The Long‐Term Stability of KO2 in K‐O2 Batteries

The rechargeable K‐O₂ battery is recognized as a promising energy storage solution owing to its large energy density, low overpotential, and high coulombic efficiency based on the single‐electron redox chemistry of potassium superoxide. However, the reactivity and long‐term stability of potassium superoxide remains ambiguous in K‐O₂ batteries. Parasitic reactions are explored and the use of ion chromatography to quantify trace amounts of side products is demonstrated. Both quantitative titrations and differential electrochemical mass spectrometry confirm the highly reversible single‐electron transfer process, with 98 % capacity attributed to the formation and decomposition of KO₂. In contrast to the Na‐O₂ counterparts, remarkable shelf‐life is demonstrated for K‐O₂ batteries owing to the thermodynamic and kinetic stability of KO₂, which prevents the spontaneous disproportionation to peroxide. This work sheds light on the reversible electrochemical process of K⁺+e^?+O₂?KO₂.     

Aqua(dipicolinato‐κ3O,N,O′)(1H‐imidazole‐κN3)(1,10‐phenanthroline‐N,N′)manganese(II)

In the title compound, [Mn(C₇H₃NO₄)(C₃H₄N₂)(C₁₂H₈N₂)(H₂O)], the Mn^II centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.383 (3) and 2.421 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.300 (3) Å, and Mn—O = 2.300 (2) and 2.357 (2) Å], one monodentate imidazole ligand [Mn—N = 2.238 (3) Å] and one water molecule [Mn—O = 2.157 (3) Å]. It displays a distorted pentagonal‐bipyramidal geometry, with neighbouring angles within the equatorial plane ranging from 68.05 (9) to 77.48 (10)°. Intermolecular O—H...O hydrogen bonds link the molecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the carboxyl O atoms of the dipicolinate ligand and the protonated imidazole N atom, leading to an infinite two‐dimensional network sheet packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and π–π stacking interactions involving the phenanthroline rings.     

Nickel(II), copper(II) and zinc(II) binding properties and cytotoxicity of tripodal, hexadentate tris(ethylenediamine)--analogue chelators

Three tripodal hexamine chelators based on cis,cis-1,3,5-triaminocyclohexane (tach) have been synthesized and their aqueous coordination chemistry with Ni(II), Cu(II) and Zn(II) is reported. The chelators have a 2-aminoethyl pendant arm attached to each nitrogen of tach, specifically 'tachen'(N,N',N'-tris(2-aminoethyl)cyclohexane-cis,cis-1,3,5-triamine), and two with S,S,S-chiral pendant arms, 'tachpn'(N,N',N'-tris(2-aminopropyl)cyclohexane-cis,cis-1,3,5-triamine) and 'tachbn'(N,N',N'-tris(2-amino-3-phenylpropyl)cyclohexane-cis,cis-1,3,5-triamine. These chelators complex Ni(II), Cu(II) and Zn(II) in aqueous or aqueous/methanolic medium. The crystalline products [M(II)L](X)2 are isolated, where M = Ni(II), Cu(II) or Zn(II), L = tachen, tachpn or tachbn, and X = ClO4-. Crystallographic study of selected tachpn and tachbn complexes shows the chelate arms are constrained in a Lambda(deltadeltadelta) configuration about M(II), which is attributed to their chirality. Solution UV-vis spectroscopy of the Ni(II) and Cu(II) complexes indicates six-coordination and little effect of the pendant arm substitution on ligand-field strength. The single exception is [Cu(tachbn)]2+, whose spectrum is consistent with five-coordination in solution. The cytotoxicities of tachen, tachpn and tachbn toward cultured cancer cells is in the order tachen < tachpn < tachbn < tachpyr, where tachpyr is the aminopyridyl chelator N,N',N'-tris(2-pyridylmethyl)cyclohexane-cis,cis-1,3,5-triamine. The cytotoxicity difference is attributed to an order of increasing lipophilicity, tachen < tachpn < tachbn.     

掺入Ni2+的LiCoO2结构与电化学性能的研究

对LixCo1-yNiyO2-δ系列化合物（x=1）,0＜y＜0．5）的合成条件和它们的非完整结构及其电化学性能间的关系进行了较系统的研究,结果表明Ni2＋掺入ABO2型的化合物中,在取代了Co离子的同时,也以一定的几率分布在A位．并使结构中的A,B和O位都出现一定程度的空位在这种非完整结构中,Co离子具有超高常的平均价态,同时也使Li（Ni）－O和O－O的间距加大,提高了该系列化合物的电导及电池的比容量．     

高价离子掺杂对Bi系成相和结构的影响(Ⅱ)

Sunshine等在BiSrCaCuO体系掺入Pb~(2+)取代部分Bi,经较长时间灼烧后.获得T_(c(0))?110 K以2223相为主的样品,Hongbao等又报导了用Sb部分取代Bi(Pb)SrCaCuO体系中的Bi的研究结果.我们曾用Sb~(5+)、Sn~(4+)、W~(6+)、Mo~(6+)等高价离子部分取代Bi,研究这些离子对BiSrCaCuO体系成相的影响,发现掺高价离子后2223相易于生成并易于得到T_(c(0))?111K的超导体.本文则进一步探讨高价离子掺入的影响及其加速2223相生成的原因。     

Saluenolide A,A Novel Eremophilanolide from Senecio saluenensis

From Senecio saluenensis, a novel eremophilanolide Saluenolide A was isolated. Its structure was elucidated by 2D-NMR technique and X-ray diffraction.     

A Styrylpyrone Dimer from the Bark of Goniothalamus leiocarpus

A dimer of styrylpyrone derivative, leiocarpin E(1), was isolated from the bark of Goniothalamus leiocarpus. Its structures was elucidated by means of spectral and chemical methods. The cytotoxicity of leiocarpin E against HL-60 cells was tested.     

容量稀土镁基贮氢合金的制备及性能研究

采用快淬法制备稀土镁基贮氢合金.研究了覆盖剂,以及镁含量、热处理工艺对合金电性能的影响.当镁含量为1.09wt%时,0.2C放电容量＞380mAh/g,以2C充放,循环寿命＞500次.经XRD分析,贮氢合金具有纳米晶结构,平均晶粒尺寸＜50nm.PCT测试结果表明,随着温度升高,合金的平台压力增加,平台区域变宽,且平坦.     

Controlling of Solution Concentration on Nucleation During Hydrothermal Synthesis of Analcime

Hydrothermal experiments of analcime nucleation and glass dissolution were carried out in autoclaves under the conditions of autogeneous pressures, temperatures of 150 °C ～ 210 °C, and 0.25 M ～ 0.75 M NaOH solutions. The curves of the glass dissolution and analcime formation are S‐shaped. Yet, the two curves are essentially parallel to each other. The time required for a complete dissolution of glass or the commencement of analcime formation is shorter when the concentration of NaOH solution or the temperature is higher. The amount of the weight percent of analcime synthesized is obviously less than the glass dissolved at a given time of an experiment. The weight difference between glass dissolved and analcime (dehydrated) formed is calculated to be represented as the solution concentration. During an experiment, the solution concentration increases gradually to a maximum, then decreases slowly to a constant value with time. On the other hand, nucleation is also gradually increased to a maximum, then is decreased finally to zero with time in a bell‐shaped curve. It is clear that nucleation of analcime is mainly controlled by the solution concentration.     

转换移动窗口因子分析法用于中药组合前后成分变化分析

以正十四烷为内标,采用气相色谱-质谱(GC/MS)联用技术对中药甘草(GUF)、甘遂(EKL)单味药材,以及其组成的药对(GUF-EKL)的挥发成分进行测定,基于一种新的化学计量学方法——转换移动窗口因子分析法(AMWFA)和直观推导式演进特征投影法(HELP)对产生的二维色谱/质谱数据同时进行分辨和解析,获取各个组分的纯色谱曲线和质谱,根据分辨得到的纯质谱在质谱库中进行相似检索以实现对组分的定性。利用AMWFA对组合前后的成分进行归属分析,然后采用面积归一法进行定量。分别在甘草、甘遂及其药对中鉴定出52、51和63个成分,占各自挥发油成分的84%、90%和75%。