含Keggin类型多酸单元和2-吡啶甲酸的杂化材料的合成、结构及表征

合成了2例基于2-吡啶甲酸（2-PA）和Keggin类型[SiW₁₂O₄₀]^4-、[PMo₁₂O₄₀]^3-多酸单元的有机-无机杂化材料：H₂[（CH₃）₄N]₆[Cu（2-PA）₂（SiW₁₂O₄₀）₂]（1）和（H₃O）[Cu₆（2-PA）₉（PMo₁₂O₄₀）（NO₃）]（2）,并用红外光谱以及X射线衍射对其进行了表征。单晶衍射结构分析表明化合物1为单斜晶系,空间群为P2₁/c,不对称单元中包含1个二价铜离子、2个2-吡啶甲酸配体以及2个Keggin类型[SiW₁₂O₄₀]^4-多酸单元并组成零维结构。循环伏安测试表明化合物1在扫速为100 mV·s^-1时,3组半波电位分别为-270、-516、-708 mV。化合物2为三方晶系,空间群为R3c,不对称单元中包含2个晶体学独立的二价铜离子并且具有2种不同的配位模式,是含六核簇合物单元的二维网络结构。     

Synthesis, structures and properties of new hybrid solids containing ruthenium complexes and polyoxometalates

Two new organic-inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV-vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy)₃]₂[H₂W₁₂O₄₀]·8H₂O (1), the [Ru(bpy)₃]²⁺ (bpy=2,2′-bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H₂W₁₂O₄₀]⁶⁻ linked through {KO₇} and {NaO₆} polyhedra, while in K₆[Ru(pzc)₃]₂[SiW₁₂O₄₀]•12H₂O (2), the [Ru(pzc)₃]⁻ (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW₁₂O₄₀]⁴⁻ clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion?π interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature.     

四硫富瓦烯衍生物/硬脂酸LB膜的导电性研究

报导了14种四硫富瓦烯衍生物／硬脂酸LB膜的导电性，并解释了硬脂酸量和碘蒸气掺杂对LB膜导电性的影响．     

钼钨钒磷杂多酸稀土衍生物的合成、表征及催化性质

报道了通式为K     

Synthesis and Characterization of Charge-transfer Complexes of Aminoethylphosphono-and Dimethylaminoethylphosphono-heteropolytungstic Acids of Keggin Type Structure

The charge-transfer complexes of heteropoly acids (HPA) possess special properties of light, electricity and magnetism, and have attracted widespread attention by researchers in the fields of functional materials and catalysis1. But until now, the electron acceptors of the charge-transfer complexes are the heteropolyanions with inorganic phosphoric acid, silicic acid etc. as the coordinate center2,3, the charge-transfer complexes of Keggin type structure of the organophosphonoheteropolytungs…     

铜二取代三元杂多化合物的制备、晶体结构和性质

The half Dawson structure complex has been prepared by reaction of Na₂WO₄·2H₂O, Na₂MoO₄·2H₂O and NaH₂PO₄ in water. [TBA]₄H₃[PW₆Mo₄Cu₂O₃₈(H₂O)₂] have been synthesized by reaction of [PW₅Mo₄O₃₄]^9- and Cu²⁺ in water and recrystallized in a mixed acetone/water solvent. They were characterized by elemental analyses, IR spectra and electronic spectra. The crystal structure of [TBA]₄H₃[PW₆Mo₄Cu₂O₃₈(H₂O)₂] has been determined by X-ray structure analysis for the first time, which belongs to trigonal with space group R-3, a=b=c=1.53081 (18) nm, α=β=γ=109.458(17)°, Z=1, D_c=3.141Mg·m^-3, R=0.0780, R_w=0.1480. The sites of the molybdenum, tungsten and copper atoms are disordered over 12 possible locations in the crystal, and the anion has a high symmetry due to the disorder of the molybdenum, tungsten and copper atoms. CCDC: 176656.     

二氧化碳与丙烯直接合成甲基丙烯酸用CuPMo／TiO2催化剂的研究

 用溶胶－凝胶法以磷钼酸（MPA）的铜盐溶液水解钛酸四丁酯制备了CuPMo／TiO2催化剂，并用ICP，XRD，TG－DTA，IR，TPD－MS和微反技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化性能．结果表明：杂多钼酸盐与TiO2表面通过O2－桥发生键联．在623K下，杂多阴离子仍保持其原有的Keggin结构；CO2在Lewis酸位Cu（Ⅱ）和Lewis碱位Cu－O－Mo桥氧的协同作用下形成卧式吸附态Cu（Ⅱ）←O－（CO）←（O－－Cu）；丙烯以分子吸附态在催化剂上吸附；在空速1500h－1，压力1MPa和温度563K的反应条件下，丙烯的转化率为4．2％，甲基丙烯酸的选择性为96％．     

柱撑杂多阴离子粘土的合成及表征

采用水热合成及离子交换法将Keggin结构三铁九钨镓酸盐杂多阴离子GaW9Fe3（H2O）3嵌入Zn2Al型阴离子粘土层间，得到了新型层柱状微孔材料Zn2Al－GaW9Fe3．用元素分析、XRD、IR、XPS等手段对产物的组成和结构进行了表征．结果表明，杂多阴离子嵌入Zn2Al型阴离子粘土层间，使柱撑杂多阴离子粘土具有1．0nm的通道高度．     

一种具有Keggin结构的固体杂多酸的合成及其晶体结构

以钨酸钠、氯化钴、醋酸钴及1,3-丙二胺为原料,利用水热合成法制备了一种具有Keggin结构的杂多酸H6[CoW12O40].2.5H2O;利用单晶X射线衍射分析了产物的晶体结构.结果表明,产物中的过渡金属Co2+离子作为中心原子与4个氧原子形成CoO4四面体;CoO4四面体被4个W3O13金属簇包围,与每个W3O13金属簇之间通过共顶点连接而形成[CoW12O40]6-阴离子;六个氢离子作为抗衡阳离子,最终形成固体杂多酸分子.     

Hydrothermal Synthesis and Structural Characterization of two Hybrid Keggin-based Polyoxometalates

Two new hybrid polyoxotungstates, [Co（2,2＇-bipy）3][a-H5PW11CoO40]-3H2O 1 and [Fe（2,2＇-bipy）3]2[a-HBW12O40]-2.5H2O 2 （2,2＇-bipy = 2,2＇-dipyridyl）, have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray structural analyses. The results of X-ray crystallography analyses exhibit that 1 consists of one a-Keggin anion [a-H5PW11CoO40]2- and one isolated [Co（2,2＇-bipy）3]2＋ complex, while 2 is constructed from one a-Keggin anion [a- HBW12O40]4- and two isolated [Fe（2,2＇-bipy）3]2＋ cations. The data for 1： orthorhombic system, space group Pbcn, a = 16.062（6）, b = 27.278（10）, c = 16.951（6）A, V = 7427（5）A3 and Z = 4; and those for 2： triclinic system, space group P1, a = 13.787（3）, b = 17.857（5）, c = 18.918（5）A, a = 88.009（12）, β = 72.768（10）, γ = 74.935（10）°, V = 4291（2）A3 and Z = 2.     

一种梳状高分子固体电解质的合成及LiSCN盐复合物的导电性

以乙烯／马来酸酐共聚物为骨架，分子量为３５０的聚乙二醇单甲醚为侧链，合成了新型的乙烯／马来酸酐共聚物多缩乙二醇酯聚合物固体电解质。用红外对该聚合物的合成过程进行了跟踪。用红外、ＤＳＣ、元素分析等对终产物进行分析，表明酯化反应进行完全，并按合成路线生成严格的半酯。产物的成膜性能好，比较柔软，电导率与盐浓度的关系在所研究的范围内存在两个峰，电导率与温度的关系符合ＶＴＦ行为。     

柠檬酸对Ru/AC氨合成催化剂结构和活性的影响

使用柠檬酸(CA)修饰石墨化活性炭(AC)和钌以改善Ru/AC催化剂中钌粒子的尺寸分布和催化剂的活性, 并通过透射电镜(TEM)、热重分析(TGA)、CO化学吸附和N2物理吸附等方法研究了柠檬酸对AC和Ru/AC催化剂织构、钌的分散度和催化剂的活性等性质的影响. 结果表明, 负载的柠檬酸优先吸附于活性炭微孔, 少量柠檬酸即可大幅度降低活性炭的比表面积, 增加活性炭表面含氧官能团的数量, 改善了钌粒子分布. 最佳负载顺序是柠檬酸和氯化钌依次负载. 在活性炭中添加适量的柠檬酸对催化剂的低温活性有显著影响. 柠檬酸处理后的Ru/AC催化剂活性最大提高幅度为21.4%.     

Synthesis and Characterization of Heteropoly Coordination Compounds Containing Optical Ligands

ＴｈｅｈｅｔｅｒｏｐｏｌｙａｎｉｏｎｐｈａｓｅｔｒａｎｓｆｅｒｃｈｅｍｉｓｔｒｙｃｒｅａｔｅｄｂｙＰｏｐｅＭ .Ｔ .ｉｎ 1 984ｈａｓｏｐｅｎｅｄｕｐａｎｅｗｆｉｅｌｄｆｏｒｈｅｔｅｒｏｐｏｌｙｃｏｍｐｏｕｎｄｒｅｓｅａｒｃｈ[1— 3] .Ｂｕｔｓｕｂｓｔｉｔｕｔｉｎｇｃｏｏｒｄｉｎａｔｉｏｎｗａｔｅｒｍｏｌｅｃｕｌｅｓｂｙｏｒｇａｎｉｃｏｐｔｉｃａｌｌｙａｃｔｉｖｅｌｉｇａｎｄｈａｓｎｏｔｂｅｅｎｒｅｐｏｒｔｅｄｉｎｌｉｔｅｒａｔｕｒｅｓｕｎｔｉｌ 1 997[4] .Ｔｈｉｓ ｐａｐｅｒｃｏｖｅｒｓｓｉｘｈｅｔ…     

功能特异性杂多酸离子液体催化丁二酸水溶液直接酯化

将以磺化六亚甲基四胺([HMT-4PS])制备的阳离子与以杂多酸([HPA])制备的阴离子结合, 制备了一系列功能特异性离子液体催化剂([HMT-4PS][HPA]); 将其用于催化甲醇(MeOH)与丁二酸(SA)水溶液的直接酯化反应. 结果表明, 该系列离子液体在反应过程中以“乳状液”的形式均匀分散在体系中. 反应结束后, 通过降低体系极性即可实现催化剂的快速分离. 在合成的系列催化剂中, [HMT-4PS]₃[PW]₄表现出最佳的催化活性. 分别探讨了反应温度、 催化剂用量、 酸醇摩尔比和反应时间等因素对反应的影响, 确定了最优反应条件: 温度80 ℃, 催化剂用量5%(质量分数, 按丁二酸水溶液计), n(SA)∶n(MeOH)=1∶30, 反应时间8 h. 最优条件下丁二酸的转化率达到79.3%, 二酯选择性达到92.9%; 该催化剂重复使用5次后, 丁二酸转化率及二酯选择性仍分别保持在77%及90%以上.     

Synthesis and Conductivity of a New Series of Organometallic Charge Transfer Salts

In order to study the relationship between structure and conductivity, ten new organometallic radical ionic salts. [CpFeBz]_n[M(mnt)₂] and [CpFeBz]_n[M(dmit)₂] (M=Ni, Pd, Pt, Cu, Co; Cp=Cydopentadienyl; Bz=Benzene; H₂mnt=maleonitriledithiole; H₂dmit=4,5-dimercapto-1, 3-dithioie-2-thione; n=1 or 2), were synthesized according to a new synthetic route. They were characterized using elemental analysis, infrared and ¹H-nuclenr magnetic reso-nance spectroscopy. The crystal structure of [CpFeBz]₂[Ni(mnt)₂] was determined using X-ray diffraction. The electrical conductivity of siolid stale was reported. Gomplexes of [CpFeBz]_n[M(mnt)₂] showed a low conductivity, while complexes of [CpKeBz]_n[M(dmit)₂] exhibited a rather high conductivity in the range of 10^-1-10^-2S·cm^-1.     

Synthesis,Molecular Structure,Optical Properties and Electrical Conductivity of Zwitterionic Ferrocenyldithiophosphonates

Ferrocenyldithiodiphosphetane [FcPS(μ‐S)]₂ [Fc = Fe(η⁵‐C₅H₄)(η⁵‐C₅H₅)] reacts with the aminoethanol derivatives 1‐ethyl‐3‐pyrrolidinol and 2‐(piperazin‐1‐yl)ethanol to give the zwitterionic (O‐ethylammonium)ferrocenyldithiophosphonates ( 2 ) and ( 3 ), which were fully characterized by elemental analysis, IR and NMR spectroscopy and mass spectrometry. The optical and electrical properties of 2 and 3 as well as those of the previously reported [FcP(S)S(OC₂H₄NHEt₂)] ( 1 ) were studied. A molecular structure determination of 1 is also reported.     

二氧化碳和丙烯直接合成甲基丙烯酸NiPMo12催化剂的研究

用硝酸镍对磷钼酸(MPA)进行改性制得NiPMo12催化剂.采用ICP,XRD,Tg-DTA,EXAFS,IR,TPD-MS和微反技术研究了催化剂的化学组成、分子结构、化学吸附性质和催化反应性能.350℃下NiPMo12催化剂仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni—O—Mo的桥氧协同作用下可生成CO2桥式吸附态Ni(Ⅱ)←O—(CO)—(O-—Ni).丙烯在催化剂上存在多种吸附态.在氢转移和碳插入作用下得到了反应产物MAA.在290℃和1MPa的反应条件下,丙烯的摩尔转化率为2.6%,产物MAA选择性为96%.     

分级结构多酸微米管的合成及对阿霉素的吸附

通过简单的无模板法,由三缺位α-SiW9多金属氧酸盐制得了饱和Keggin结构SiW12多金属氧酸盐的微米管状晶体,并通过红外光谱、热重分析和X射线粉末衍射对其进行了表征.采用光学显微镜和扫描电子显微镜观察到所合成的分级结构管状晶体具有微米级空腔和管壁的纳米级孔隙.将阿霉素(DOX)吸附于所制备的SiW12微米管中,得到了负载阿霉素的DOX@SiW12微米管,其在紫光和绿光的激发下可显示阿霉素的特征红光.     

两种结构钼磷酸的催化氧化行为

考察了Dawson与Keggin结构钼磷酸的催化氧化行为,并与结构特性进行了关联,结果发现,Dawson结构的杂多酸对氧化脱氢及插入氧反应均有更高的活性。     

杂多配合物（X（NbO2）W11O39）^n—的合成与性质研究

钼钨的杂多配合物可作催化剂、电子显微镜的"着色剂"和分析试剂等[1]．近年来,含银的杂多配合物越来越引起人们重视[2]．Hill和Kim[3]报道了过氧化铌取代的杂多钨硅酸盐的合成及抗病毒性实验,指出含过氧化铌的杂多化合物对人体无害且对HIV－1病毒具有很高的活性．为了深人研究此类化合物,本文报道了具有Keggin结构的「X（NbO2）W1;O39]n-（X=Ga,Ge）杂多配合物的合成及性质,为抗病毒试验提供了4个新化合物．1实验部分1.1仪器与试剂BECKMAN－DU8B紫外分光光度计;ALPHACENTAURTFTIR红外分光光度计;384B型极谱分析仪…