基于1-(2-吡啶甲基)-1, 2, 4-三唑的金属有机化合物的合成及反应研究

本文合成了1-（2-吡啶甲基）-1,2,4-三唑（L）,并研究了其与有机锡和羰基钼（钨）的配位反应,合成了通过三唑4位氮原子以单齿形式配位的有机锡衍生物L₂SnR₂Cl₂（R=Me,n-Bu或Ph）和羰基金属配合物LM（CO）₅（M=Mo或W）,以及N,N螯合双齿配位的四羰基金属配合物LM（CO）₄。当用氯化苄处理L时,制得了相应的三唑盐,该盐用氧化银处理后与M（CO）₅THF或M（CO）₄（NHC₅H₁₀）₂（NHC₅H₁₀为哌啶）反应,得到了基于三唑的氮杂环卡宾衍生物L’M（CO）₅和L’M（CO）₄（L’=1-（2-吡啶甲基）-4-苄基-1,2,4-三唑-5-碳烯）。X-射线单晶衍射分析表明,在L’M（CO）₅中氮杂环卡宾配体L’表现为通过卡宾碳配位的单齿配体;而在L’M（CO）₄中,L’表现为通过卡宾碳和吡啶氮原子配位的螯合[C,N]双齿配体。     

电感耦合等离子体原子发射光谱法测定钛合金中钨、铌、钽

采用电感耦合等离子体原子发射光谱法（ICP-AES）法测定钛合金中W,Nb,Ta元素的含量。样品采用盐酸、氢氟酸和硝酸溶解,并对仪器工作参数和试验条件进行了优化试验,确定了仪器最佳工作条件,考察了钛合金基体和共存元素对待测元素的影响,确定了各待测元素谱线为W207．911nm,Nb309．418nm,Ta240．063nm。选定的待测元素分析线不受合金基体和共存元素的干扰,通过基体匹配消除基体的影响。加标回收率在98％104％之间,测定结果的相对标准偏差为0．3％～2．4％（n=8）,方法的检出限为0．003-0．013μg／mL。进行了标准物质对照试验,试验结果与标准值相符。     

Determination of Cr(VI) by portable tungsten coil electrothermal atomic absorption spectrometer after surfactant-assisted dispersive liquid-liquid microextraction

As a new developed instrument, a portable tungsten coil electrothermal atomic absorption spectrometer (W-coil ET-AAS) was first coupled with surfactant assisted dispersive liquid–liquid microextraction (SA-DLLME) to improve its analytical performance and expand its applications in this work. SA-DLLME was very simple, rapid and the extraction efficiency was considerably improved by the effect of surfactant, which was suitable to be coupled with the portable instrument in field analysis. After SA-DLLME, concentrated chromium in organic phase was directly determined on W-coil atomiser. The influence factors relevant to SA-DLLME and instrumental conditions were studied systematically. Under the optimal conditions, the limit of detection (LOD) for Cr(VI) was 0.016 µg L^?1, with sensitivity enhancement factor (EF) of 107. The relative standard deviation (RSD) for seven replicate measurements of 0.5 µg L^?1 of Cr(VI) was 4.6%. The recoveries for the spiked samples were in the acceptable range of 96.8–104%. The rapid, simple and high effective method greatly improved the sensitivity of this portable spectrometer for the determination of Cr(VI) and was applied to the analysis of ultra-trace Cr(VI) in real and certified water samples with satisfactory results.     

Electrothermal atomic absorption spectrometric determination of cadmium in environmental samples with niobium wire preconcentration method

A preconcentration method by adsorption of cadmium on a niobium wire was developed for the environmental waters, followed by electrothermal atomic absorption spectrometry with a tungsten tube atomizer. After the preconcentration, the niobium wire was directly inserted into the tungsten tube atomizer. In the preconcentration (adsorption) process of cadmium, the optimal immersing time was 60?s. The effects of large amounts of concomitants on the preconcentration of cadmium were evaluated. When 10³–10⁴ fold excess of matrix elements existed in aqueous solution at pH 4 and 9, the cadmium response was profoundly affected by the matrix elements. However, the cadmium absorption signal was not significantly influenced at pH 7. Therefore, pH 7 was selected for the application into the real environmental samples. Under the optimal conditions, the detection limit (3S/N) for cadmium by the niobium wire preconcentration method was 7.0?pg?mL^?1 and the relative standard deviation was 6.8%. The method with preconcentration on a niobium wire was applied to the determination of cadmium in water and proved to be sensitive, simple and convenient. Because this preconcentration method can be utilized in the in situ treatment of trace cadmium in environmental water samples, it was unnecessary to carry the water samples to the analytical work place. The technique was shown to be useful for the determination of cadmium in environmental water samples at 0.1–1?µg?L^?1 levels.     

A Click Approach to Polymetallic Chromium(0) and Tungsten(0) Fischer‐Carbene Complexes and Their Use in the Synthesis of Functionalized Polymetallic Metal?Carbene Complexes

Alkynylamino Cr⁰ and W⁰ Fischer carbenes undergo a CuAAC reaction with a diverse range of di‐, tri‐, and tetra‐azides to produce polymetallic chromium(0) and tungsten(0) (Fischer)‐carbene complexes in good‐to‐excellent yields. This method is simple, versatile, and is suitable for the preparation of a diverse range of structures with a high level of symmetry. Moreover, the resulting polymetallic carbene complexes are suitable partners for the peripheral functionalization of the metal nuclei, whilst retaining the metal fragment. This fact has been demonstrated in a simultaneous Pauson–Khand reaction, which, in some cases, allows for the generation of four bicyclic [5,5] rings on the periphery of a tetrametallic molecule in a process that involves the formation of 12 new C? C bonds, with four simultaneous CO‐insertion processes. The electrochemistry of the polymetallic Fischer carbenes show completely independent behavior for each nucleus, as well as an anomalous observation of the reversible oxidation of the allyl substituents, which has not been reported before in this class of chemistry.     

氮化钨-钨/掺氮有序介孔碳复合材料的制备及其氧还原性能

采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料（WN-W/NOMC）,作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量,在掺氮量为7%（w/w）时,实验发现材料能够保持完整有序介孔结构,测试其比表面积高达835 m²·g^-1,透射电子显微镜（TEM）测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O₂饱和的0.1 mol·L^-1 KOH溶液中测试了材料的氧还原催化性能（ORR）,显示其起始电位为0.87 V（vs RHE）,极限电流密度为4.49 mA·cm^-2,氧还原反应的转移电子数为3.4,接近于20%（w/w）商业Pt/C的3.8,说明该材料表现出近似4电子的氧还原反应途径。研究结果表明,WN-W/NOMC的催化性能虽然稍弱于商业铂碳（0.99 V,5.1 mA·cm^-2）,但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。     

桥头碳上氮杂芳基功能化的双吡唑甲烷与羰基钨反应

研究了(氮甲基咪唑-2-基)双(3,5-二甲基吡唑)甲烷(L¹),2-吡啶基双(3,5-二甲基吡唑)甲烷(L²)及4-吡啶基双(3,5-二甲基吡唑)甲烷(L³)与羰基钨的反应,合成了一系列以单齿,双齿及三齿氮配位的羰基金属衍生物LW(CO)₅ (L=L¹或L³),LW(CO)₄ (L=L¹,L²或L³)和LW(CO)₃ (L=L¹或L²).核磁,红外及X-射线单晶衍射分析表明这3种配体表现出了可变的配位方式.在LW(CO)₅中,当配体为L¹时,其倾向于通过咪唑氮与金属配位,而为L³则倾向于利用吡啶氮与金属作用;在LW(CO)₄中,配体L¹表现为通过咪唑氮和吡唑氮原子配位的[N,N']双齿配体,而L²和L³表现为通过吡唑氮原子配位的[N,N]双齿配体;在LW(CO)₃中,L¹和L²起着[N,N,N']三齿螯合配体的作用.     

离子液体辅助水热法合成六方WO3纳米棒束

提出了利用简单的离子液体1-甲基-3-乙基-咪唑溴辅助水热法合成六方WO₃纳米棒束的方法,对其结构进行了表征,并讨论其形成机理。TEM照片表明：WO₃纳米棒束由长200~300 nm、直径25~30 nm的纳米棒组装而成。离子液体1-甲基-3-乙基-咪唑溴在纳米棒的形成过程中起到了结构导向剂的作用。     

Inverse Hall–Petch like behaviour in a mechanically milled nanocrystalline Al5Fe2 intermetallic phase

In the present investigation, the indentation study on the high-energy ball-milled nanocrystalline Al₅Fe₂ intermetallic compound has established the inverse Hall–Petch (IHP) behaviour. The structural characterisation of the milled powder particles by X-ray diffraction (XRD) and transmission electron microscopy has shown the evolution of nanocrystalline phase. Micro-indentation measurements have revealed the increase in hardness with decreasing grain size, reaching to a maximum of 9.0 ± 0.3 GPa up to a grain size of 32 ± 4 nm, followed by a decrease. The decrease in hardness with further refinement, an indication of grain size softening, demonstrates the IHP-like behaviour. The deviation from the Hall–Petch behaviour has been discussed using various models based on the dislocations and grain boundary-mediated processes. From the analysis, it appears that the model based on mesocopic grain boundary sliding phenomena is more appropriate to account for the observed grain size softening.