新型氧离子导体La_2Mo_2O_9

La2Mo2O9是一种具有高离子导电性的新型氧离子导体,其氧离子电导率在1073K时高达0.06S/cm,与YSZ在1273K时的电导率相当。这种高的离子导电性使它在中温固体氧化物燃料电池、氧传感器、透氧膜、固态离子器件等领域有着重要的潜在应用前景。本文从La2Mo2O9的结构、性质、氧离子扩散机理及其掺杂改性4个方面综述了近年来La2Mo2O9基固体电解质的研究热点和新进展,为该固体电解质材料的研究提供了有价值的信息。     

2-甲基-9-芴酮的合成

对甲苯胺与苯甲酰氯经酰胺化反应制得N-对甲苯基苯甲酰胺(1);1经傅克酰基化反应和脱酰胺保护制得2-氨基-5-甲基二苯甲酮(2);2经Pschorr环合反应合成了2-甲基-9-芴酮,总收率64%,其结构经1H NMR和HR-ESI-MS确证。     

Synthesis of New Solid Solutions on Neodymium-stabilized La2Mo2O9

Oxide ion conductors form a class of materials which are widely sought for and studied since they can be used in different field among solid oxide fuel cells (FOFC), oxygen sensors, oxygen pumping devices, or oxygen-permeable membrane catalysts, for instance1-3. Now research focuses on the oxide ion conductors with new structure and improving the conductivity or lowering the operating temperature. Recently P.Lacorre et al.4 have reported a novel oxide-ion conductor based on La2Mo2O9. F.…     

新型固体电解质La2Mo2O9的制备及其性能

用固相法制备了新型固体电解质La2Mo2O9, 用热膨胀仪、 X射线衍射仪和Raman光谱分析了La2Mo2O9相的形成过程. 用交流阻抗谱和热膨胀仪对合成样品的电学和热学性能进行了研究, 分析了热处理温度对La2Mo2O9相的形成过程和电学性能的影响, 确定了样品获得高电学性能的最佳条件. 研究结果表明: 600 ℃时样品中开始形成La2Mo2O9相, 700 ℃以上烧结的样品可获得具有完整氧空位的La2Mo2O9相. 900 ℃烧结10 h可获得具有高密度和高电导率的La2Mo2O9氧离子导体. 样品的电学性能随烧结温度的升高而增大, 900 ℃时烧结的样品在800 ℃时的电导率为0.067 S·cm-1, 远高于同温度下YSZ的电导率, 与晶粒电阻相比, 晶界电阻非常小. 用热膨胀仪测得La2Mo2O9在555 ℃时有一个一级相变, 对应α-La2Mo2O9到β-La2Mo2O9的相变.     

超声波合成2，7-二溴-9，9-二烷基芴

以2,7-二溴芴(1)和溴代烷(2)为原料,二甲亚砜为溶剂,四丁基溴化铵为相转移催化剂,超声波辐射合成了3个2,7-二溴-9,9-二烷基芴(3),其结构经1H NMR,IR,MS和元素分析表征.考察了超声波辐射时间和辐射功率对反应的影响,结果表明,在1 16 mmol,n(1):n(2)=1:1,于45 W辐射反应1 h的反应条件下,3的收率达92%.     

N-(9,9-二苯基-9H-芴-2-基)-N,9-二苯基-9H-咔唑-2-胺的合成

以邻溴硝基苯为起始原料,经Suzuki偶联反应、Cadogan关环反应、Ullmam反应、Buchwald反应等合成了目标产物N-(9,9-二苯基-9H-芴-2-基)-N,9-二苯基-9H-咔唑-2-胺,其结构经¹H NMR、 ¹³C NMR和HR-MS(ESI)确证,并采用TG-DSC、 UV-Vis对产物的热稳定性能和光学性能进行了研究。      

超高温压电陶瓷CaBi2Nb2O9的定向生长及性能

将熔盐法制备的片状CaBi2Nb2O9（CBNO）前驱体在1050℃烧结成陶瓷,对陶瓷晶粒取向和形貌进行了分析和表征,研究了其介电、铁电和压电性能.与传统固相法制备的样品相比较,新工艺制备出的CaBi2Nb2O9陶瓷,烧结温度降低,晶粒定向生长,具有明显织构特征,室温时极化变得容易,介电损耗减小,压电系数明显提高.     

Syntheses,Crystal Structures and Properties of Three New Complexes [Ni（C9N2O2H7）2（CH3OH）2],[Zn（C9N2O2H7）2（H2O）2] and [Cd（C9N2O2H7）2（CH3OH）2]

Three novel metal-organic complexes with formulas [Ni(C9N2O2H7)2(CH3OH)2](1),[Zn(C9N2O2H7)2(H2O)2](2) and [Cd(C9N2O2H7)2(CH3OH)2](3) were synthesized by the reactions of Ni,Zn and Cd salts with ethyl 2-benzimidazolylacetate under hydrothermal conditions or layering technique,and characterized by single-crystal X-ray diffraction analysis,IR spec-troscopy,solid-state luminescent properties and thermogravimetric(TG) analysis.The crystal data for these three complexes are as follows:for 1,monoclinic,space group P21/c,a = 9.384(3),b = 9.634(3),c = 11.292(3) ,β = 95.787(5)°,V = 1015.7(5) 3,Z = 2,F(000) = 492,Dc = 1.547 Kg/m3,μ = 1.002 mm-1,the final R = 0.0451 and wR = 0.0900 for 1833 observed reflections with Ⅰ 2σ(Ⅰ);for 2,orthorhombic,space group Pbca,a = 10.031(4),b = 10.379(4),c = 17.525(7),V = 1824.6(12) 3,Z = 4,F(000) = 928,Dc = 1.645 Kg/m3,μ = 1.392 mm-1,the final R = 0.0452 and wR = 0.0996 for 1661 observed reflections with Ⅰ 2σ(Ⅰ);for 3,monoclinic,space group P21/c,a = 9.9114(13),b =10.4852(15),c = 10.4120(14) ,β = 108.453(5)°,V = 1026.4(2) 3,Z = 2,F(000) = 532,Dc = 1.705 Kg/m3,μ = 1.110 mm-1,the final R = 0.0322 and wR = 0.0805 for 1822 observed reflections with Ⅰ 2σ(Ⅰ).In the three complexes,the ethyl 2-benzimidazolylacetate shows the same chelating mode,and the adjacent units are interlinked into a two-dimensional layer through hydrogen-bonds(O-H···O,N-H···O).     

Cationic arenerhodacarboranes [(ν-arene) Rh(ν-7,8-Me2-7,8-C2B9H9)]BF4

A new procedure was developed for the synthesis of (η³-C₈H₁₃)Rh(η-7,8-C₂B₉H₉) (1). This method involves the interaction of [codRhCl]₂ with Cs[7,8-Me₂-7,8-C₂B₉H₁₀] in CH₂Cl₂. The reactions of compound1 with arenes in trifluoroacetic acid afforded, the previously unknown cationic arenerhodacarboranes [(ν-arene) Rh(ν-7,8-Me₂-7,8-C₂B₉H₉)]BF₄ in high yields. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 592–594, March, 1999.     

铁钴三核原子簇氢化物HFe2Co(CO)9PR和HFe2Co(CO)9Se的合成

在THF 中反应, 合成了以有机膦作μ3-配位体的新型铁钴三核原子簇羰基氢化物HFe2Co(CO)9PR.又用高压法合成FeCo2(CO)2Se, 它与Na2[Fe(CO)4] 在THE 中反应, 得到另一个以硒作μ3-配位体的新型铁钴三核原子簇羰基氢化物式电离成-价阴离子, 再与反应生成     

溶胶-凝胶法制备SrBi2Ta2O9铁电陶瓷薄膜

溶胶-凝胶法制备SrBi2Ta2O9铁电陶瓷薄膜     

碳包覆Ti_2Nb_2O_9纳米片的制备及其储钠性能

具有两种不同阳离子的二元金属氧化物在钠离子电池中可发生可逆的多电子反应,是一类非常具有应用前景的高容量负极材料。在本项工作中,通过离子交换法和化学剥离法得到HTiNbO_5纳米片,采用水热法将其与蔗糖复合再经由后续热处理得到碳包覆的Ti_2Nb_2O_9纳米片材料。碳包覆的Ti_2Nb_2O_9纳米片可用作钠离子电池的负极材料,具有更高的电子导电性和多的反应活性点以及快速的离子传输通道,在50 m A?g~(-1)的电流密度下具有265.2 m Ah?g~(-1)的可逆容量。在0.5A?g~(-1)的大电流密度下,循环200圈之后比容量为160.9 m Ah?g~(-1) (容量保持率75.3%)。研究结果表明Ti_2Nb_2O_9/C纳米片在钠离子电池中具有出色的充放电性能和循环稳定性,为钠离子电池负极材料提供了可行的新选择。     

Synthesis of rhodacarborane halide complexes [(η-9-Me2S-7,8-C2B9H10)RhX2]2 (X=Cl, Br, or I)

The reactions of the complex (η-9-Me₂S-7,8-C₂B₉H₁₀)Rh(η-cod) (cod is 1,5-cyclo-octadiene) with HX acids (X=Cl, Br, or I) in acetone afforded rhodacarborane halide complexes [(η-9-Me₂S-7,8-C₂B₉H₁₀)RhX₂]₂, which are carborane analogs of cyclopentadienyl halide rhodium complexes [(η-C₅R₅)RhX₂]₂. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1817–1819, September, 1999.     

Synthesis, IR spectra, and solid-state luminescence of triphenylguanidinium salts with the anions B10H 10 2− , B12H 12 2− , B9C2H 12 2− , [Co(C2B9H11)2]−, and [Ni(C2B9H11)2]−

Triphenylguanidinium Ph₃GH⁺ salts with the anions B₁₀H ₁₀ ^2? , B₁₂H ₁₂ ^2? , B₉C₂H ₁₂ ^2? , [Co(C₂B₉H₁₁)₂]^?, and [Ni(C₂B₉H₁₁)₂]^? were synthesized and described by DTA, IR spectroscopy, and solid-state luminescence. By IR spectroscopy, it was shown that intermolecular interactions involving the NH groups of the cation are enhanced in the sequence [Co(C₂B₉H₁₁)₂]^? ～ [Ni(C₂B₉H₁₁)₂]^? < B₉C₂H ₁₂ ^2? < B₁₂H ₁₂ ^2? < B₁₀H ₁₀ ^2? .     

Molecular Packing in the Crystal Structures of the Mixed-Ligand Complexes [CdPhen{(i-C4H9)2PS2}2] and [Cd(2,2′-Bipy){(i-C4H9)2PS2}2]

Single crystals of the mixed-ligand complex compounds of Cd(i-Bu₂PS₂)₂ with Phen and 2,2-Bipy have been obtained. The crystal structures of the complexes [CdPhen{(i-C₄H₉)₂PS₂}₂] (I) and [Cd(2,2-Bipy){(i-C₄H₉)₂PS₂}₂] (II) were determined by X-ray diffraction (CAD-4 diffractometer, MoK radiation, 1739 F _{F hkl} , R = 0.0417 for I and 2612 F _hkl , R = 0.0442 for II). Monoclinic crystals with unit cell parameters a = 15.640(3), b = 20.797(4), c = 11.559(2) , = 111.21(3)°, V = 3505(1) ³, Z = 4, d _calc = 1.348 g/cm³, space group (I); a = 14.737(3), b = 20.918(4), c = 11.517(2) , = 105.53(3)°, V = 3421(1) ³, Z = 4, d _calc = 1.334 g/cm³, space group (II). The structures consist of discrete monomer molecules. The coordination polyhedra of the Cd atoms are distorted octahedra formed by four S atoms of two cyclic bidentate ligands i-Bu₂ and two N atoms of the cyclic bidentate ligands — Phen or 2, -Bipy molecules. The interaction between molecules I and II in the structures and the packing modes are considered.     

CRYSTAL STRUCTURE OF {Ni[(C_4H_9O)_2PS_2](C_(12)H_8N_2)_2} -[(C_4H_9O)_2PS_2]

<正> {Ni C(C4H9O)2PS2] (C12H8N2)2} [C(C4H9O)2PS2], Mr= 795. 60, Monocinic,P2,/n,a=16. 806(2), b=12. 720(2), c=21. 248(2) A. β=98. 454(7)°, V = 4493A3,Z=4,Dc= 1. 18g·cm-3,Mo Ka radiation,A=0. 71069A ,F(000) = 1664, R=0. 102 for 4154 reflections with I≥3σ(I).The crystal structure consists of complex cation {NiC(C4H9O)2PS2](C12H8N2)2}+ and complex anion C(C4H9O)2PS2]-. In the cation, nickel (Ⅱ) atom is coordinated by four nitrogen atoms and two sulfur atoms to form a distorted octahedron.     

Synthesis of the iridacarborane halide complexes [(η-9-SMe2-7,8-C2B9H10)IrX2]2 (X = Cl,Br, or I)

The reaction of Na[9-SMe₂-7,8-C₂B₉H₁₀] with [(Cod)IrCl]₂ (Cod is cycloocta-1,5-diene) gave rise to the iridium complex (-9-SMe₂-7,8-C₂B₉H₁₀)Ir(Cod). Treatment of the latter with anhydrous acids HX (X = Cl, Br, or I) afforded the corresponding iridacarborane halide complexes [(-9-SMe₂-7,8-C₂B₉H₁₀)IrX₂]₂ analogous to the cyclopentadienyl complexes [(C₅Me₅)IrX₂]₂.     

La2(Mo1-xVx)2O9-α的制备及其导电性

采用固相法合成了系列陶瓷样品La₂(Mo_1-xV_x)₂O_9-α (x=0.02, 0.04, 0.06, 0.08). 粉末X射线衍射(XRD)结果表明样品具有单一立方相La₂Mo₂O₉结构. 采用气体浓差电池、电化学阻抗等电化学方法研究了陶瓷样品在823-1123 K下的导电特性. 系列陶瓷样品已完全抑制La₂Mo₂O₉母体在853 K附近的相变; 各样品在干燥及湿润氧气气氛中几乎为纯氧离子导体, 质子导电性可忽略不计; 氧离子电导率σ随掺杂离子浓度的变化为σ(x=0.02)<σ(x=0.08)<σ(x=0.06)<σ(x=0.04), 这与晶胞自由体积大小的次序完全一致, x=0.04样品具有最高的氧离子电导率0.051 S·cm^-1; 氧分压与电导率的关系表明, 在高氧分压气氛中样品是纯的氧离子导体, 在低氧分压气氛中是氧离子与电子的混合导体.     

La2-xSrxMo2O9-α仅的制备及氧离子导电性能

用固相反应法合成了立方相陶瓷样品La2-xSrxMo2O9-α(x=0.05,0.10,0.15).采用交流阻抗谱、气体浓差电池和氧泵(氧的电化学透过)等多种电化学方法研究了样品在550～1000℃下氧离子的导电性质.结果表明:La2-xSrxMo2O9-α陶瓷在氧化性气氛中几乎是纯的氧离子导体;在还原性气氛中为氧离子和电子的混合导体;掺杂量x对样品的电导率有着明显影响,其中x=0.10的样品La1.9Sr0.1Mo2O9具有最高的氧离子电导率,1000℃时的氧离子电导率约为0.17 S·cm-1.     

(CH2 )2 (C9 H6 )2 YbN(SiMe3 )2 的合成与催化活性研究

用1,2-二茚基乙烷[(CH2)2(C9H7)2]与四配位的三[三甲基硅基胺基]镱的络合物{[(Me3Si)2N]3Yb(Ⅲ)(μ-Cl)Li(THF),}反应,生成桥联二茚基镱的胺基配合物[(CH2)2(C9H6)2YbN(SiMe3)2],其结构经^1HNMR,IR,XFD),GPC和元素分析表征,并初步研究了其对甲基丙烯酸甲酯聚合反应的催化活性。