超临界流体干燥过程的分析

以ZrOCl2•8H2O为原料，采用超临界流体干燥（SCFD）法，在短时间内制备出大孔体积高比表面ZrO2气凝胶超细粉．该法具有良好的稳定性和可靠性．建立了醇凝胶中液相含水量的分析方法，为产品质量控制及确认体系是否处于超临界状态提供了依据．对抽提后的溶剂分析表明，SCFD过程是一物理过程．对水的抽提干燥过程亦进行了初步的理论探讨．     

Sm, Pr掺杂CeO2和CeMoO15基固体电解质的结构与性能

采用溶胶凝胶法制备了Sm和Pr掺杂的CeO2和CeMoO15基固体电解质, 通过X射线衍射(XRD)、拉曼光谱(Raman)、场发射扫描电镜(FE-SEM)等手段对氧化物结构进行了分析, 用交流阻抗谱测试了其电性能, 并比较了不同基体及其掺杂体系的结构与电性能. 结果表明, Ce6MoO15基掺杂体系的导电性能高于CeO2基掺杂体系; 元素Mo的加入使Ce6MoO15基材料的晶粒尺寸增大, 晶界相成分减少, 材料的晶界电导率增加, 600 ℃以下材料导电性能明显提高; Pr的掺入减小了材料的晶粒尺寸, 提高了材料的晶界电导率.     

Vapor pressure measurement for water,methanol, ethanol,and their binary mixtures in the presence of an ionic liquid 1-ethyl-3-methylimidazolium dimethylphosphate

Vapor pressure data were measured for water, methanol and ethanol as well as their binary mixtures with an ionic liquid (IL) 1-ethyl-3-methylimidazolium dimethylphosphate ([EMIM][DMP]) at varying temperature and IL-content ranging from mass fraction of 0.10–0.70 by a quasi-static method. The vapor pressure data for the IL-containing binary systems were correlated using NRTL equation with average absolute relative deviation (ARD) within 0.0076, and the binary NRTL parameters was used for predicting the vapor pressure of the IL-containing ternary systems with reasonable accuracy. In addition, the infinite activity coefficients of solvents in [EMIM][DMP] and isobaric vapor–liquid equilibrium for IL-containing ternary systems at 101.325 kPa and mass fraction of IL being 0.5 were predicted with the regressed NRTL parameters. The results indicate that ionic liquid [EMIM][DMP] can depress the volatility of the solvents of water, methanol and ethanol but to a varying degree, leading to the variation of relative volatility of a solvent and even removal of azeotrope for water–ethanol mixture.     

An in situ STM study on the long-range surface restructuring of Au(1 1 1) in a non-chloroaluminumated ionic liquid

We report an in situ STM study of a potential-dependent long-range surface restructuring of Au(1 1 1) electrode in neat 1-butyl-3-methylimidazolium tetrafluoroborates (BMIBF₄) ionic liquid. Au(1 1 1) undergoes a significant long-range surface restructuring upon cathodic excursion to −1.0 V vs. Pt quasi-reference. The restructuring involves the formation of tiny pits, which then develops into a stable worm-like network with an average width of the network grids 2 nm. Electrochemical annealing occurs at the cathodic limit with the presence of a reduction product of cation BMI⁺. A smooth surface is recovered with the appearance of the typical (√3 × 22) reconstruction of Au(1 1 1). The surface restructuring is reestablished upon anodic excursion to −1.3 V after the adsorbed reduction product is oxidized. The long-range surface restructuring phenomenon is tentatively explained as a result of partial charge transfer to the weakly adsorbed BMI⁺, which reduces the metal–metal cohesive energy. In addition, the synergetic effect of the counter anion BF₄⁻ may also be involved. The results provide a knowledge of Au(1 1 1) electrode behavior in the neat ionic liquid and are beneficial to understanding in situ STM results involving surface morphological changes in such a media.     

手性5-l-(艹孟)氧基丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物的合成

研究了手性元5-(R)-(l-(艹孟)氧基)-2(5H)-呋喃酮与取代苯甲醛肟以次氯酸钙作为氧化剂进行的区域选择性原位1,3-偶极环加成反应,同步生成两个新的手性中心,得到了一系列光学纯丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物;应用波谱学手段及X射线单晶衍射法确证了产物的绝对构型,并对产物的核磁共振氢谱规律性加以总结.     

Preconcentration of copper with multi-walled carbon nanotubes pretreated by potassium permanganate cartridge for solid phase extraction prior to flame atomic absorption spectrometry

A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water samples. Important parameters, such as the sample pH, the concentration and volume of eluent, sample flow rate and volume, and interference of coexisting ions, were investigated. The obtained results indicated that proposed method possessed an excellent analytical performance. The linear range, the detection limit, and precison (RSD) were 1-100 ng/mL (R2 = 0.9993), 0.32 ng/mL and 2.88%, respectively. The results showed that copper could be adsorbed quantitatively on the pretreated MWCNTs with potassium permanganate, and proposed method was very useful in the monitoring of copper in the environment.     

包覆型纳米铜-银双金属粉研究

目前,导电胶或者电磁波屏蔽涂料用的导电性填料主要有三类,一是铜粉,二是银粉,三是铜-银双金属粉。铜粉具有来源广、价格低廉、导电性好等优点,但其抗氧化性能弱;银粉导电性与抗氧化性好,但其资源日益匮乏。大量的研究试图通过对铜粉进行表面改性来提高其性能。表面改性有两种方法,一是包膜处理,用SiO2溶胶处理铜粉,铜粉抗氧化性能提高,但其表面导电性能大大降低犤1犦;另一类方法是在铜粉表面覆盖一层导电性能与抗氧化性能均佳的银或金而制成双金属粉末犤2～5犦。制取高性能的铜-银双金属粉是该领域的研究重点。目前获得铜-银双金属粉的方…     

Aggregate, Polymer and Cluster Formation from Metal-Imino Carboxylate Complexes

Reaction of tris-(2-aminoethyl)amine (tren) andthe sodium salt of an -ketocarboxylic acid, typically sodium pyruvate, affordsin the presence of a lanthanide ion aseries of complexes and aggregates includingmononuclear, cyclic tetranuclear and polymerspecies of [L¹]^3- ([L¹]^3-=N[CH₂CH₂N=C(CH₃)COO^-]³).The aggregation of these and related d-block elementcomplexes with Na⁺ ions leadsto the formation of polymeric materials, and thefactors influencing the formation and controlof these various aggregation states are discussed.Metal cations also template the aggregationof the fragment [Ni(L²)] ([L²]^2- =CH₂[CH₂N = C(CH₃)COO^-]₂)to give, in high yield, the polynuclearaggregates {[Ni(L²)]₆M}^x+(M = Nd, Pr, Ce, La, x = 3; M = Sr, Ba, x = 2). The structures of{[Ni(L²)]₆M}^x+ show aninterstitial twelve co-ordinate, icosahedralcation M^x+ encapsulated by six [Ni(L²)]fragments. In the presence ofNa⁺, aggregation of [Ni(L²)] fragments affords {[Ni(L²)]₉Na₄(H₂O)(MeOH)(ClO₄)}³⁺ thestructure of whichshows four Na⁺ ions templating the formation ofa distorted tricapped trigonal prismatic[Ni(L²)]₉ cage. Thus, control overconstruction of various polynuclear cages viaself-assembly at octahedral junctions can beachieved using main group, transition metaland lanthanide ion templates.     

Biosorption of copper(II) and zinc(II) from aqueous solution by Pseudomonas putida CZ1

To study Pseudomonas putida CZ1, having high tolerance to copper and zinc on the removal of toxic metals from aqueous solutions, the biosorption of Cu(II) and Zn(II) by living and nonliving P. putida CZ1 were studied as functions of reaction time, initial pH of the solution and metal concentration. It was found that the optimum pH for Zn(II) removal by living and nonliving cells was 5.0, while it was 5.0 and 4.5, respectively, for Cu(II) removal. At the optimal conditions, metal ion biosorption was increased as the initial metal concentration increased. The adsorption data with respect to both metals provide an excellent fit to the Langmuir isotherm. The binding capacity of living cells is significantly higher than that of nonliving cells at tested conditions. It demonstrated that about 40-50% of the metals were actively taken up by P. putida CZ1, with the remainder being passively bound to the bacterium. Moreover, desorption efficiency of Cu(II) and Zn(II) by living cells was 72.5 and 45.6% under 0.1M HCl and it was 95.3 and 83.8% by nonliving cells, respectively. It may be due to Cu(II) and Zn(II) uptake by the living cells enhanced by intracellular accumulation.     

MCM-41-HY复合分子筛的合成及其在深度加氢脱硫中的应用

在水热条件下合成了包覆型MCM-41-HY复合分子筛.采用XRD、N2气吸附和SEM等方法对其进行了表征.结果表明,MCM-41-HY复合分子筛和MCM-41与H型Y沸石(HY)的机械混合物明显不同,在复合分子筛MCM-41-HY中,中孔相MCM-41附晶生长在HY沸石上,将HY包覆起来.以二苯并噻吩为模型化合物,考察了该材料担载NiMo催化剂的加氢脱硫活性.结果表明,MCM-41-HY复合分子筛与MCM-41和HY的机械混合物担载NiMo催化剂的加氢脱硫(HDS)活性相当,但MCM-41-HY复合分子筛担载NiMo催化剂的裂化活性较低.其裂化活性不同的原因在于其载体孔道结构和酸性位的分布不同.