Chemistry of polyfunctional molecules-123. Reactions of BiBr3, SbI3 and AsI3 with LiN(PPh2)2; X-ray structure of a cyclophosphazene salt containing arsenic(I)

BiBr₃ or SbI₃ react at 20°C with LiN(PPh₂)₂ (1) to give elementary Bi or Sb and the P---P coupled phosphazene ligand Ph₂P---N=PPh₂---PPh₂=N---PPh₂ (2). The reaction of AsI₃ with 1 at room temperature formed yellow needles of the eight-membered heterocycle (3), whereas AsI₃ interacted at 80°C with 1 in the molar ratio of 1:3 to give elementary arsenic and 2. Treatment of AsI₃ and 1 at 20°C in a 1:2 stoichiometry yielded the seven-membered, cyclic arsenium(I) salt

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I·4THF (5·4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis.     

(Ba, Sr)TiO3纳米棒的反相微乳法制备与表征

在氢氧化钡和氢氧化锶水溶液/Triton X-100/环己烷/正己醇四元W/O型反相微乳液中制备了钛酸锶钡纳米棒, 研究了ω₀值(水与表面活性剂Triton X-100的物质的量之比)、反应物浓度、陈化时间对产品形貌和尺寸的影响, 用TEM, SAED, SEM, EDS和XRD等技术对产品进行了表征. 结果表明, 所得Ba_0.7Sr_0.3TiO₃纳米棒长约500～1200 nm、直径约为50～120 nm; 具有立方相单晶结构. 产品中钡、锶、钛的物质的量之比约为0.7∶0.3∶1.     

偶联剂对钛酸钾晶须/双马来酰亚胺树脂摩擦磨损性能的影响

研究了不同偶联剂及钛酸钾晶须添加量对钛酸钾晶须 /双马来酰亚胺树脂复合材料的摩擦磨损性能的影响 .结果发现 ,钛酸钾晶须能明显提高复合材料的耐磨性 ,晶须的加入使材料的磨损率得到显著降低 ;钛酸钾晶须对材料具有一定的润滑性 ,添加晶须后材料的摩擦系数与树脂基体基本相当 ;偶联剂对复合材料的摩擦系数影响不大 ,但是合适的偶联剂对材料耐磨性的提高则具有明显的作用 .晶须添加量较低时 ,复合材料的磨损机理主要为较严重的粘着磨损 ,晶须添加量较高时 ,疲劳磨损占主导地位 .     

Hydrated Bi-Ti-Bimetal Ethylene Glycol: A New High-Capacity and Stable Anode Material for Potassium-Ion Batteries

Potassium-ion batteries have emerged not only as low-cost alternatives to lithium-ion batteries, but also as high-voltage energy storage systems. However, their development is still encumbered by the scarcity of high-performance electrode materials that can endure successive potassium-ion uptake. Herein, a hydrated Bi-Ti bimetallic ethylene glycol (H-Bi-Ti-EG) compound is reported as a new high-capacity and stable anode material for potassium storage. H-Bi-Ti-EG possesses a long-range disordered layered framework, which helps to facilitate electrolyte ingress into the entire Bi nanoparticles. A suite of spectroscopic analyses reveals the in situ formation Bi nanoparticles within the organic polymer matrix, which can alleviate stresses caused by the huge volume expansion/contraction during deep cycles, thereby maintaining the superior structural integrity of H-Bi-Ti-EG organic anode. As expected, H-Bi-Ti-EG anode exhibits a high capacity and superior long-term cycling stability. Importantly for potassium storage, it can be cycled at current densities of 0.1, 0.5, 1, and 2 Ag⁻¹ for 800, 700, 1000, and even 6000 cycles, retaining charging capacities of 361, 206, 185, and 85.8 mAh g⁻¹, respectively. The scalable synthetic method along with the outstanding electrochemical performance of hydrated Bi-Ti-EG, which is superior to other reported Bi-based anode materials, places it as a promising anode material for high-performance potassium storage.     

Intercalative Motifs-Induced Space Confinement and Bonding Covalency Enhancement Enable Ultrafast and Large Sodium Storage

Alloying-type metal sulfides with high theoretical capacities are promising anodes for sodium-ion batteries, but suffer from sluggish sodiation kinetics and huge volume expansion. Introducing intercalative motifs into alloying-type metal sulfides is an efficient strategy to solve the above issues. Herein, robust intercalative In S motifs are grafted to high-capacity layered Bi₂S₃ to form a cation-disordered (BiIn)₂S₃, synergistically realizing high-rate and large-capacity sodium storage. The In S motif with strong bonding serves as a space-confinement unit to buffer the volume expansion, maintaining superior structural stability. Moreover, the grafted high-metallicity Indium increases the bonding covalency of Bi S, realizing controllable reconstruction of Bi S bond during cycling to effectively prevent the migration and aggregation of atomic Bi. The novel (BiIn)₂S₃ anode delivers a high capacity of 537 mAh g⁻¹ at 0.4 C and a superior high-rate stability of 247 mAh g⁻¹ at 40 C over 10000 cycles. Further in situ and ex situ characterizations reveal the in-depth reaction mechanism and the breakage and formation of reversible Bi S bonds. The proposed space confinement and bonding covalency enhancement strategy via grafting intercalative motifs can be conducive to developing novel high-rate and large-capacity anodes.     

超细粉Pb0.75Ca0.25[(Ni1/3Nb2/3)0.08Ti0.912Mn0.008]O3的制备与表征

报道了用化学共沉淀法制备掺杂Ca、Ni、Nb、Mn钛酸铅超细陶瓷粉末的方法。制得的粉料化学式为:Pb_0.75Ca_0.25[(Ni_1/3Nb_2/3)_0.08Ti_0.912Mn_0.008]O₃,粒径小于0.1μm,所有的掺杂元素均能定量掺入。     

Sm~(3 )在硼酸盐玻璃中的发光及Bi~(3 )对Sm~(3 )的敏化作用

早在六十年代,人们为了寻找较好的激光玻璃,曾对Sm~(3 )离子掺杂的玻璃中的光谱进行过研究。为了探寻新型的激光,发光玻璃,又进一步研究了Sm~(3 )在玻璃中的发光和敏化。我们以寻找一种高亮度,低成本的发光玻璃为目的,研究了基质玻璃组成,敏化离子及其浓度对Sm~(3 )发光性质的影响。 选择B_2O_3-BaO-M_mO_n(M_mO_n=Li_2O,Na_2O,K_2O,MgO,CaO,SrO)玻璃体系,所用原料的纯度皆为分析纯以上,用陶瓷坩埚在1250℃掺杂氧化钐(纯度均大于99％),玻璃的荧光谱和激发光谱,用MPF-4型荧光分光光度计测定。     

Electrical conduction nature and phase transition in CaTi1−x FexO3−δ (x = 0.1–0.5)

Transport numbers for oxygen ions and protons are measured by an emf method in the system CaTi_1?x Fe_xO_3?δ (x = 0.1–0.5) in the oxidizing and reducing atmospheres in the temperature interval 973–1173 K. It is shown that the compounds under study are mixed ion-electron conductors at small iron concentrations and electron conductors, at large iron contents. The proton conductivity in the compounds is very poor and does not exceed 0.5% in air. On the basis of the temperature dependences of transport numbers for ions and linear expansion, it is established that the CaTi_0.9Fe_0.1O_3?δ system has a phase transition of a second order in a reducing environment at 1020–1050 K. The total and partial electron conductivities of CaTi_0.9Fe_0.1O_3?δ are studied as a function of the partial pressure of oxygen at 1173 K. The nature of electroconduction in CaTi_1?x Fe_xO_3?δ is discussed.     

The Effect of the Catalyst Used on the Kinetics of Di-2-Ethylhexyl Maleate Synthesis

Kinetics of the esterification of maleic anhydride with 2-ethylhexanol in the presence of sulfuric acid, amphoteric tetrabutyl titanate or in the absence of external catalyst has been studied. The kinetic equations and kinetic parameters have been determined.