过氧铌杂多配合物位置异构体的合成、表征及催化性能

合成了6种钨硅杂多配合物异构体α、β_i-M₃H₂[SiW₁₁(NbO₂)O₃₉]·H₂O(M=Me₄N⁺(TMA),Bu₄N⁺(TBA),Et₄N⁺(TEA);β_i=β₁,β₂,β₃)。IR光谱、UV光谱、极谱、I^--S₂O₃^2-滴定证明合成的杂多配合物中有NbO₂基存在, ¹⁸³W NMR光谱证明其阴离子具有Keggin结构,催化实验结果表明,合成的化合物对烯烃环氧化反应具有催化活性,且过氧杂多配合物的催化活性高于非过氧杂多配合物,β异构体的催化活性高于α。     

Ln(NO3)3·C26H38N2O4(Ln=La、Ce)配合物的合成和La(NO3)3·C26H38N2O4·CH3CN的晶体结构

合成了2个新的希土冠醚配合物Ln(NO₃)₃·C₂₆H₃₈N₂O₄(Ln=La、Ce; C₂₆H₃₈N₂O₄=1, 7, 10, 16-四氧-4，13-二氮杂-N，N′-二苄基环十八烷)。通过元素分析，红外光谱，拉曼光谱及其 ¹H核磁共振谱进行表征。用四圆衍射仪测定了La(NO₃)₃·C₂₆H₃₈N₂O₄·CH₃CN的晶体结构。晶体属三斜晶系，P1空间群，晶胞参数：a=1.2869(4) nm, b=1.5868(6) nm, c=0.9147(2) nm; α=101.89(2)°, β=105.38(2)°, γ=71.96(3)°; Z=2。d_cald.=1.58 g·cm^-3, μ(MoKα)=13.25 cm^-1。中心镧离子与冠醚配体中的4个氧原子和2个氮原子配位，3个硝酸根中的6个氧原子也与La³⁺配位，形成配位数为12的配合物。     

三维异核Mn-Na配合物[MnNa(N3)4(C5H5N)4]的合成与表征

Azide-containing coordination polymers have received considerable attention for the construction of new molecule-based magnets. A three dimensional heteronuclear Mn-Na compound [MnNa(N₃)₄(C₅H₅N)₄] was obtained by reaction of [Mn₃O(O₂CCH₃)₆(py)₃]ClO₄ and NaN₃ in pyridine solvents. The title compound crystallizes in monoclinic space group C2/c, a=1.536 6(2), b=1.045 3(2), c=1.576 3(2) nm, β=90.309(3)°, V=2.531 8(6) nm³, Z=4. In the structure, each Mn³⁺ and Na⁺ ion coordinated with four N atoms from four N₃^- and two N atoms from two pyridine molecules. Each pair of Mn³⁺ and Na⁺ ion are linked by N₃^- bridges into a 3D polymer with PtS topology. CCDC: 706250.     

γ-AlOOH/Al2O3修饰硅藻土的制备与Cs+、Pb2+吸附性能

以结晶氯化铝(AlCl₃·6H₂O)作为铝源,十二烷基苯磺酸钠(SDBS)为模板剂,采用水热法在硅藻土盘上制备了束状纳米结构γ-AlOOH/Al₂O₃复合吸附剂。采用XRD、SEM、TEM、TG/DSC、N₂吸脱附等对样品进行了表征。研究了样品对¹³³Cs⁺及Pb²⁺的吸附能力。研究表明,样品γ-AlOOH/硅藻土、γ-Al₂O₃/硅藻土,对Cs⁺及Pb²⁺均具有良好的吸附性能,两者对Cs⁺的去除率分别为98.9%和99.6%;对Pb²⁺的最大吸附量分别为357.1、416.7 mg·g^-1。两种样品对Pb²⁺的吸附均符合Langmuir吸附模型。     

EDTA有效促进石墨相氮化碳(g-C3N4)光催化降解甲基橙

研究了在光照下,乙二胺四乙酸（EDTA）的添加促进石墨相氮化碳（g-C₃N₄）光催化降解甲基橙（MO）.研究了H⁺和羧酸根负离子对光降解MO的影响.紫外-可见漫反射光谱（DRS）研究表明,EDTA的加入并没有改变g-C₃N₄的电子结构和光电特性.EDTA的加入捕获了空穴（h⁺）,促进了光生e^-/h⁺对的分离,从而使光降解活性提高.证明了·O₂^-是光催化降解过程中的主要活性物种.基于上述研究结果,我们提出了一种可能的EDTA促进g-C₃N₄光催化降解MO的机理.这些结果为提高g-C₃N₄光催化降解水体中有机污染物的性能提供了一种新方法.     

层状类钙钛矿结构新铌酸盐KSr2Nb3O10

A new niobate compound KSr₂Nb₃O₁₀ was synthesized for the first time. The chemical compositions, crystal structure, optical property, density and melting point of the new compound were characterized by EPMA, TEM, XRD, DTA and so on. KSr₂Nb₃O₁₀ crystallizes the orthorhombic system with unit cell parameters a=0.7816(1) nm, b=0.7764(2) nm, c=2.9995(2) nm, V=1.8114(4) nm³, and space group P2₁2₁2₁, Z=8. The structure may be described as treble perovskite sheets ［Sr₂Nb₃O₁₀］^- interleaved with K⁺. Further, it was found that KSr₂Nb₃O₁₀ has intercalation phenomenon. Na⁺, Li⁺, H⁺, NH⁺₄ could exchange the interlayer cations K⁺ of KSr₂Nb₃O₁₀, and n-hexylamine also could intercalate into the place between the layers of ［Sr₂Nb₃O₁₀］^-.     

Dawson结构聚金属氧酸盐有机-无机复合物[{Y(DMSO)5(H2O)3}{Y(DMSO)8}][P2W18O62]·2DMSO·2H2O的合成、性质及晶体结构

以α-H₆P₂W₁₈O₆₂·nH₂O，Y₂O₃，DMSO(二甲亚砜)为原料合成了Dawson结构聚金属氧酸盐有机-无机复合物[{Y(DMSO)₅(H₂O)₃}{Y(DMSO)₈}][P₂W₁₈O₆₂]·2DMSO·2H₂O(1)，化合物晶体属于单斜晶系，P2₁/c空间群，M_r=5803.06，a=1.7614(4)nm，b=3.1527(6)nm，c=2.1523(4)nm，β=90.40(3)°，V=11.963(4)nm³，D_c=3.222g·cm^-3，μ=18.566mm^-1，Z=4，F(000)=10464。由17342个可观测衍射点[I≥ 2σ(I)]用于精修所有的结构参数，得一致性因子R=0.0745，wR=0.1438。结构解析表明，化合物中两个Y³⁺离子的配位环境均为八配位的畸变双冠三棱柱构型。CV行为研究表明，标题化合物中阴离子(pH=5.5)存在五步还原过程，得电子数依次为1，1，1，1，2。化合物的IR光谱和X-射线衍射结果表明，固态条件下配阳离子与杂多阴离子之间存在较强的相互作用。     

三元混合配合物Cu(C10H8N2O3)·(C5H5N)·(H2O)的合成和晶体结构

The novel copper(Ⅱ) complex with 2-oxo-propionic acid benzoyl hydrazone and pyridine ligands, Cu(C₁₀H₈N₂O₃)·(C₅H₅N)·(H₂O) (C₁₀H₈N₂O₃^2- is the dinegative ion of 2-oxo-propionicacid benzoyl hydrazone), has been synthesized and characterized by elemental analysis and IR. The crystal structure of the title complex was determined by single crystal X-ray diffraction technique. Complex crystallized in the triclinic space group P1 with a = 0.729 08(10) nm, b= 1.020 01(14) nm, c= 1.126 28(15) nm, α = 71.644(2) °, β = 80.437(2) °, γ = 89.160(2)°, V= 0.78328(18) nm³, Z= 2, D_c= 1.547 Mg·m^-3, μ(MoKα) = 1.417 mm^-1, F(000) = 374. The final R₁ = 0.030 6, wR₂= 0.084 2 for 2 992 observed reflections [I≥2σ(I)] out of 3357 unique reflections. In this complex, copper(Ⅱ) ion is square-pyramidally coordinated by two oxygen atoms and one nitrogen atom of tridentate C₁₀H₈N₂O₃^2- ligand, one nitrogen atom of the pyridine ligand, and one oxygen atom of water molecule with the oxygen atom of water molecule locating at the apical position. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 222656.     

配合物Cu(C15H12N2O3)(C5H5N)的合成和晶体结构

The title coordination compound with N-substituted-salicyl Schiff ligand, Cu(C₁₅H₁₂N₂O₃)(C₅H₅N), has been synthesized. The coordination compound crystallizes in orthorhombic system, space group Pbca with a=2.037 62(7) nm, b=0.698 45(2)nm, c=2.508 76(9)nm, V=3.570 4(2) nm³, Z=8, F(000)=1 688, D_c=1.529 g·cm^-3, M_r=410.91, μ=1.250 mm^-1, R=0.031 3 and wR=0.077 0. In the coordination compound, one phenolate oxygen, one carbonyl oxygen and one hydrazine nitrogen atom from the dianionic ligand N-salicylaldehyde-N′-(4-methoxybenzoyl) hydrazone and one pyridine nitrogen atom coordinate to Cu(Ⅱ) ion, forming a distorted square plane. CCDC: 218182.     

N2O+经由B2Пi←X2П跃迁的光解离机理研究

在超声分子束条件下,利用360.50 nm的电离激光使N₂O分子经由[3+1]共振增强多光子电离（REMPI）产生纯净的N₂O⁺（X²Π（000））分子离子,用另一束解离激光在230-275 nm范围扫描获得N₂O⁺经由B²П_i←X²Π跃迁产生的光解碎片（NO⁺和N₂⁺）激发（PHOFEX）谱. 获得的光解碎片激发谱可以归属为B²П_i（00n）←X²Π（000）序列跃迁. 我们分别将线性三原子分子离子N₂O⁺中N―N伸缩振动简化成NO和N之间的简谐振动,N―O伸缩振动简化成N₂和O之间的简谐振动,用谐振子的简谐势能曲线和波函数对N₂O⁺分子离子X²Π和B²П_i电子态振动能级间跃迁的Franck-Condon因子进行计算,和实验得到的碎片离子增强谱实验强度进行比较,对前人给出的分子数据（分子平衡核间距）进行验证,讨论了N₂O⁺经由B²П_i（00n）←X²Π（000）电子态跃迁的光解离机理和碎片离子的分支比.     

具有N…Cu作用的一维链状配合物Cu(C8H9N2O2)2的合成和晶体结构

The title complex Cu(L)₂ (HL=o-vanillin hydrazone) was synthesized by the reaction of Cu(CH₃COO)₂·H₂O with o-vanillin hydrazone in the ethanol. It was characterized by elemental analysis, IR and X-ray single crystal structure analysis. The crystal of the title complex [Cu(C₈H₉N₂O₂)₂] belongs to triclinic, space group P1 with a=0.457 57(8) nm, b=1.333 2(2) nm, c=1.386 0(3) nm, α=108.955(2)°, β=90.868(2)°, γ=95.859(2)°, V=0.794 4(2) nm³, Z=2, D_c=1.647 Mg·m^-3, μ=1.406 mm^-1, F(000)=406, and final R₁=0.035 1, wR₂=0.096 3. The complex comprises a four-coordinated copper(Ⅱ) center, with an N₂O₂ planar coordination environment. The molecules are packed in one-dimensional chain polymer though the N…Cu interaction from adjacent molecules, respectively. CCDC: 634854.     

Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄)、2,2-联吡啶(C₁₀H₈N₂, 简写bipy)与Eu(NO₃)₃•4H₂O反应, 首次培养出黄色单晶[Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]•0.5bipy•3H₂O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507, GOF＝0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C＝N中的氮与Eu^3＋配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.     

配合物{(n-Bu)2Sn[(η5-C5H5)Fe(η5-C5H4)COO]2}2的合成、谱学表征及晶体结构

合成了新型配合物{(n-Bu)₂Sn[(η⁵-C₅H₅)Fe(η⁵-C₅H₄)COO]₂}₂，用元素分析、红外光谱和核磁共振谱( ¹H、¹³C、¹¹⁹Sn)进行了表征，并用X-射线单晶衍射分析法测定其晶体结构。晶体属单斜晶系，空间群P2₁/c，晶胞参数a=11.753(4)?，b=21.133(7)?，c=23.374(9)?，β=101.62(3)°，V=5687(4)?³，Z=4，D_c=1.614Mg·m^-3，μ(MoKα)=1.912mm^-1，F(000)=2800，最终可靠因子R₁=0.0827，wR₂=0.2085。配合物分子呈中心对称，是具有Sn₂O₂中心内环的二聚体结构;每个锡原子与5个O原子和2个C原子形成扭曲的五角双锥几何构型，其中5个O原子为赤道配位原子，而C-Sn-C为配合物的轴。     

碳酸盐共沉淀法可控制备超高倍率锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2

采用碳酸盐共沉淀法通过调节NH₃·H₂O用量来实现可控制备超高倍率纳米结构LiNi_1/3Co_1/3Mn_1/3O₂正极材料。NH₃·H₂O用量会对颗粒的形貌、粒径、晶体结构以及材料电化学性能产生较大的影响。X射线衍射（XRD）分析和扫描电镜（SEM）结果表明,随着NH₃·H₂O用量的降低,一次颗粒形貌由纳米片状逐渐过渡到纳米球状,且n_NH3·H2O：（n_Ni+n_Co+n_Mn）=1：2样品晶体层状结构最完善、Li⁺/Ni²⁺阳离子混排程度最低。电化学性能测试结果也证实了n_NH3·H2O：（n_Ni+n_Co+n_Mn）=1：2样品具有最优异的循环稳定性和超高倍率性能。具体而言,在2.7~4.3 V,1C下循环300次后的放电比容量为119 mAh·g^-1,容量保持率为81%,中值电压基本无衰减（保持率为97%）。在100C（18 Ah·g^-1）的超高倍率下,放电比容量还能达到56 mAh·g^-1,具有应用于高功率型锂离子电池的前景。此NH₃·H₂O比例值对于共沉淀法制备其他高倍率、高容量的正/负极氧化物材料具有一定的工艺参考价值。     

二维层状结构十钒酸盐[K(H2O)2Ni(H2O)6]2[V10O28]的合成及性质(英)

A novel heteropoly compound, containing two kinds of coordinated cations, [K(H₂O)₂Ni(H₂O)₆]₂[V₁₀O₂₈], has been synthesized through routine process and characterized by elemental analyses, IR, ⁵¹V NMR and single crystal X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a=0.87382(17) nm, b=1.075 4(2) nm, c=1.111 1(2) nm, α=65.10(3)°, β=75.01(3)°, γ=70.63(3)°, V=0.884 8(3) nm³ and Z=1. The X-ray analysis reveals that the two kinds of coordinated cations are linked by three shared coordinated water molecules, and K⁺ cations coordinate with ten oxygen atoms: five of which come from V₁₀O₂₈^6- anion, the other five from water molecules. The title compound exhibits extended 2D array building up of V₁₀O₂₈^6- groups connected by ten-coordinated K⁺ cations. The hexahydrated nickel cations Ni(H₂O)₆²⁺ lie in neat apposition to three adjacent V₁₀O₂₈^6- clusters. CSD: 413271.     

{(n-Bu4N)2[Mo2O2S6Cu6Br4(4，4′-bipy)3]·0.5H2O}n的合成与晶体结构

Cluster coordination polymer {(n-Bu₄N)₂[Mo₂O₂S₆Cu₆Br₄(4,4′-bipy)₃]·0.5H₂O}_n (4,4′-bipy=4,4′-bipyridine), has been synthesized and characterized by X-ray crystallography. The polymeric anion {[Mo₂O₂S₆Cu₆Br₄(4,4′-bipy)₃]^2-}_n is composed of secondary building units (SBUs) [MoOS₃Cu₃], Br atoms and 4,4′-bipy ligands. Two secondary building units [MoOS₃Cu₃] and a double parallel 4,4′-bipy ligands form an octanuclear rectangular metallamacrocycle with the dimension of 1.13×0.39 nm², which is further connected by single bridging 4,4′-bipy ligands to form a 1D zigzag structure. Crystal data for compound 1: C₆₂H₉₇N₈O_2.50S₆Br₄Cu₆Mo₂, M=2 079.68, Triclinic, P1, a=0.982 40(10) nm, b=1.293 70(10) nm, c=1.737 4(2) nm, α=97.810(10)°, β=101.390(10)°, γ=108.520(10)°, V=2.005 1(4) nm³, Z=2, D_c=1.722 g·cm^-3, F(000)=1 039, μ(Mo Kα)=4.055 mm^-1, the final R=0.040 7, wR₂=0.097 2. CCDC: 236407.     

有机-无机复合物[H2(PW12O40){Zn(C10H8N2)2(H2O)}]·1.5[Zn(C10H8N2)3]·1.75H2O的合成、结构及性能

An organic-inorganic hybrid complex, [H₂(PW₁₂O₄₀){Zn(C₁₀H₈N₂)₂(H₂O)}]·1.5[Zn(C₁₀H₈N₂)₃]·1.75H₂O has been synthesized hydrothermally and structurally characterized by X-ray crystallography. The crystal belongs to monoclinic, space grounp C2/c, with a=4.709 4(2) nm, b=1.431 77(7) nm, c=2.621 07(1) nm, β=90.125(4)°, V=17.673 4(2) nm³, Z=8, D_c=3.087 Mg·m^-3, F(000)=14 884, μ(Mo Kα)=16.327 mm^-1. The structure was refined to R₁=0.068 7 and wR₂=0.158 0 for 20 128 observed reflections with I>2σ(I). Single crystal structure shows that the title compound is constructed from [PW₁₂O₄₀]^3- cluster anion and [Zn(C₁₀H₈N₂)₂(H₂O)]²⁺ metal-organic complex cation, in which metal Zn(Ⅱ) cation are coordinately bonded to the terminal oxygen of Keggin polyanions. The title compound exhibits good catalytic activity for oxidation of benzaldehyde to benzoic acid. CCDC: 624772.     

溶胶-凝胶法合成Li1-xNaxMn2O4及其作为水系锂离子电池正极材料的电化学性能

用溶胶凝胶法合成了Na⁺离子掺杂的Li_1-xNa_xMn₂O₄(x=0,0.01,0.03,0.05)。X射线衍射图表明Na⁺取代Li⁺进入Li_1-xNa_x Mn₂O₄晶格中,扫描电镜图看出产物是粒径为100~300 nm的颗粒。恒流充放电测试结果表明,Li_0.97Na_0.03Mn₂O₄在2C倍率下循环100圈后放电容量保持率比未掺杂的LiMn₂O₄从51.2%提升到84.1%。循环伏安测试表明Na⁺离子掺杂降低了材料极化且增大了锂离子扩散系数。10C倍率下Li_0.97Na_0.03Mn₂O₄仍有79.0 mAh·g^-1的放电容量,高于未掺杂样品的52.1 mAh·g^-1。Na⁺离子掺杂可以稳定材料结构并提高锂离子扩散系数,从而提高LiMn₂O₄的电化学性能,是一种可行的改性方法。     

纳米Fe3O4及Ni2 掺杂Fe3O4的制备、表征及吸附Pb(Ⅱ)的特性

采用一种改进的共沉淀法制备了纳米磁铁矿(Fe₃O₄)及Ni²⁺掺杂磁铁矿(Ni_xFe_3-xO₄,x=0.1,0.3,0.6),用X-射线衍射(XRD)、扫描电镜(SEM)、氮气物理性吸附、酸碱滴定等手段对产物进行了表征,用平衡吸附法研究了4种样品对Pb(Ⅱ)离子的吸附容量及吸附模型。结果表明,Fe₃O₄和3种Ni_xFe_3-xO₄均为近似球形的单相晶质纳米颗粒;与Fe₃O₄比较,Ni_xFe_3-xO₄的颗粒尺寸变小、表面电荷零点和pH＝5.0时的表面正电荷量降低;样品的孔体积、比表面积和表面分形度以及表面羟基含量都随产物中Ni²⁺掺杂量的增加而升高。4种样品对Pb(Ⅱ)的等温吸附数据均适合用Langmuir模型拟合(R²=0.9942~0.9858),其相关系数的大小表现为：Fe₃O₄>Ni_0.1Fe_2.9O₄>Ni_0.3Fe_2.7O₄=Ni_0.6Fe_2.4O₄;Freundlich模型对样品等温吸附Pb(Ⅱ)的实验数据拟合度较低(R²=0.981 3~0.947 7),4种样品的Freundlich相关系数的大小关系与Langmuir相关系数相反。初始pH=5.0时,Fe₃O₄,Ni_0.1Fe_2.9O₄,Ni_0.3Fe_2.7O₄和Ni_0.6Fe_2.4O₄对Pb(Ⅱ)的最大吸附容量分别为6.02,6.68,7.29和8.34 mg·g^-1。可见,Ni_xFe_3-xO₄(尤其是Ni²⁺掺杂量较高的产物)对水环境中重金属Pb(Ⅱ)的去除能力明显高于Fe₃O₄。     

一种新颖一维铅碘聚合物[(Pb2I5)(L-H+)·2DMF]n (L=Piperazine)的自组装合成和晶体结构(英)

The lead iodide adduct [(Pb₂I₅)(L-H⁺)·2DMF]_n(L=piperazine) has been prepared by self-assembly and structurally characterized. It presents one dimensional structure and crystallizes in Triclinic, P1 space group with the crystal cell parameter: a=0.922 06(18) nm, b=1.237 5(3) nm, c=1.297 2(3) nm, α=99.05(3)°, β=102.98(3)°, γ=105.30(3)°, and V=1.353 8(6) nm³, Z=2, D_c=3.078 Mg·m^-3, μ(Mo Kα)=18.127 mm^-1, F(000)=1 085, chemical formula C₁₆H₄₃N₈O₄Pb₄I₁₀ and M_r=2 509.39, the final R=0.053 3 and wR=0.146 4 for 3 889 observed reflections with I>2σ(I). CCDC: 250760.