X射线衍射仪)、FTIR(傅里叶变换红外光谱)、SEM(扫描电镜)、TG(热重分析)对改性胶黏剂结构进行表征.实验结果表明,随着OMMT的加入,胶黏剂的游离甲醛含量降低,胶合强度增加.第一阶段投入OMMT,降醛效果明显,第二阶段投入OMMT,补强效果明显.SEM图显示,改性胶黏剂中被剥离成片层状的OMMT因受基体的包覆或挤压,呈现出蜷曲的形状;XRD图谱显示,OMMT/UF胶黏剂的结晶度低于UF胶黏剂的结晶度,有机蒙脱土的加入,破坏了脲醛树脂中羰基和氨基的规整性排列;FTIR图谱表明,改性脲醛树脂胶黏剂中存在大量游离的尿素,胶黏剂的游离甲醛含量低;TG分析得出,改性胶黏剂的TG曲线移向高温方向,材料的热分解温度提高.     

基于特征值分析的正癸烷骨架和总包简化机理

使用基于特征值分析的骨架简化方法对由118 个组分和527 个反应构成的正癸烷详细机理进行了简化,获得了一个由70 个组分、327 个基元反应组成的骨架机理; 采用基于特征值分析的计算奇异摄动(CSP)简化方法对骨架机理进行进一步简化,得到一个38 组分、34 步的总包简化机理. 通过对简化机理、骨架机理和详细机理的对比发现,简化机理和骨架机理能够很好地再现详细机理的特性,并能够描述正癸烷的主要燃烧特性,为进一步实现耦合化学反应动力学与流体力学的工程计算,提高计算效率提供了可用的燃烧模型.     

卡波普改性纳米纤维基复合纳滤膜的结构与性能

以仿生胶黏剂卡波普(carbopol,CP)改性的聚丙烯腈(polyacrylonitrile,PAN)纳米纤维膜为基膜,以哌嗪和均苯三甲酰氯分别为水相单体和有机相单体采用界面聚合法制备得到一种功能阻隔层为聚哌嗪酰胺(polypiperazine-amide,PA)的纳米纤维基复合纳滤膜(PAN/CP/PA).傅里叶红外光谱表明CP凝胶中的羧基(—COOH)与PAN纳米纤维层中的氰基(—CN)形成氢键,同时与水相单体哌嗪上的仲胺基形成羧酸铵盐离子键(—COO-H2N+),使得复合纳滤膜各层之间相互作用增强.分别以卡波普改性前后的PAN纳米纤维膜为基膜,采用相同界面聚合工艺制备PAN/PA和PAN/CP/PA复合滤膜,其力学性能测试表明,CP凝胶的引入将PAN纳米纤维基膜与功能阻隔层之间有效黏合在一起,实现了复合膜结构的一体性,整体的断裂强度由15.1 MPa提高至24.2 MPa.对比2种复合膜的盐水过滤性能,PAN/CP/PA复合膜对二价硫酸盐的截留效果与PAN/PA复合膜保持一致,对硝酸盐类和MgCl2的截留效果明显优于PAN/PA复合膜,其缘由归因于CP凝胶层中含有大量的羧基增强了PAN/CP/PA复合纳滤膜荷负电性.同时,CP凝胶本身的亲水性使得PAN/CP/PA复合膜的平均过滤水通量(20.3 L/m2h)与PAN/PA复合膜的平均过滤水通量(20.9 L/m2h)相比基本保持不变.