A novel threefold‐interpenetrating primitive cubic network based on a dinuclear Zn2 node

In the mixed‐ligand metal–organic polymeric compound poly[[μ₂‐1,4‐bis(imidazol‐1‐yl)benzene](μ₂‐terephthalato)dizinc(II)], [Zn₂(C₈H₄O₄)₂(C₁₂H₁₀N₄)]_n or [Zn₂(bdc)₂(bib)]_n [H₂bdc is terephthalic acid and bib is 1,4‐bis(imidazol‐1‐yl)benzene], the asymmetric unit contains one Zn^II ion, with two half bdc anions and one half bib molecule lying around inversion centers. The Zn^II ion is in a slightly distorted tetrahedral environment, coordinated by three carboxylate O atoms from three different bdc anions and by one bib N atom. The crystal structure is constructed from the secondary building unit (SBU) [Zn₂(CO₂)₂N₂O₂], in which the two metal centers are held together by two bdc linkers with bis(syn,syn‐bridging bidentate) bonding modes. The SBU is connected by bdc bridges to form a two‐dimensional grid‐like (4,4)‐layer, which is further pillared by the bib ligand. Topologically, the dinuclear SBU can be considered to be a six‐connected node, and the extended structure exhibits an elongated primitive approximately cubic framework. The three‐dimensional framework possesses a large cavity with dimensions of approximately 10 × 13 × 17 Å in cross‐section. The potential porosity is filled with mutual interpenetration of two identical equivalent frameworks, generating a novel threefold interpenetrating network with an α‐polonium topology [Abrahams, Hoskins, Robson & Slizys (2002). CrystEngComm, 4 , 478–482].     

基于全息液晶/聚合物光栅的分布反馈式激光器的波长调谐特性研究

首先制备了不同周期的染料掺杂全息液晶/聚合物光栅并进行激光抽运实验, 得到了激光器的调谐曲线,确定了激光器在574 nm到685 nm的谱带里均可以实现激光输出, 即激光器具有110 nm左右的可调谐范围. 之后, 通过温控仪控制样品的温度, 对周期为610 nm的染料掺杂全息液晶/聚合物光栅进行激光抽运, 探测不同温度下的输出激光光谱, 观察到随着温度由20℃升高到65℃, 激光器的中心波长由627.9 nm减小到623 nm, 产生了4.9 nm的波长蓝移.     

2-呋喃甲硫醇修饰环糊精形成互锁式螺旋柱状超分子的自组装行为

利用单-(6-氧-对甲基苯磺酰基)-β-环糊精和2-呋喃甲硫醇反应得到单修饰环糊精, 单[6-硫-6-(2-甲基呋喃)]-β-环糊精. 通过X-ray衍射分析及核磁光谱等方法研究了其在溶液和固态中形成线状超分子的分子自组装行为. 结果表明, 化合物在固态中通过呋喃基团从第二面羟基连续插入到另一个环糊精的空腔, 形成了互锁式螺旋柱状超分子, 而且在溶液中也显示了相似的自组装行为, 其键合常数K及聚合度n分别为450 mol^-1·L和1.9.     

Li-S电池硫正极性能衰减机理分析及研究现状概述

由于汽车工业的持续发展, 对高能量密度二次电池的需求逐步增加, 锂硫电池开始走进人们的视野. 锂硫电池的理论比能量高达2600 Wh/kg, 而单质硫的理论比容量达1680 mAh/g. 同时, 硫的储量丰富, 廉价, 并且环境友好. 虽然可充电锂硫电池相比于传统锂离子电池有诸多优势, 但目前其可实现的实际比容量远低于理论比容量, 循环寿命也较短等弊端限制了其大规模应用. 作者从Li-S电池正极的工作原理出发, 对硫正极容量损失及衰减机理做了深刻的解析, 并结合本实验室的工作归纳总结了导致硫正极容量衰减的主要因素. 针对硫正极容量衰减因素, 从碳导电结构、聚合物包覆以及纳米金属氧化物添加剂等方面, 对近年来提高硫正极性能的主要研究方向及最新研究进展进行了综述, 并对其中存在的问题进行分析, 最后对提高Li-S电池的整体性能提出展望.     

电沉积法制备铂纳米粒子过程中卤素阴离子对粒子形貌及电催化性质的影响

在电化学沉积铂纳米粒子的过程中, 通过添加卤素阴离子, 可以显著地改变纳米粒子的形貌. 通过添加氯离子、溴离子和碘离子, 可以在导电基底上分别获得球形、片状及立方结构的铂纳米粒子. 对卤素阴离子影响电沉积铂纳米粒子形貌的原因进行了探讨. 研究了铂纳米粒子的电催化活性, 发现通过添加卤素阴离子制备得到的铂纳米粒子对于甲醇的电化学催化氧化表现出较低的电化学催化活性. 通过电化学氧化法全部或部分除去铂表面吸附的卤素阴离子后, 纳米粒子对甲醇的电化学催化氧化活性显著提高.     

Synthesis and Structure of Three Novel Complexes Based on 4-Chlorophenyloxyacetic Acid

Three new metal–organic complexes, [CoL₂(H₂O)₄] 1, [CdL₂(H₂O)₂] 2, and [CuL₂(H₂O)₂] 3 [HL = 4-chlorophenyloxyacetic acid], have been synthesized and characterized by IR spectra, elemental analysis, fluorescence spectra, and single-crystal X-ray diffraction. Compounds 1, 2, and 3 are all zero-dimensional dimers. The carboxylate ligand exhibits different coordination modes in all compounds. These compounds exhibit interesting supramolecular architecture according to O–H···O and C–H···Cl interactions. Compounds 1, 2, and 3 develop to different framework though they all are from same ligands, which will be helpful to design of different materials.

[Supplemental materials are available for this article. Go to the publisher's online edition of Molecular Crystals and Liquid Crystals to view the free supplemental file: CCDC 902676, 902674, 902675 contains the supplementary crystallographic data for this article. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax: C44 1223 336033; e-mail: deposit@ccdc.cam.ac.uk).]     

门电压控制的硅烯量子线中电子输运性质

硅烯是由单层硅原子形成的二维蜂窝状晶格结构,具有石墨烯类似的电学性质,由于硅烯中存在比较强的自旋轨道耦合而备受关注.本文利用非平衡格林函数方法研究了门电压控制的硅烯量子线中电子输运性质和能带结构.研究发现,只有在较强的门电压下,而且硅烯量子线具有较好的锯齿形或扶手椅形边界而不存在额外硅原子时,硅烯量子线中才存在无能隙的自旋极化边缘态.另外,计算结果表明这种门电压控制的硅烯量子线中边缘态在每个能谷处自旋是极化的.这些计算结果将为实验上利用电场制作硅烯纳米结构提供理论支持.     

Rapid determination of anilines in water samples by dispersive liquid-liquid microextraction based on solidification of floating organic drop prior to gas chromatography-mass spectrometry

A rapid, sensitive and environmentally friendly method for the analysis of 14 anilines in water samples by dispersive liquid–liquid microextraction based on solidification of floating organic drop (DLLME-SFO) prior to gas chromatography–mass spectrometry (GC-MS) was developed and optimized. In the proposed method, cyclohexane was used as the extraction solvent as its toxicity was much lower than that of the solvent usually used in dispersive liquid–liquid microextraction (DLLME). In the optimized conditions, the method exhibited good analytical performance. Based on a signal-to-noise ratio of 3, limits of detection for anilines were in the range of 0.07 to 0.29 μg L⁻¹, and the linear range was 0.5–200 μg L⁻¹ with regression coefficients (r ²) higher than 0.9977. It was efficient for qualitative and quantitative analysis of anilines in water samples. The relative standard deviations varied from 2.9 to 8.6 % depending on different compounds indicating good precision. Tap water and river water were selected for evaluating the application to real water samples. The relative recoveries of anilines for the two real samples spiked with 10 μg L⁻¹ anilines were in the scope of 78.2–114.6 % and 77.3–115.6 %, respectively.     

Lanthanide-ion-tuned magnetic properties in a series of three-dimensional cyano-bridged Ln(III)W(V) assemblies

The reaction of [W(CN)(8)](3-) with Ln(3+) and pyrazine in acetonitrile yielded a series of isostructural compounds formulated as Ln(H(2)O)(4)(pyrazine)(0.5)W(CN)(8) (Ln = La(1), Ce(2), Pr(3), Nd(4), Sm(5), Eu(6), Gd(7)). The Ln(iii) and W(v) centers in the structure are linked through cyanide groups to form two-dimensional (2D) layers, which are further pillared by pyrazine, generating 3D frameworks. The magnetic behavior for compounds 1-7 were driven by the lanthanide ions involved. The Ln(iii) and W(v) ions in compounds 2 and 5 are ferromagnetically coupled with magnetic ordering occurring at 2.8 K, comparable with magnetic ordering with the critical temperature of 1.9 K for compound 4. In addition, the antiferromagnetic interactions were observed in compounds 3 and 7, while no significant magnetic couplings were found in compounds 1 and 6.