A cluster with a mixed M6X12/M6X8 environment: The La6Cl11Co structure

The title compound was synthesized from La, LaCl₃ and Co under Ar atmosphere at 800 °C. It crystallizes in space group P4₂/n (no. 86) with lattice constants a=11.308(2) Å and c=14.441(3) Å. The structure features an isolated Co-centered La₆ octahedron with all corners and edges, and 2 of its 8 triangular faces coordinated by Cl atoms. The La₆Co octahedron is significantly distorted, and the La coordination by Cl atoms deviates from the common close-packing arrangements found in other reduced rare earth metal halides. Structure, bonding and physical properties of the compound have been investigated.     

LiNi0.6Co0.2Mn0.2O2单晶的简易制备及其电化学性能

以Ni_0.6Co_0.2Mn_0.2(OH)₂和LiOH·H₂O为前驱体,在LiOH·H₂O不过量的条件下,采用简单的固相焙烧法,在910℃下制备出单晶LiNi_0.6Co_0.2Mn_0.2O₂(NCM622)。所得材料无需水洗、烘干、退火等处理,可直接用于电极浆料的制备。电化学测试表明,所得NCM622单晶具有较高的比容量和优异的循环稳定性。在0.1C电流下的首次放电比容量达到181.2 mAh·g^-1,0.3C下的首次放电比容量为174.4 m Ah·g^-1。在0.3C的电流密度下,经过300次循环,放电比容量为150.7 mAh·g^-1,容量保持率为86.4%,经500次循环后,放电比容量仍有141.2 mAh·g^-1,容量保持率为81.0%。该电化学性能优于850℃下焙烧的多晶NCM...     

CTAB辅助水热合成高镍三元材料LiNi0.6Co0.2Mn0.2O2及其高低温性能研究

以醋酸盐为原料, 以十六烷基三甲基溴化铵(CTAB)为分散剂, 通过水热合成-高温烧结的方法制备高镍三元正极材料LiNi_0.6Co_0.2Mn_0.2O₂. 结果表明, 适量分散剂CTAB的加入可有效调节材料的颗粒形貌尺寸, 降低锂镍混排, 改善材料的电化学性能. 加入2%(质量分数) CTAB时, 制备的电池材料具有完整有序的层状结构, 且颗粒均匀分散, 具有最佳的循环性能和高低温性能. 该材料在室温及倍率1C下循环100次后, 容量保持率为88.5%. 在?20, 25和55 ℃条件下及倍率0.1C充放电时, 首次放电比容量分别为60.3, 168.5和207.2 mA·h/g.     

Survey of the quasi-ternary system La0.8Sr0.2MnO3–La0.8Sr0.2CoO3–La0.8Sr0.2FeO3

An overview on the variation of the thermal expansion, the electrical conductivity as well as non-stoichiometry of the oxide content as a function of composition within the quasi-ternary system La_0.8Sr_0.2MnO_3−δ–La_0.8Sr_0.2CoO_3−δ–La_0.8Sr_0.2FeO_3−δ in air is presented. The various powders were synthesized under identical conditions. The DC electrical conductivity values of the compositions at 800 °C in air vary in a wide range from 15 to 1338 S cm⁻¹. The magnitude of electrical conductivity of the perovskites is mainly determined by the percentage of cobalt in the compositions. A similar behaviour was observed for the measured thermal expansion coefficients between room temperature and 1000 °C in air, increasing from 10.9 to 19.4 × 10⁻⁶ K⁻¹ as a function of cobalt content. Changes in the oxygen stoichiometry of the materials were characterized by temperature-programmed oxidation measurements.     

Synthesis of new enantiomerically pure C1- and C2-symmetric N-alkyl-benzimidazolium and thiazolium salts

Starting from the commercially available enantiopure (1S,2S)-2-amino-1-phenyl-1,3-propanediol novel enantiomerically pure benzimidazoles were prepared; N-alkylation gave chiral benzimidazolium salts, which were tested in asymmetric benzoin condensations. The synthesis of conceptually new, enantiomerically pure, C₂ symmetric bis-thiazolium and bis-benzimidazolium salts was also developed. These new chiral heterocycles were employed as catalysts in the asymmetric dimerisation of benzaldehyde to give benzoin with moderate enantioselectivity.     

锂离子电池正极材料Li[Li0.2Ni0.2Mn0.6]O2的酸浸改性研究

为提高锂离子电池正极材料Li[Li0.2Ni0.2Mn0.6]O2的首次充放电效率,对固相法合成的该材料进行了酸浸的改性研究。通过X射线衍射(XRD)、扫描电子显微镜(SEM)对所得样品的结构、形貌进行了表征。结果表明,Li[Li0.2Ni0.2Mn0.6]O2经过酸处理后,首次放电效率得到了较大的提高,但是放电中值电压明显下降。其中,0.5 mol.L-1的硝酸浸泡5 h的效果最佳,首次放电效率达到了86.7%,同时放电容量达到最大值的循环次数大大减少。酸浸改性的原因被归结于材料表面出现了富锂尖晶石结构Li4Mn5O12相。     

溶胶凝胶法合成富锂正极材料Li[Li0.2Ni0.2Mn0.6]O2及性能表征

以LiOH.H2O、Mn(CH3COO)2.4H2O和Ni(CH3COO)2.4H2O为原料,分别用柠檬酸(CA)与乙二胺四乙酸(EDTA)为配位剂,采用溶胶凝胶法结合固相烧结法制备富锂固溶体正极材料Li[Li0.2Ni0.2Mn0.6]O2。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、激光粒度仪对所得样品的结构、形貌、粒径分布进行了表征,并测试了材料的电化学性能。采用CA配位制备的材料的电化学性能优于用EDTA配位制备的材料的电化学性能,室温下以18 mA.g-1的电流密度,在2.0~4.8 V电压范围内充放电,用CA制备的材料首次充电比容量高达324 mAh.g-1,首次库伦效率达82%;在180 mA.g-1的电流下,其可逆比容量保持在120 mAh.g-1。     

细胞内不同形态Gd基MRI造影剂的T1/T2弛豫性能及造影效果

将具有良好生物膜穿透性的异烟肼(INH)和Gd-DO3A偶联,合成了小分子MRI造影剂Gd-DO3A-INH;利用脉冲电转染技术标记间充质干细胞,有效提高了进入细胞的Gd-DO3A-INH浓度,并诱导部分游离态Gd-DO3A-INH在细胞质中自组装成纳米粒子。细胞样品的TEM观察到细胞内形成了Gd-DO3A-INH纳米粒子;细胞传代实验和体外MRI揭示了2种不同状态的Gd-DO3A-INH对细胞水质子弛豫速率的影响机制,以及细胞传代过程中细胞内2种不同状态Gd-DO3A-INH的浓度涨落引起的MRI造影效果的变化机制。     

Comparison of the force field in various pyrochlore families. I. The A2B2O7 oxides

A complete vibrational study of various pyrochlore compounds A₂B₂O₇ shows the role of the different chemical bonds in the structure and how the physico-chemical characteristics of the A and B cations influence these bonds and the rigidity of the two lattices of the structure. Relations between vibrational spectra and structural features are established.     

亲锂电解液在LiNi0.6Mn0.2Co0.2O2／Li二次锂金属电池中的电化学性能

金属锂电池被认为是具有良好前景的下一代高能量密度电池。然而,传统的碳酸酯类电解液与锂的亲和性差,在循环过程中由于锂枝晶的生长和固体电解质膜（SEI）的不稳定导致金属锂电池性能快速衰减。采用1.2 mol／L六氟磷酸锂（LiPF₆）／二氟草酸硼酸锂（LiDFOB）／氟代碳酸乙烯酯（FEC）／碳酸二乙酯（DEC）,并添加了双三氟甲磺酰亚胺锂（LiTFSI）作为电解液,对其在LiNi_0.6Mn_0.2Co_0.2O₂／40 μm-Li（单位面积上负／正极材料的实际容量的比N／P＝2.85）电池中的电化学性能进行了研究。LiNi_0.6Mn_0.2Co_0.2O₂／40 μm-Li电池表现出优异的循环稳定性（循环120圈后,容量保持率>93%）和倍率性能（3C倍率下放电比容量为110 mA·h／g）。良好的电化学性能主要归因于该电解液可以在金属锂表面形成致密且稳定的SEI,并抑制锂枝晶的产生。     

水热法合成Ce0.67Zr0.33O0.2固溶体研究

采用两种不同前驱体通过水热法合成了Ce0.67Zr0.33O0.2固溶体,并通过XRD,BET,TPR等手段考察了样品的相结构,比表面及还原特性.结果表明,在180℃,12 h的水热条件下,以共沉淀产物为前驱体所制得的Ce0.67Zr0.33O0.2固溶体比表面积较高,但存在一定程度的相分离;以凝胶产物为前驱体制得的Ce0.67Zr0.33O0.2固溶体结构更完整,具有良好的还原特性及热稳定性.     

Tetra(μ3-hydroxo)hexa(μ2-carboxylato-O,O′)-bridged tetranuclear terbium(III) cubane complex

A novel tetranuclear terbium(III) complex [Tb₄(OH)₄(pybet)₆(H₂O)₈][Tb₄(OH)₄(pybet)₆(H₂O)₇ (NO₃)](ClO₄)₁₄·6H₂O has been synthesized and shown by X-ray crystallography to have a cubane-like Tb₄(μ₃-OH)₄(μ₂-carboxylato-O,O′)₆ core. The ligand pybet is pyridinoacetate, C₅H₅⁺N-CH₂CO₂⁻. Magnetic susceptibility data were measured for this Tb₄ complex in the range of 2.0–320 K and in fields of 1.0 G to 50.0 kG. It is concluded that either there is very weak antiferromagnetic exchange interaction (J = −0.015 cm⁻¹) or there is a small crystal-field splitting of the ⁷F₆ Tb^III ground state.     

T-x1-x2 model phase diagrams with upper and lower critical stratification temperatures in the starting binary systems

T-x ₁-x ₂ model phase diagrams have been developed under the condition that the component binary systems had closed regions with upper and lower critical stratification temperatures, as well as monotectic equilibria. Isothermal sections in different interinvariant intervals are given.     

固-溶法制备中温固体氧化物燃料电池高性能La0.8Sr0.2MnO3-Ba0.5Sr0.5Co0.8Fe0.2O3阴极

研究了新型固溶法合成La_0.8Sr_0.2MnO₃（LSM）包覆Ba_0.5Sr_0.5Co_0.8Fe_0.2O₃（BSCF）复合粉体（LSM-BSCF）,并探讨了其作为中温固体氧化物燃料电池阴极材料的电化学性能。LSM-BSCF阴极结合了LSM和BSCF阴极的优点,不仅增大了三相界面,而且稳定了微观结构。当温度为600-750℃时,其极化阻抗为0.61-0.09 Ω·cm²。与溶液注入法制备的高性能电极相比,极大地提高了性能稳定性。     

On the phase transition of acetylene-d2

The solid-solid phase transition of acetylene-d₂ at 149 ± 1 K was investigated using a thermal neutron powder diffraction technique. Due to a rapid recrystallization in the vicinity of the transition point the study of the kinetics of the transition was not successful.     

Trace element determination in beauty products by k0-instrumental neutron activation analysis

A recent study on trace elements in beauty products and cosmetics sold on the Asian market has shown the presence of high levels of U, Th and rare earth elements in so called “Hormesis cosmetics.” For the purpose of comparison, some more information about trace elements in European cosmetics would be useful. In this paper the results obtained using k ₀-standardised Instrumental Neutron Activation Analysis (k ₀-INAA) for more than 20 trace elements in 20 different beauty products collected from the European market are presented. We found traces of Ba, As and Sb which is in breach with European legislation. For some of the other elements like Cr and Co further speciation is needed in order to evaluate their presence in beauty products.     

Electronic effects on enantioselectivity in epoxidation catalyzed by D4-symmetric chiral porphyrins

Asymmetric epoxidation of various aromatic olefins was examined with our D₄-symmetric chiral porphyrin. The enantioselectivity was greatly improved upon when the substrates contained electron-deficient groups. Moreover, examination of electronic effects in the porphyrin catalyst revealed that electron-deficient groups lowered and electron-donating groups raised the enantioselectivity. Hammett plot analysis suggested that these electronic effects could be interpreted in terms of the Hammond postulate.     

Synthesis and study of Iron(II) perrhenate complexes with 4-propyl-1,2,4-triazole exhibiting 1A1 ? 5T2 spin transition

Coordination compounds of iron(II) perrhenate with 4-propyl-1,2,4-triazole (L), [Fe₃L₆(ReO₄)₄(H₂O)₂](ReO₄)₂(I), [Fe₃L₆(H₂O)₆](ReO₄)₆·H₂O(II), and FeL₃(ReO₄)₂(III), were synthesized. Compounds I and III were studied by static magnetic susceptibility measurements and by IR and electronic spectroscopy. These complexes exhibit a reversible ¹ A ₁ ⇄ ⁵ T ₂ spin transition and thermochromism. Compound I exhibits a spin transition without hysteresis at 185 K. The temperatures of forward and reverse transition for III are 250 and 244 K, respectively. Complex II isolated by crystallization from an acidified aqueous solution of compound I has a linear trinuclear structure of the cation (X-ray diffraction data). The structure of complex I was assumed to be similar, while compound III has a polymeric structure. Original Russian Text ? M.B. Bushuev, L.G. Lavrenova, Yu.G. Shvedenkov, A.V. Virovets, L.A. Sheludyakova, S.V. Larionov, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 1, pp. 51–56.     

Influence of the S0−T1 structural changes on the triplet–triplet sensitization of dienes

The triplet–triplet energy transfer properties of different dienes were examined through time-resolved laser spectroscopy, and the different structural changes between ground and triplet states were investigated by molecular modeling. It was found that these compounds exhibit very different behaviors depending on their molecular structure. The calculations of ground- and triplet-state potential energy surfaces (PESs) at the B3LYP/6-31+G(d) level clearly evidenced the crucial role of the thermal activation of a single bond torsion in order to decrease the energetic requirement for the transition. A recently developed model, that included the influence of such a torsional mode, was successfully used to support this hypothesis.