The use of sulfide cluster-derived catalysts to understand the promotional effect in hydrotreatment catalysis

Sulfide cluster-derived ensembles are promising models of the active sites in commercial hydrotreatment catalysts. A series of sulfide clusters were adsorbed intact onto high-surface-area γ-alumina, magnesium oxide and activated carbon supports, then pretreated to produce highly dispersed catalytic ensembles with sizes similar to those of their precursor clusters. The activities of the bimetallic cluster-derived catalysts were significantly higher than those of the monometallic catalysts. We took this as evidence that direct interactions between molybdenum and the promoter element cause the promotional effect observed in commercial hydrotreatment catalysts. The hydrodesulfurization and hydrodenitrogenation activities correlated with the extent of molybdenum reduction. Our results suggested that the active sites in promoted hydrotreatment catalysts are centered on molecular-scale ensembles containing molybdenum, sulfur and the promoter element.     

论砂金矿物的表面生长结构和砂金矿床成因

经对采自砂金矿床，金矿床氧化带和块金（狗头金）样品的观察研究，特别是采用电子显微镜进行精细矿物学研究后发现，所研究的样品无一例外地均具有代表性，它是表生电流动溶液中生成的表面生长结构图象，证明它们均是在天然水系和开放式物化环境中白含金溶液不断的淀积作用生成的。因而砂金颗粒均属表生条件下形成的溶液沉积矿物，砂金矿床从成因上说应属表生化学沉积矿床。砂金颗粒是在原地生成的。金粒表面生长结构应作为标型特征。     

Regio- and Stereocontrolled Nucleophilic Addition Reactions of An Unsymmetrically Disbustituted Butadiene η4-Molybdenum Cationic Complex

The reactions of a new cationic complex, [Cp(CO)₂Mo(η⁴-2-methyl-3-SPh-C₄H₄)]⁺ PF^?₆ (3), with carbon, hydride, and nitrogen nucleophiles were found to give only the C-1 addition products in good yield. The X-ray crystal structures of two of the addition products 4a and 4e confirm the regio- and stereochemistry of the nucleophilic additions.     

茶叶矿质元素浸出量与茶叶冲泡时间及冲泡次数的关系

研究了茶汤中茶叶１０种矿质元素（Ｋ、Ｃａ、Ｍｇ、Ｐ、Ａｌ、Ｆｅ、Ｍｎ、Ｓｒ、Ｂａ、Ｚｎ）的浸出量与茶叶冲泡次数以及冲泡时间的关系．结果表明：（１）茶叶中１０种元素的浸出量与茶叶冲泡次数之间具有显著的指数函数相关,相关方程为ｙ＝ａｅ－ｂｘ,１０种元素的浸出量与茶叶冲泡时间之间具有显著的对数函数相关,相关方程为ｙ＝ａ＋ｂｌｇｘ,各元素在两方程中的相关显著性均为α＜０．０１;（２）性质相近的元素,如Ｂａ与Ｓｒ在上述函数中的变化行为更为相近;（３）元素Ｋ、Ｚｎ、Ａｌ、Ｍｇ浸出比在３０％以上,可认为是易浸出元素,而元素Ｍｎ、Ｆｅ、Ｓｒ、Ｂａ、Ｃａ的浸出比低于３０％,可认为是较难浸出元素;（４）茶叶与茶汤之比为１∶１０,冲泡水温１００℃,冲泡时间２分钟,３泡茶汤已能充分利用茶叶中常见的人体营养元素Ｋ、Ｍｇ、Ｐ、Ｍｎ、Ｚｎ,元素浸出量与总浸出量之比在６０％以上．     

3,5-diBr-PADAP作锆(Ⅳ)显色剂的分光光度法研究与应用

本文研究了在非离子表面活性剂存在下,用3,5-diBr-PADAP作锆显色剂的胶束增溶分光光度法。在pH1.0～2.0的HCl介质中,配合物吸光度最大且稳定,最大吸收值在610nm处。Zr(Ⅳ)与试剂形成1:2的配合物,摩尔吸光系数为1.10×10~5L·mol~(-1)·cm~(-1),zr(Ⅳ)量在0～30μg/25mL范围内遵守比尔定律。采用钽试剂一苯苹取分离法,适合于钽铌矿中微量锆的测定。     

Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐Molybdate(II) Anions: Synthesis,Spectroscopy, and Density Functional Theory Calculations

Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐molybdate‐(II) anions, [fac‐M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo), which are novel weakly coordinating anions that contain a metal carbonyl/nitrosyl moiety, have been generated in fluorosulfonic acid and completely characterized by multinuclear NMR, IR, and Raman spectroscopy as well as ESI mass spectrometry. ESI MS measurements performed for the first time on a superacidic solution system unambiguously reveal the formation of the monoanionic, mononuclear W and Mo complexes formulated as [M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo). Multinuclear NMR spectroscopic studies at natural abundance and ¹³C and ¹⁵N enrichment clearly indicate the presence of one CO ligand, two equivalent NO ligands, and two types of nonequivalent SO₃F^? groups in a 2:1 ratio. The IR and Raman spectra reveal that the two equivalent NO ligands have a cis conformation, thus indicating a fac structure. Density functional calculations at the B3LYP level of theory predict that these anions have a singlet ground state (¹A′) with a C_s symmetry along with C–O and N–O vibrational frequencies that are in agreement with the experimental observations. Mulliken population analysis shows that the monovalent negative charge is dispersed on the bulky sphere, the surface of which is covered by all the negatively charged O and F atoms with charge densities much lower than SO₃F^?, suggesting that [fac‐M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo) are weakly nucleophilic and poorly coordinating anions.     

VIB金属蝎型配合物(Scorpionate)的研究进展

综述了VIB金属(Mo、W)多吡唑硼配合物近年来的研究进展。详细地叙述了第二代多吡唑硼配体的合成与表征。     

Effect of Neck Formation on the Measurement of Dynamic Interfacial Tension in a Drop Volume Tensiometer

Dynamic interfacial tension values obtained by drop volume tensiometry will be affected under certain experimental conditions by the formation of a neck between the drop and the capillary tip. This phenomenon must be accounted for to obtain accurate values of interfacial tension. In this work, neck formation for a water–mineral oil system is studied under conditions where hydrodynamic effects can be neglected. A model originally developed for the determination of the surface tension of a suspended drop is modified for application to dynamic interfacial tensions of surfactant-containing liquids. The model relates apparent values of interfacial tension calculated from drops possessing necks to actual values. Experiments with Span 80 (sorbitan monooleate) and sodium dodecyl sulfate (SDS) surfactants in a mineral oil–water system are used to test the validity of the developed model. For the small tip diameter used, good agreement is obtained for Span 80 up to the critical micelle concentration, and for low concentrations of SDS, when the surfactant adsorption is diffusion-limited. In both cases, the neck diameter of the growing drop can be considered constant over the range of dynamic interfacial tensions tested.     

矿物的荧光性

文章介绍了矿物发光机理的基本概念以及在生活上的应用，分析、研究了不同产地的同种天然萤石光致荧光光谱特性，给出天然萤石荧光机理。     

Pt/陶瓷电极上醇类的阳极氧化作用及其钼和钨的添加对电极活性的影响

采用电沉积Pt在陶瓷膜的方法制得了一种新型的可用于醇类阳极氧化的陶瓷基底电极,采用在电沉积前用氧化钨的溶胶或硅钨酸或硅钼酸的溶液浸渍陶瓷膜的方法可将钨和钼添加到电极中.实验发现钨和钼的添加可以十分显著地提高催化剂的活性,如对于甲醇的阳极氧化,添加硅钼酸的电极上的电流密度可达到187 mA/cm2,为相同条件下不含硅钼酸的电极的5倍多.对于乙醇的阳极氧化也得到了相同的结果.