Li2SO4-Na2SO4-H2O和Li2SO4- K2SO4-H2O溶液的体积性质

本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li₂SO₄ + Na₂SO₄ + H₂O和 Li₂SO₄ + K₂SO₄ + H₂O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg_–1,混合溶液中Na₂SO₄和K₂SO₄的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θ_V和 ψ_V,模型的计算值与实验值的偏差在±0.002 g.cm_–3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。     

新型层状磷酸铝[Al6P8O32][(C2H5)2NHCH2CH2NH3]2·[C2H5NH2CH2CH2NH2C2H5] 的合成、表征及其共模板作用

在溶剂热体系中,以N,N-二乙基乙二胺为结构导向剂,合成了Al/P为3/4的层状磷酸铝[Al6P8O32][(C2H5)2NHCH2CH2NH3]2·[C2H5NH2CH2CH2NH2C2H5]单晶,并通过X射线单晶衍射结构分析.XRD,ICP,元素分析,差热-热重分析等手段进行了表征.该化合物属单斜晶系,P2(1)/c空间群,晶胞参数:a=0.90945(2)nm,b=1.46424(4)nm,c=1.87572(5)nm,β=102.672(2)°,Z=4.其阴离子层由AlO4四面体和PO3(=O)四面体单元交替连接构成,形成四、六、八元环拓扑结构,无机层以ABAB方式堆积,两种质子化的有机胺分子N,N-二乙基乙二胺及其重排产物N,N′-二乙基乙二胺填充在层间.用分子动力学模拟方法,考察了标题化合物中有机胺与无机层间的相互作用,讨论了这两种有机胺的共模板作用.     

Ce0.67Zr0.33O2对CH4燃烧催化剂Fe2O3/Al2O3的改性作用

固定n(Ce)/n(Zr)比为0.67/0.33, 用共沉淀法制得一系列CeO2-ZrO2-Al2O3固溶体. 采用这些固溶体作载体, 以Fe2O3为活性组分, 用浸渍法制备了一系列催化剂. BET结果显示, 将适量Ce0.67Zr0.33O2引入到Al2O3载体中有助于催化剂保持较高的比表面积. TPR结果显示, 载体中引入适量的Ce0.67Zr0.33O2可以改善催化剂的氧化还原性能. XRD结果表明, Fe2O3在CeO2-ZrO2-Al2O3载体上呈现出良好的分散状况, 老化前后催化剂的晶相结构基本无明显变化. 特别是当载体中m(Ce0.67Zr0.33O2)∶m(Al2O3)的值为1∶2时, Fe2O3/CeO2-ZrO2-Al2O3催化剂在甲烷催化燃烧中显示出最佳的催化性能和抗高温老化性能.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

[(NH2CH2CH2NH3)2WⅥO2(NHC6H4NH)2]2(NH2CH2CH2NH2)·H2O配合物的合成与晶体结构

Cis-dioxo-tungsten(Ⅵ) complex, (NH₂CH₂CH₂NH₂)[(NH₂CH₂CH₂NH₃)₂W^ⅥO₂(NHC₆H₄NH)₂]₂·H₂O is synthesized at room temperature by the reaction of sodium tungstate with o-phenylenediamine. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/ c, a=0.712 8(2) nm, b=3.081 1(10) nm, c=0.981 9(3) nm, β=102.615(4)°, V=2.104 4(11) nm³, Z=2, μ=55.26 cm^-1, F(000)=1 176. Compared the complex with its analogous biomimetic complexes of the cofactor of molybdoenzymes and tungstoenzymses, it is found that the variance of the coordination atoms and the metal ions center have no influence on the coordination feature, and exhibits distored octahedral coordination with cis-dioxo o-phenylenediamine. CCDC: 252834.     

Eu0.5RE0.5Fe0.5Mn0.5O3的57Fe Msosbauer谱研究

利用固相反应合成了Eu0.5RE0.5Fe0.5Mn0.5O3(RE=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Y)等化合物。测量了其XRD谱及57FeMssbauer谱。实验发现,随着RE原子序数的增加,样品的晶胞体积减小,Fe在化合物中处于Fe3+的高自旋状态,57Fe的四极裂矩与样品的畸变参数D成线性关系。     

Eu3+-Tb3+共掺杂SiO2-B2O3-Na2O-Y2O3-P2O5玻璃陶瓷的制备与发光性能

采用高温熔融法制备Eu3+?Tb3+共掺杂SiO2?B2O3?Na2O?Y2O3?P2O5前驱体玻璃。对前驱体玻璃粉末进行差示扫描量热(DSC)分析,确定玻璃陶瓷样品的热处理温度。前驱体玻璃热处理后,采用X射线衍射(XRD)和扫描电镜(SEM)分析可知前驱体玻璃中有Na3.6Y1.8(PO4)3晶粒析出。利用荧光光谱对玻璃陶瓷样品的发光性能进行表征,同时分析了Tb3+离子的荧光衰减曲线,确定Eu3+、Tb3+离子的发光机理以及能量传递过程。通过对Eu3+?Tb3+共掺杂玻璃陶瓷样品的发射光谱采集并用色坐标软件和色温计算程序,获得玻璃陶瓷样品的色坐标和相关色温。     

Ce0.67Zr0.33O2对CH4燃烧催化剂Fe2O3/Al2O3的改性作用

固定n(Ce)/n(Zr)比为0.67/0.33,用共沉淀法制得一系列CeO2-ZrO2-Al2O3固溶体.采用这些固溶体作载体,以Fe2O3为活性组分,用浸渍法制备了一系列催化剂.BET结果显示,将适量Ce0.67Zr0.33O2引入到Al2O3载体中有助于催化剂保持较高的比表面积.TPR结果显示,载体中引入适量的Ce0.67Zr0.33O2可以改善催化剂的氧化还原性能.XRD结果表明,Fe2O3在CeO2-ZrO2-Al2O3载体上呈现出良好的分散状况,老化前后催化剂的晶相结构基本无明显变化.特别是当载体中m(Ce0.67Zr0.33O2)∶m(Al2O3)的值为1∶2时,Fe2O3/CeO2-ZrO2-Al2O3催化剂在甲烷催化燃烧中显示出最佳的催化性能和抗高温老化性能.     

Mm0.78Mg0.22Ni2.48Mn0.09Al0.23Co0.47储氢合金的表面改性

为了提高AB3型合金Mm_0.78Mg_0.22Ni_2.48Mn_0.09Al_0.23Co_0.47（Mm由82.3%La和17.7%Nd组成）的电化学性能,将石墨烯添加到合金中。通过XRD和SEM可以看出,石墨烯并没有改变合金的相结构,仅是简单地附在合金表面。当加入质量分数为2%的石墨烯时,合金电极的最大放电容量C_max达到364.9 mAh·g^-1。石墨烯的添加加速了合金表面的电化学反应。     

Fe3+/Ba2+/Co2+/Zn2+/Cu2+在NH4HCO3-NH3·H2O和NaOH-Na2CO3体系中的热力学分析

通过对Fe3+/Ba2+/Co2+/Zn2+/Cu2+在NH4HCO3-NH3·H2O和NaOH-Na2CO3体系中的热力学分析,得到各金属离子总浓度(cMe)与pH值的关系,确定了2种体系中5种离子完全共沉淀的pH值范围.结果表明:在NH4HCO3-NH3·H2O体系中,Co2+、Zn2+、Cu2+3种离子和氨的配位能力很强,其中Cu2+与氨的配位能力最强,在相同的pH值条件下,Cu2+沉淀困难,5种金属离子的完全共沉淀区域由Cu2+决定.在NaOH-Na2CO3体系中,随总碳浓度(cc)的增加,Ba、Co、Zn、Cu的溶解度都随之减小,当cc=1.0 mol·L-1时,各金属离子完全共沉淀的pH值范围为7.5～11.在两种体系中,Fe的溶解度都是随pH值的增大而减小,最终达到平衡.以NaOH-Na2CO3 为沉淀剂.在pH=10.0的条件下,采用化学共沉淀法合成出了晶粒细小、粒度均匀的Y型纯相结构的平面六角铁氧体微粉.     

Crystal structure of [(C5Me4Et)3Rh3(μ3-Se)2](PF6)2CH3CN and [(C5Me4Et)2Rh2(μ2-Cl)3]PF6

The crystal structure of [(C₅Me₄Et)₃Rh₃(μ₃-Se)₂](PF₆)₂ and [(C₅Me₄Et)₂Rh₂(μ₂-Cl)₃]PF₆, obtained in the reaction of [(C₅Me₄Et)Rh(C₆H₆)](PF₆)₂ with ZnSe in 4M HCl under hydrothermal conditions, is determined. In agreement with the 18VE rule, the triangular cluster contains single metal-metal bonds (Rh-Rh 2.864(1) ?), whereas they are absent in the binuclear complex (Rh ...Rh 3,216(1) ?). Original Russian Text Copyright ? 2009 by P. A. Abramov, M. N. Sokolov, A. V. Virovets, and V. P. Fedin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 1, pp. 169–172, January–February, 2009.     

Mm0.78Mg0.22Ni2.48Mn0.09Al0.23Co0.47储氢合金的表面改性

为了提高AB3型合金Mm_(0.78)Mg_(0.22)Ni_(2.48)Mn_(0.09)Al_(0.23)Co_(0.47)(Mm由82.3%La和17.7%Nd组成)的电化学性能,将石墨烯添加到合金中。通过XRD和SEM可以看出,石墨烯并没有改变合金的相结构,仅是简单地附在合金表面。当加入质量分数为2%的石墨烯时,合金电极的最大放电容量Cmax达到364.9 m Ah·g-1。石墨烯的添加加速了合金表面的电化学反应。     

Ionic diffusion mastering using crystal-chemistry parameters: τ-Cu1/2Ag1/2V2O5 structure determination and comparison with refined δ-AgxV2O5 and ε-CuxV2O5 ones

τ-Ag_1/2Cu_1/2V₂O₅ compound crystallises in the monoclinic system space group C2/m with cell parameters a=11.757(4) Å, b=3.6942(5) Å, c=9.463(2) Å, and β=114.62(2)°. The structure is build up with V₄O₁₀ D4 double layer. The silver and copper ions are located in two different oxygenated tunnels. Examination of electronic density maps shows that while the silver ions are located in defined crystallographic sites, the copper ones are fully delocalised over the whole tunnel. Comparison with δ-Ag_xV₂O₅ and ε-Cu_xV₂O₅ refined structure allows to define crystal chemistry parameters governing the ionic delocalisation and give clues to predict from structural consideration the expected electrical behaviour with the aim to make possible a structural design to enhance guest species reactivity.     

(NH2CH2CH2NH3)4[WⅤO2(OC6H4O)2]2(NH3CH2CH2NH3)·H2O的合成、晶体结构、EPR以及与同构物的比较

Cis-dioxo-catecholatotungsten(Ⅴ) complex (NH₂CH₂CH₂NH₃)₄[W^ⅤO₂(OC₆H₄O)₂]₂(NH₃CH₂CH₂NH₃)·H₂O (1) was synthesized at room temperature by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH₃OH, CH₃CN and NH₂CH₂CH₂NH₂. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/c,a=0.712 8(3) nm, b=3.082 3(11) nm, c=0.982 8(4) nm, β=102.639(6)°, V=2.106 8(14) nm³, Z=2, R₁=0.062 8, wR₂=0.183 7. Compared the complex with its analogous complexes (NH₂CH₂CH₂NH₃)₃[Mo^ⅤO₂(OC₆H₄O)₂], it is found that the coordination structure of W have no changes in the processing of electron transfer of tungsten-containing enzymes from the result of the similarity of the EPR spectra of the complexes and flavoenzyme from milk. CCDC: 272937.     

(C6H8N3)+I3-和[(Cu3I4)(C8H17N2)]配体原位合成与结构表征

在溶剂热条件下, 以原位反应为基础合成了两个碘化物(C6H8N3)+I3-(1, C6H8N3=2,3-dihydroimi-dazo[1,2-a]pyrimidin-1-ium, 2,3-二氢咪唑[1,2-α]-嘧啶鎓阳离子)和[(Cu3I4)(C8H17N2)](2, C8H17N2=N-ethyl-4-aza-1-azonia-bicyclo[2.2.2]octane, N-乙基三乙烯二铵阳离子). 用元素分析、粉末X射线衍射及单晶X射线衍射等对化合物进行了表征. 结果表明, 化合物1属于三斜晶系, P1空间群, a=0.74281(15) nm, b=0.84241(17) nm, c=0.9993(2) nm, α=82.02(3)°, β=83.30(3)°, γ=82.92(3)°, V=0.6114(2) nm3. 化合物2属于单斜晶系, P21/c空间群, a=0.68924(14) nm, b=1.0786(2) nm, c=2.2779(5) nm, β=94.84(3)°, V=1.6874(6) nm3. 在两个化合物合成中存在两种不同类型的配体原位合成反应, 即化合物1的2-氨基嘧啶和乙醇的成环反应与化合物2的三乙烯二胺和乙醇的烷基化反应.     

锂离子电池正极材料Li1.2Mn0.54Ni0.13Co0.13O2研究进展

富锂锰基正极材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂因具有超过250 mA·h·g^-1的可逆比容量和高工作电压(>3.5 V. Li/Li⁺)以及经济成本低的特点，在便携式电子设备中发挥着重要的作用，也被认为是下一代混合动力汽车(HEV)和电动汽车(EV)的理想动力源，是一种有前途的正极材料。由于富锂锰基正极材料存在低倍率容量、电压衰减严重、初始容量损失大的问题，因此提高电池的容量和寿命是目前研究的重点。为此综述了锂离子电池富锂锰基正极材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂的储锂机理、制备方法以及改性研究。     

Preparation and characterization of Co0.5Zn0.5Fe2(C4H2O4)3·6N2H4 A precursor to prepare Co0.5Zn0.5Fe2O4 nanoparticles

A good precursor is foremost in the preparation of nanosized metal or mixed metal oxides. In the present study a novel precursor, cobalt zinc fumarato-hydrazinate Co_0.5Zn_0.5Fe₂(C₄H₂O₄)₃·6N₂H₄ has been prepared which decompose at a much lower temperature to give nanosized mixed-metal oxides. X-ray investigations, confirms the formation of single spinel phase. The FTIR spectra show N-N stretching vibration at 965 cm⁻¹ which confirms the bidentate bridging hydrazine. The thermal decomposition of the precursor has been studied by isothermal, thermogravimetric and differential scanning calorimetric analysis. The precursor shows two-step dehydrazination followed by decarboxylation to form Co_0.5Zn_0.5Fe₂O₄, the chemical analysis of the sample is corroborative of this.     

Na2B4O7-Na2SO4-NaCl-H2O四元体系288K相平衡研究

采用等温溶解平衡法研究了四元体系Na2B4O7-Na2SO4-NaCl-H2O在288 K的相平衡关系,测定了平衡液相的溶解度及其密度。由研究结果知该四元体系为简单共饱和型,无复盐及固溶体形成。根据实验数据绘制了相应的相图。相图中有一个共饱点,三条单变曲线,三个结晶区平衡固相分别为:Na2B4O7·10H2O,Na2SO4·10H2O和NaCl。实验结果表明NaCl对Na2B4O7和Na2SO4有盐析作用,并简要讨论了实验结果。     

Crystal structure of [MnII (1,10-C12H8N2)3]2+[(B9C2H11)CoIII(B8C2H10)CoIII(B9C2H11)]2?·CH3CN

A novel compound, [MnPhen₃][(B₉C₂H₁₁)Co(B₈C₂H₁₀)Co(B₉C₂H₁₁)]· CH₃CN (Phen = 1,10-phenantroline), comprising a Co(III) dicobaltacarborane cluster anion has been prepared and characterized by single crystal X-ray diffraction. Crystal data are the following: C₄₄H₅₉B₂₆N₇Co₂Mn, M = 1139.84, triclinic, space group , unit cell parameters: a = 13.2465(11) Å, b = 14.521(2) Å, c = 15.2536(15) Å; α = 77.027(9)°, β = 88.500(8)°, γ = 77.274(9)°; V = 2788.5(5) ų, Z = 2, d _calc = 1.358 g/cm³, T = 295 K, F(000) = 1162, μ = 0.853 mm⁻¹. The structure was solved by the direct and Fourier methods and refined anisotropically (isotropically for hydrogen atoms) using the full-matrix technique to final factors R ₁ = 0.0374, wR ₂ = 0.0915 for 7397 I _hkl ≥2σ_I of 9779 I _hkl measured (diffractometer Enraf-Nonius CAD-4, λMoK _α , graphite monochromator, θ/2θ-scanning). The structure is formed from [MnPhen₃]²⁺ cations, [(B₉C₂H₁₁)×Co(B₈C₂H₁₀)Co(B₉C₂H₁₁)]₂₋ anions, and acetonitrile molecules CH₃CN. Central Mn atom in the cation has a distorted octahedral coordination environment formed by six nitrogen atoms of three bi-dentate Phen ligands, average Mn-N bond length being 2.263(2) Å. The anion has a chain-like structure built from three icosahedra sharing common vertices occupied by the cobalt atoms. The central icosahedron including ten light atoms (8B, 2C) provides two vertices for the cobalt atoms shared with the other icosahedra having 11 light atoms (9B, 2C). The arrangement of-C₂-groups in the anion corresponds to a quasi-gauche-configuration of asymmetric sandwich complexes of both cobalt atoms. Original Russian Text Copyright ? 2005 by T. M. Polyanskaya, V. V. Volkov, and M. K. Drozdova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp.730–740, July–August, 2005.