Synthesis and crystal structure of [La(NO3)3(H2O)2(BiPy)]·1.5(BiPy)

The molecular and crystal structure of the [La(NO₃)₃(H₂O)₂(2.2′-BiPy)]·1.5(2.2′-BiPy) compound is determined. The metal coordination polyhedron in the La(III) complex is formed from 10 donor atoms of O₈N₂: 6 oxygen atoms belong to three chelate-coordinated NO ₃ ^? anions, 2 oxygen atoms belong to two water molecules, and 2 nitrogen atoms belong to a bidentate bipyridine molecule coordinated in the neutral form. The structure is based on the metal complexes linked together in chains through the O(W)-H...O hydrogen bonds, in which oxygen atoms of the coordinated NO ₃ ^? anions act as acceptors. It is a framework structure, further stabilized by a system of O(W)-H...N and C-H...N hydrogen bonds, in which nitrogen atoms of the uncoordinated bipyridine molecules act as proton acceptors.     

Hydrothermal Synthesis of Pb_(1-1.5x)La_xZr_(0.5)Ti_(0.5)O_3 (x = 0.01-0.06) Nanocrystallites

Lanthanum doped lead zirconate titanate (PLZT) ceramics display excellent electrooptic and photostriction properties because of the existence of cavities in the perovskite structure1-3. The PLZT powders are conventionally prepared by solid state reaction4-5, and the wet chemical methods such as sol-gel techniques are then introduced6-7. However, the homogeneity, morphology and size of the particles, which greatly affect the sinterability and the property of the resulting ceramics, are dif…     

Distorted colloidal crystal of similar-sized aggregates (1.5 μm in diameter) of nano-sized diamond particles (4 nm in diameter)

Distorted colloidal crystal suspension of similar-sized aggregates of diamonds (1.5 μm in diameter) was obtained by the deionization of aqueous suspension of the pre-particles of diamond, 4 nm in diameter. The stability, characteristics, and the rigidity of the crystal-like suspensions were studied. The main cause for the formation of the similar-sized aggregates is deduced to be the cooperation between the van de Waals inter-particle attraction and the repulsion induced by the vigorous thermal motion of the pre-particles. The rigidity was evaluated from the microscopic observation in the sedimentation equilibrium. Fluctuation parameters of the distorted colloidal crystals estimated from the rigidities were between 0.03 and 0.06, which are quite similar to those of typical colloidal crystals and solids of hard spheres.     

NTC陶瓷材料Co_(1.5)Mn_(1.5-X)Ni_XO_4中阳离子分布与导电性间的关系

本文通过溶胶-凝胶法制备三元系Co1.5Mn1.5-XNiXO4(X=0,0.1,0.3,0.5,0.7,1.0)NTC热敏电阻粉体材料,采用激光粒度分析、X射线衍射分析、红外光谱分析、电阻测量等手段,表征了煅烧材料的颗粒尺寸、烧结体的物相、红外吸收光谱以及陶瓷材料的电学特性。结合XRD、IR的分析结果,探讨了阳离子分布与热敏电阻电性能之间的关系,为解决热敏电阻材料高精度、高可靠性方面提供了依据。结果表明:随着Ni离子的增加,所得热敏材料的电阻率呈U型变化,材料常数B值从4427减小到2429K,该系列的电阻率、B25/50值调整范围较大,是一种具有实际应用价值的NTC热敏电阻。     

Drying dissipative structure of similar sized aggregates (1.5 μm in diameter) of nano-sized diamond particles (4 nm in diameter)

Macroscopic and microscopic drying patterns were observed on a cover glass, a watch glass, and a Petri glass dish during the course of dryness of aqueous suspensions of similar sized aggregates of diamonds (CD1), which formed from the deionization of the pre-particles of diamond 4 nm in diameter. Two kinds of macroscopic patterns, i.e., outer and inner broad rings, and spoke lines were formed. Cooperative drying processes of the convection, sedimentation, and solidification were clarified. Microscopic drying patterns showing the formation of very large dendritic aggregates from the CD1 particles were observed only when the excess amount of sodium chloride higher than 2 mM coexisted in the initial suspensions before dryness and further initial CD1 concentration is lower than 0.17 wt%.     

锂离子交换体Li_(1.5)Ti_(1.625)O_4的研究(Ⅲ)——Li_(1.5)Ti_(1.625)O_4的造粒、改型及油田咸水中锂的回收

对锂离子交换体前驱体Li1.5Ti1.625O4的造粒、改型及改型后的锂离子交换体H1.5Ti1.625O4用于油田咸水中微量锂的提取进行了实验室研究。结果表明,锂离子交换体H1.5Ti1.625O4对油田咸水中微量锂离子有很好的记忆性交换,有效交换容量达11.54mg/g,对锂离子表现出良好的离子筛效应。     

复合金属氧化物Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4的锂离子交换性能研究

具有尖晶石型结构的化合物能够在插入大量替代离子改变自身锂和氧化学计量数的同时保持结构的稳定性,这种特性能够被用于离子交换研究,用来满足提取锂的需求。通过检测尖晶石型复合金属氧化物的饱和交换能力、分配系数等,可以确定其具体特性。本文利用共沉淀/固相反应热结晶方法,合成尖晶石型复合金属氧化物Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4。实验结果表明,经酸化的Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4,其Mg~(2+)的抽出比率高达72%,Mn~(4+)和Ti~(4+)的溶解比率低于8.2%。实验分析表明,无机离子交换剂Mg_(1.5)Mn_(0.5)Ti_(0.75)O_4对Li~+有较好的离子筛效应,离子选择性较好,酸化后的样品对Li~+的离子交换能力高达10.6mmol·g~(-1)。     

Two-step hydrothermal synthesis of submicron Li(1+x)Ni(0.5)Mn(1.5)O(4-δ) for lithium-ion battery cathodes (x = 0.02, δ = 0.12)

A facile two-step hydrothermal method is developed for the large-scale preparation of lithium nickel manganese oxide spinel as a cathode material for lithium ion batteries. In the reaction, nickel is introduced in a first step at neutral pH, followed by lithium insertion under base to form a product having composition Li(1.02)Ni(0.5)Mn(1.5)O(3.88). The X-ray diffraction pattern and Raman spectroscopy of the synthesized material support a cubic Fd3m structure in which Ni and Mn are disordered on the 16d Wyckoff site, necessary for good cycling characteristics. XP spectroscopy and elemental analysis confirms that Mn remains reduced in the final product (Z(Mn) = 3.82) and that two different chemical environments for Ni exist on the surface. SEM imaging shows a primary particle size of ~200 nm, and galvanostatic cycling of the material vs. Li(+/0) gives a reversible gravimetric capacity of ~120 mA h g(-1) at 1 C rate (147 mA g(-1)) with reversible cycling up to 1470 mA g(-1), supported by rapid Li(+) diffusion. The capacity fade at 1 C is substantial, 17.3% over the first 100 cycles between 3.4 and 5.0 V. However, when the voltage limits are altered, the capacity retention is excellent: nearly 100% when cycled either between 3.4 and 4.4 V (where oxygen vacancies are not electrochemically active) or 89% when cycled between 4.4 and 5.0 V (where the Jahn-Teller active Mn(4+/3+) couple is not accessed).     

Synthesis of a Nine-atom Germanium Cluster K_(0.5)[K(18-crown-6)]_(1.5)Ge_9·1.5en with Unprecedented “up” and “down” Chain Arrangement of Unit [-(Ge_9-K-Ge_9)~(3-)-]

A new complex K0.5[K(18-crown-6)]1.5Ge9·1.5en(1) which contains unprecedented "up" and "down" chain arrangement of unit [-(Ge-9-K-Ge9)3-] has been prepared by the reaction of K4Ge9 with HgS in ethylenediamine(en) in the presence of 18-crown-6(1,4,7,10,13,16-hexaoxacyclooctadecane), and characterized by X-ray structure analysis. The color of the title crystals(black), which is darker than that of the reported three compounds with chains of germanium clusters, may result from the naked K+ and their interactions with the chain. And the structure differences between 1 and the reported three compounds with chains of germanium have also been discussed.     

High performance and stability of double perovskite-type oxide NdBa_(0.5)Ca_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ) as an oxygen electrode for reversible solid oxide electrochemical cell

In this study,we successfully synthesized double perovskite-type oxide NdBa_(0.5)Ca_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(NBCCF) using a conventional wet chemical method as the oxygen electrode for reversible solid oxide electrochemical cells (RSOCs).The polarization resistance (R_p) of the composite electrode NBCCFGd_(0.1)Ce_(0.9)O_2 (GDC) is only 0.079Ωcm~2 at 800℃under air.The single cell based on NBCCF-GDC electrode displays a peak power density of 0.941 W/cm~2 in fuel cell mode and a low R_p value of 0.134Ωcm~2.In electrolysis cell mode,the cell displays an outstanding oxygen evolution reaction (OER) activity and shows current density as high as 0.92 A/cm~2 with 50 vol%AH (Absolute Humidity) at 800℃and applied voltage of 1.3 V.Most importantly,the cell exhibits admirable durability of 60 h both in electrolysis mode and fuel cell mode with distinguished reversibility.All these results suggest that NBCCF is a promising candidate electrode for RSOC.     

水合肼对锂离子正极材料LiNi_(0.5)Mn_(1.5)O_4性能的影响

以NiSO4和MnSO4为原料,在用共沉淀法经二次干燥制备锂离子电池正极材料LiNi0.5Mn1.5O4的前驱体时,加入水合肼进行还原处理.实验结果发现:经还原处理的前驱体制备正极材料LiNi0.5Mn1.5O4的充放电比容量远远高于同样条件下不经水合肼还原处理的前驱体制备的正极材料的充放电比容量,而且处理前驱体制备的正极材料在高倍率放电条件下电化学行为更好.粉末X射线衍射(XRD)和扫描电镜(SEM)测试结果表明,用还原剂水合肼处理的前驱体合成的样品为单一的尖晶石结构,晶粒呈规则的八面体形貌,没有杂质相,而未处理前驱体合成的样品则含有少量的杂质相.这种杂质相是在前驱体的制备过程中由于Mn(OH)2被O2氧化而形成难溶Na0.55Mn2O4.1.5H2O化合物,最终转变为Na0.7MnO2.05.     

Investigation of Absorption Spectra of Bis(alkylxanthato)-platinum(Ⅱ) Complexs

Being widely used as good ligands,xanthates and related compounds have been extensively investigated.However,reports on Pt(Ⅱ) xanthates have been sparse so far.Watt et al.reported the synthesis and characterization of Pt(S_2COR)_2(R=Me,Et),but did not provide any absorption spectra of these complexes.We prepared twelve platinum (Ⅱ) xanthate complexes and examined their absorption spectra in detail.     

熔盐法合成电化学性能优异的富锂层状正极材料Li_(1.5)Ni_(0.25)Mn_(0.75)O_(2.5)

采用氢氧化物共沉淀和熔盐法相结合的方法制备得到了电化学性能优异的富锂锰基Li_(1.5)Ni_(0.25)Mn_(0.75)O_(2.5)正极材料。借助X射线衍射(XRD)分析、扫描电镜(SEM)、感应耦合等离子体原子发射光谱(ICP-AES)、X射线光电子能谱(XPS)、电化学阻抗谱(EIS)和恒电流充放电测试等表征手段对材料的颗粒形貌、晶体结构和电化学性能进行了系统研究。XRD结果表明该材料具有完善的α-NaFeO2层状结构(空间群为R3m)和较低的Li~+/Ni~(2+)阳离子混排。电化学性能测试表明该材料的首次不可逆容量损失较小,且倍率性能和循环稳定性能十分优异。具体而言,在2.0~4.8V,0.1C时的首次不可逆容量损失为50mAh·g~(-1)(首次库伦效率84%);在10C时的放电比容量还能达到102mAh·g~(-1);在0.5C下循环100次后,放电比容量为205mAh·g~(-1)(容量保持率90%)。     

Synthesis and X‐Ray Study of Single Crystals of K5(Cd0.5Zr1.5)(MoO4)6 Triple Molybdate

Single crystals of K₅(Cd_0.5Zr_1.5)₂(MoO₄)₆ molybdate have been grown. Its composition and crystal structure have been established from Xray diffraction data CAD4 automatic diffractometer, MoK radiation, 940 F(hkl), R = 0.0234. The crystals have a trigonal unit cell a = b = 10.624(1), c = 37.694(6), V = 3684.5(8)³, and space group R3c. The 3D mixed framework of the molybdate structure is formed by two kinds of Mo tetrahedra and (Cd, Zr) octahedra joined by shared O vertices. The large cavities in the framework are occupied by K atoms of three kinds. The distribution of Cd²⁺ and Zr⁴⁺ cations over two crystallographic positions has been refined.     

Donor-Acceptor Complexes in Copolymerization. VIII. Evidence of Participation of Complexes in Copolymerization of Styrene and Methyl Methacrylate… Al(C2H5))1.5Cl1.5

The copolymerization of styrene and methyl methacrylate in the presence of ethylaluminum sesquichloride in toluene yields alternating copoly-mers, independent of initial monomer ratio. The rate of polymerization is not influenced by the presence of an excess of either monomer, the conversion curves following a parallel course at a given total monomer concentration. When the concentration of the AlEt_1.5Cl_1.5 and the S/MMA ratio are kept constant and the total monomer concentration is increased, the polymerization rate increases and reaches a limiting value at a S/MMA/Al ratio of 2:2:1. A similar result is obtained when the total monomer and the AlEt_1.5Cl_1.5 concentrations are kept constant and the S/MMA ratio is varied. When the concentration of either monomer and the AlEt_1.5Cl_1.5 concentration are kept constant and the concentration of the other monomer is varied, the polymerization rate reaches a limiting value at the same mole ratio, irrespective of which monomer is varied. The rate of polymerization is decreased in the presence of a small amount as well as a large amount of benzoquinone. However, the rate is higher than in the absence of the quinone when the Al/benzoquinone ratio is 2:1. The conductivity of a toluene solution of AlEt_1.5Cl_1.5 increases only slightly upon the addition of methyl methacrylate, a further small increase occurring upon the addition of styrene. The results provide evidence for the participation of a comonomer complex in the polymerization, the optimum composition resulting either from the simultaneous interaction of several equilibria or the alignment of the complexes in the form of a matrix.     

Reactivity of Geometric Isomers of (–)-Dichloropyridine(methyl-para-tolylsulfoxide)platinum(II) by Optical Rotatory Dispersion

The reactions of the optically active geometric isomers of the platinum(II) complex (–)-[Pt(Me-p-TolSO)(Py)Cl₂] with several nucleophilic reagents (Py, Ph₃PS, Ph₃P, Ph₃As, and Me₂SO) were studied by optical rotatory dispersion, IR spectroscopy, and ¹H and ³¹P NMR spectroscopy. A mechanism for the reaction is proposed.     

Synthesis and crystal structure of Mo6−x Nb x I11 (x = 1–1.5)

A solid solution Mo_{6 ? x} Nb _x I₁₁ (x = 1.1–1.5) containing cluster cores {Mo₅NbI₈} is obtained by the high-temperature reaction of molybdenum, niobium, and iodine (550°C, 70 h, quartz ampule). According to the X-ray diffraction data, heating at 800°C in a molybdenum container results in the decomposition of the solution to Mo₆I₁₂ and Nb₆I₁₁. According to the X-ray structure analysis data, the compounds are isostructural to the high-spin modification Nb₆I₁₁ (space group Pccn). The presence of Nb atoms in the structure changes the structural type from the layered (Mo₆I₁₂) to framework structure, noticeably increases the metalmetal distances (2.661–2.716 Å, 2.695 Å) Mo₆ octahedron with the retention of the distance from the metal (M) to the μ₃-“capped” I atoms, and strongly elongates the M₆-I-M₆ bridges almost to the value observed in Nb₆I₁₁.     

Synthesis and Crystal Structure of a Two-dimensional Polymeric Holmium Complex〔Ho(H_2saln)_(1.5)(NO_3)_3〕

１ＩＮＴＲＯＤＵＣＴＩＯＮＭｅｔａｌｉｃｃｏｍｐｌｅｘｅｓｏｆｓｃｈｉｆｂａｓｅｓｈａｖｅａｔｒａｃｔｅｄｔｈｅａｔｅｎｔｉｏｎｏｆｒｅｓｅａｒｃｈｅｒｓｄｕｅｔｏｔｈｅｉｒａｎｔｉｖｉｒａｌ，ｆｕｎｇｉｓｔａｔｉｃ，ａｎｄｃａｔａｌｙｔｉｃａｃｔｉ...     

Synthesis of (±)-Bimatoprost

A general synthetic approach has been developed for the synthesis of a key intermediate (6) that can be elaborated into several ophthalmic prostaglandins and their derivatives. Using these strategy, we have obtained (±)-bimatoprost (1) and its analog, (±)-homobimatoprost (5).