水热法合成纳米花状二硫化钼及其微观结构表征

本文以钼酸钠、硫代乙酰胺为前驱体, 硅钨酸为添加剂, 成功用水热法合成高纯度纳米花状二硫化钼. 产物特性用X射线衍射(XRD)、能量色散谱(EDS)、扫描电子显微镜(SEM)进行表征. XRD和EDS图显示实验产物为二硫化钼, 且其结晶度和层状堆垛良好. SEM图谱则表明二硫化钼为纳米花状结构, 颗粒直径300 nm左右, 由几十上百片花瓣组成, 每片花瓣厚度十个纳米左右. 通过以硅钨酸为变量的梯度实验, 研究发现, 硅钨酸对于纳米花状MoS₂的形成具有重要作用, 不添加硅钨酸, 无法形成纳米花状MoS₂, 此外, 硅钨酸的剂量会影响合成MoS₂的大小和形貌. 本文还对纳米花状二硫化钼的形成机理做了初步的讨论.     

机载腔增强吸收光谱系统应用于大气NO_2空间高时间分辨率测量

介绍了一套用于机载平台测量的非相干宽带腔增强吸收光谱(IBBCEAS)系统,并应用于实际大气NO_2空间分布的高时间分辨率观测.为满足机载测量中对时间分辨率的需求,系统采用离轴抛物面镜代替消色差透镜提高光学耦合效率;并运用Allan方差,对系统性能进行了分析.通过腔增强吸收光谱系统与长光程吸收光谱系统对实际大气NO_2的对比测试,两者线性相关系数R~2达到0.86.将IBBCEAS系统应用于机载平台,在时间分辨率为2 s的情况下,探测限达到95 ppt(1σ).通过机载观测,获得了华北地区石家庄等地上空对流层大气NO_2的廓线信息.     

Ce掺杂K_2La_2Ti_3O_(10)催化剂的可见光高效催化制氢的研究

采用高温固相法合成了铈掺杂的K2La2Ti3O10催化剂,利用X射线衍射(XRD)、紫外-可见漫反射(UV-visDRS)、透射电镜(TEM)和X射线光电子能谱(XPS)对催化剂进行了表征.考察了催化剂的可见光催化分解甲醇水溶液制氢的活性,并对可见光催化机理进行了分析.研究表明,铈的掺杂没有改变K2La2Ti3O10的微晶结构,并使催化剂粒径有所减小.紫外可见漫反射分析表明禁带宽度为2.3eV左右,对可见光具有较高吸收.XPS表明La和Ti为+3和+4价,而Ce则是+3和+4的混合价态.担载2wt%Pt后,在可见光下光催化活性大大提高,当铈的掺杂量为0.5mol%(即Ce取代La的摩尔百分量)时,光催化活性达到最大,产氢速率为0.05mmol/h;光照5h后产氢量为0.22mmol,而纯K2La2Ti3O10的产氢量只有0.037mmol.     

气相渗透法中的溶质吸附效应

在气相渗透仪上，用四个低分子量有机化合物和五个已知平均分子量的窄分布聚苯乙烯低聚体，对ＶＰＯ方法中的溶质吸附效应作了研究，提出了一种对吸附效应作改正的方法．所得结果表明，在扣除溶质吸附效应后，仪器常数Ｋ无分子量依赖性，提高了测定低分子量聚合物数均分子量的准确性．     

Activation of Hydrogen Peroxide by Ionic Liquids: Mechanistic Studies and Application in the Epoxidation of Olefins

Imidazolium‐based ionic liquids that contain perrhenate anions are very efficient reaction media for the epoxidation of olefins with H₂O₂ as an oxidant, thus affording cyclooctene in almost quantitative yields. The mechanism of this reaction does not follow the usual pathway through peroxo complexes, as is the case with long‐known molecular transition‐metal catalysts. By using in situ Raman, FTIR, and NMR spectroscopy and DFT calculations, we have shown that the formation of hydrogen bonds between the oxidant and perrhenate activates the oxidant, thereby leading to the transfer of an oxygen atom onto the olefin demonstrating the special features of an ionic liquid as a reaction environment. The influence of the imidazolium cation and the oxidant (aqueous H₂O₂, urea hydrogen peroxide, and tert‐butyl hydrogen peroxide) on the efficiency of the epoxidation of cis‐cyclooctene were examined. Other olefinic substrates were also used in this study and they exhibited good yields of the corresponding epoxides. This report shows the potential of using simple complexes or salts for the activation of hydrogen peroxide, owing to the interactions between the solvent medium and the active complex.     

基于离散小波变换的岩石SHPB测试信号去噪

运用离散小波阈值去噪原理对SHPB测试信号进行了处理,针对SHPB测试信号持时短、突变快等特性,并根据各小波基对信号的重构均方根误差,选择Symlets小波系中的小波基Sym5为适合SHPB测试信号小波分析的最佳小波基,并运用无偏估计程序SURE确定了各分解层的阈值。比较了小波阈值去噪与动态应变仪中常规低通滤波器去噪的信噪比和均方根误差,研究结果表明,相对于常规低通滤波器的去噪处理,离散小波变换不仅有良好的去噪效果,而且能得到更精确的重构信号,可以取代动态应变仪中的低通滤波器对SHPB测试信号进行去噪处理。     

Synthesis,Characterization and Self‐Assembly of Novel Amphiphilic Block Copolymers with a Polyhedral Oligomeric Silsesquioxanes Moiety Attached at the Junction of the Two Blocks

A novel well‐defined amphiphilic block copolymer, with the polyhedral oligomeric silsesquioxane (POSS) moiety at the junction of the two blocks of polystyrene and poly(ethylene oxide) (PEO), was designed and synthesized. First, a macroinitiator containing a POSS moiety and a PEO chain was prepared and then atom transfer radical polymerization of styrene was carried out in the presence of the macroinitiator in bulk. The polymerization results show that the process bears the characteristics of controlled/living free radical polymerizations. The structure and molecular weight of the polymers were characterized by GPC, ¹H NMR, and FT‐IR spectroscopy. The self‐assembly behaviors of the polymers was investigated by TEM and SEM. It was observed that the polymers can self‐assemble into vesicles in aqueous solution.

     

Separation, concentration and determination of chloramphenicol in environment and food using an ionic liquid/salt aqueous two-phase flotation system coupled with high-performance liquid chromatography

Ionic liquid–salt aqueous two-phase flotation (ILATPF) is a novel, green, non-toxic and sensitive samples pretreatment technique. ILATPF coupled with high-performance liquid chromatography (HPLC) was developed for the analysis of chloramphenicol, which combines ionic liquid aqueous two-phase system (ILATPS) based on imidazolium ionic liquid (1-butyl-3-methylimidazolium chloride, [C₄mim]Cl) and inorganic salt (K₂HPO₄) with solvent sublation. In ILATPF systems, phase behaviors of the ILATPF were studied for different types of ionic liquids and salts. The sublation efficiency of chloramphenicol in [C₄mim]Cl–K₂HPO₄ ILATPF was influenced by the types of salts, concentration of K₂HPO₄ in aqueous solution, solution pH, nitrogen flow rate, sublation time and the amount of [C₄mim]Cl. Under the optimum conditions, the average sublation efficiency is up to 98.5%. The mechanism of ILATPF contains two principal processes. One is the mechanism of IL–salt ILATPS formation, the other is solvent sublation. This method was practical when applied to the analysis of chloramphenicol in lake water, feed water, milk, and honey samples with the linear range of 0.5–500 ng mL⁻¹. The method yielded limit of detection (LOD) of 0.1 ng mL⁻¹ and limit of quantification (LOQ) of 0.3 ng mL⁻¹. The recovery of CAP was 97.1–101.9% from aqueous samples of environmental and food samples by the proposed method. Compared with liquid–liquid extraction, solvent sublation and ionic liquid aqueous two-phase extraction, ILATPF can not only separate and concentrate chloramphenicol with high sublation efficiency, but also efficiently reduce the wastage of IL. This novel technique is much simpler and more environmentally friendly and is suggested to have important applications for the concentration and separation of other small biomolecules.     

介质对配合物稳定性的影响——Ⅱ.Cu(SCN)+—NaNO3—二氧六环—水体系

本文用分光光度法确定了25℃时配阳离子Cu(SCN)~+在NaNO_3—二氧六环—H_2O介质中的稳定常数。溶剂组成变化范围为0,5,10,15和20wt％二氧六环,离子强度范围为0.2～3.0moledm~(-3),溶液的pH=1.5～1.6。本文提出了基于Pitzer方程式的最小二乘多项式逼近法,确定出各种不同组成混合溶剂中配合物的热力学稳定常数。讨论了该常数和一级介质效应与溶剂组成和介电常数的关系。     

Carbon nanotube salts. Arylation of single-wall carbon nanotubes

[reaction: see text] Carbon nanotube salts prepared by treating single-wall carbon nanotubes (SWNTs) with lithium in liquid ammonia react readily with aryl iodides to give SWNTs functionalized by aryl groups.