A Structural Diversity of Molecular Alkaline-Earth-Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion

A series of molecular group 2 polyphosphides has been synthesized by using air-stable [Cp*Fe(η⁵-P₅)] (Cp*=C₅Me₅) or white phosphorus as polyphosphorus precursors. Different types of group 2 reagents such as organo-magnesium, mono-valent magnesium, and molecular calcium hydride complexes have been investigated to activate these polyphosphorus sources. The organo-magnesium complex [(^DippBDI−Mg(CH₃))₂] (^DippBDI={[2,6-ⁱPr₂C₆H₃NCMe]₂CH}⁻) reacts with [Cp*Fe(η⁵-P₅)] to give an unprecedented Mg/Fe-supramolecular wheel. Kinetically controlled activation of [Cp*Fe(η⁵-P₅)] by different mono-valent magnesium complexes allowed the isolation of Mg-coordinated formally mono- and di-reduced products of [Cp*Fe(η⁵-P₅)]. To obtain the first examples of molecular calcium-polyphosphides, a molecular calcium hydride complex was used to reduce the aromatic cyclo-P₅ ring of [Cp*Fe(η⁵-P₅)]. The Ca-Fe-polyphosphide is also characterized by quantum chemical calculations and compared with the corresponding Mg complex. Moreover, a calcium coordinated Zintl ion (P₇)³⁻ was obtained by molecular calcium hydride mediated P₄ reduction.     

电化学法提锂技术的研究进展及展望

随着新能源产业的不断发展,锂资源的需求量急剧增加。我国具有丰富盐湖锂资源,随着技术的革新与产业化的实践,盐湖提锂技术逐渐走向成熟。电化学法提锂作为众多提锂技术中的新秀,因绿色环保、选择性高、低能耗而备受国内外研究者的关注。本文对国内外电化学提锂技术的研究进展进行综述,并对未来电化学提锂技术的发展给出建议与展望。     

非晶态介孔 FeAlP 催化剂用于合成 1,5-苯二氮类化合物

 A simple and versatile method for the synthesis of 1,5-benzodiazepines from o-phenylenediamine and ketones in the presence of solvents and under solvent-free conditions that used an amorphous mesoporous iron aluminophosphate as catalyst was developed. High yields with excellent selectivity were obtained with a wide variety of ketones under mild reaction conditions. The catalyst had the advantages of ease of preparation, ease of handling, simple recovery, reusability, non toxicity, and being inexpensive.     

无氯 Cu/AC 催化剂的制备及其催化气相甲醇氧化羰基化反应性能

 以 Cu2(NO3)(OH)3/AC (活性碳) 为催化剂前驱体, 在惰性气氛中于不同温度热处理分别制得无氯的 CuO/AC, Cu2O/AC 和 Cu0/AC 催化剂, 并用于甲醇直接气相氧化羰基化合成碳酸二甲酯 (DMC) 反应. 结果表明, 200 °C 处理制得的催化剂中, Cu 物种以 CuO 为主. 随着处理温度的升高, 催化剂中 CuO 含量逐渐降低, 而 Cu2O 含量增加; 400 °C 制备的催化剂中, Cu 物种仅以 Cu2O 形式存在; 而 450 °C 以上处理时则以 Cu0 形式存在. 随着热处理温度的提高, 相应催化剂活性逐渐增加, 表明 CuO, Cu2O 和 Cu0 均具有催化活性, 其活性大小的顺序为 CuO < Cu2O < Cu0. 在 140 °C, CO:MeOH:O2 = 4:10:1, SV = 5 600 h1 条件下, 450 °C 处理制备的 Cu0/AC 催化剂表现出较高的催化甲醇氧化羰基化活性, 其中甲醇转化率达 11.5%, DMC 的时空收率和选择性分别为 261.9 mg/(g•h) 和 76.0%.     

Growth and Spectral Characteristics of Yb3＋-doped LiGd（MoO4）2 Crystal

The Yb3+-doped LiGd(MoO4)2 crystal with the size up to Φ20×30 mm3 has been grown by Czochralski technique.The polarized room temperature absorption and emission spectra have been investigated.This crystal exhibits a broad absorption band centered at 975 nm with an FWHM of 43 and 59 nm for π-and σ-polarization,respectively,and the corresponding maximal absorption cross-sections are 3.36 and 2.42×10-20 cm2.The emission broadband has an FWHM of 47 and 54 nm for π-and σ-polarization,respectively,with the corresponding emission cross sections of 3.92 and 3.34 × 10-20 cm2 at 1020 nm.The measured fluorescence lifetime is 287 μs.     

Effect of indium content and rapid solidification on microhardness and micro‐creep of Sn‐Zn eutectic lead free solder alloy

The Sn‐Zn alloys have been considered as lead‐free solders. In this paper, the effect of 0.0, 0.5, 1.0, 1.5 and 2.0 wt.% Indium as ternary additions on melting temperature, structure, microhardness and micro‐creep of the Sn‐9Zn lead‐free solders were investigated. It is shown that the alloying additions of Indium to the Sn‐Zn binary system result in a suppression of the melting point to 187.9 °C. From x‐ray diffraction analysis, a new intermetallic compound phase, designated β‐In₃Sn is detected. The formation of an intermetallic compound phase causes a pronounced increase in the electrical resistivity and mechanical strength. Also, an interesting connection between dynamic Young's modulus and the axial ratio (c/a) of the unit cell of the β‐Sn was found in which Young's modulus increases with increasing the axial ratio (c/a). The ternary Sn‐9Zn‐xIn exhibits creep resistance superior to Sn‐9Zn binary alloy. The better creep resistance of the ternary alloy is attributed to solid solution effect and precipitation of In₃Sn in the Sn matrix. The addition of small amounts of In is found to refine the effective grain size and consequently, improves hardness. The 89%Sn‐9%Zn‐2%In alloy is a lead‐free solder designed for possible drop‐in replacement of Pb‐Sn solders. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

铷原子饱和吸收光谱与偏振光谱对780nm半导体激光器稳频的比较

将激光频率锁定于合适的参考频率,可以有效地抑制激光器的频率起伏。本文采用铷原子D2线超精细跃迁线的饱和吸收光谱和偏振光谱分别获得鉴频曲线,通过电子伺服系统将频率校正信号负反馈到780 nm光栅外腔反馈半导体激光器外腔的压电陶瓷上的方法对激光器进行稳频。介绍了两种方法的基本原理和实验方案。与激光器自由运转300s时激光器典型的频率起伏约6.6 MHz相比,采用饱和吸收光谱和偏振光谱进行稳频,运转300 s时激光器典型的残余频率起伏分别约为1.5 MHz和0.6 MHz。分析表明,饱和吸收光谱稳频采用了相敏检波技术,需要对激光器进行频率调制,带来了额外的频率噪声,而偏振光谱稳频则是一种完全无频率调制的稳频方案。     

微波消解-FAAS测定皖南茶园土壤中矿质元素含量

采用微波消解-FAAS测定了皖南休宁县茶园不同深度土壤中的矿质元素Cu、Cd、Mn、Zn、Fe、Pb的含量,分析了不同深度土壤中矿质元素的分布特征,结果表明,皖南土壤中矿质元素Cu、Cd、Mn、Zn、Pb 5元素含量随土壤深度呈递减趋势,土壤表层的矿质元素(Cu、Cd、Mn、Zn、Pb)含量高于深层的,这与施肥有关,土...     

Mechanisms of Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation

For the last decade, a variant of pulsed laser ablation, Resonant-Infrared Matrix-Assisted Pulsed Laser Evaporation (RIR-MAPLE), has been studied as a deposition technique for organic and polymeric materials. RIR-MAPLE minimizes photochemical damage from direct interaction with the intense laser beam by encapsulating the polymer in a high infrared-absorption solvent matrix. This review critically examines the thermally-induced ablation mechanisms resulting from irradiation of cryogenic solvent matrices by a tunable free electron laser (FEL). A semi-empirical model is used to calculate temperatures as a function of time in the focal volume and determine heating rates for different resonant modes in two model solvents, based on the thermodynamics and kinetics of the phase transitions induced in the solvent matrices. Three principal ablation mechanisms are discussed, namely normal vaporization at the surface, normal boiling, and phase explosion. Normal vaporization is a highly inefficient polymer deposition mechanism as it relies on collective collisions with evaporating solvent molecules. Diffusion length calculations for heterogeneously nucleated vapor bubbles show that normal boiling is kinetically limited. During high-power pulsed-FEL irradiation, phase explosion is shown to be the most significant contribution to polymer deposition in RIR-MAPLE. Phase explosion occurs when the target is rapidly heated (10⁸ to 10¹⁰ K/s) and the solvent matrix approaches its critical temperature. Spontaneous density stratification (spinodal decay) within the condensed metastable phase leads to rapid homogeneous nucleation of vapor bubbles. As these vapor bubbles interconnect, large pressures build up within the condensed phase, leading to target explosions and recoil-induced ejections of polymer to a near substrate. Phase explosion is a temperature (fluence) threshold-limited process, while surface evaporation can occur even at very low fluences.     

关于Haar 酉元的一个注记

设M 是一个Ⅱ₁ 型因子, τ 是M 的正规的、忠实的迹态, U ∈ M 是一个Haar 酉元, p ∈ M是一个投影, τ (p) = (1/n) (n > 3, n ∈ Z), p 和U 自由. 我们用初等方法证明了若pUp = wh 是pUp 的极分解, 则w 也是一个Haar 酉元且w 和h 是自由的. 我们还给出了pUp 的矩的刻画.