高岭石/二甲基亚砜插层复合物结构模拟

以张家口宣化高岭土为原料,制备高岭石/二甲基亚砜( dimethylsulfoxide, DMSO)插层复合物。利用X射线衍射( X-ray diffraction, XRD ),傅里叶红外光谱( Fourier transform infrared spectracopy, FT-IR ),热重-差热分析( Thermogravimetric-differential thermal analysis, TG-DTA)对制备的复合物进行表征。其中,XRD和FT-IR显示二甲基亚砜分子已进入高岭石层间,使其层间距由0.718 nm增加至1.130 nm。 TG-DTA结果表明插层复合物热相变经历以下三个阶段：二甲基亚砜分子脱嵌(约199℃),脱羟基(约522℃),高岭石重结晶(997℃)。此外,依据表征结果推测二甲基亚砜分子在高岭石层间存在形式,构建了复合物体系的结构模型,并对高岭石/二甲基亚砜插层作用机理进行了讨论。     

黏土矿物-十六烷基三甲基氯化铵作用机理及其结构

黏土矿物有机插层复合物作为重要的功能材料现已被广泛应用于吸附、化工和环保等众多领域.采用插层法将十六烷基三甲基氯化铵(CTAC)插入到黏土矿物高岭石、钠基蒙脱石和蛭石层间,利用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、热重-差示扫描量热(TG-DSC)及扫描电镜(SEM)等表征方法对插层复合物的作用机理及结构进行研究.结果表明:高岭石在经过多次"替代"插层后,层间氢键被破坏,层间作用力减弱,CTAC分子进入其层间,这引起高岭石片层由于层间的束缚力释放形成卷曲形貌.蒙脱石与蛭石以离子交换的形式与CTAC分子发生反应,该过程尚未对它们的形貌产生明显影响.此外,进一步建立了黏土矿物-CTAC插层复合物的结构模型,提出CTAC分子在高岭石和蒙脱石层间分别以35°和32°的夹角双层斜立,在蛭石层间以44°的夹角单层斜立.     

插层法制备g-C3N4/高岭石复合材料及其光学性能

高岭石表面与层间具有较高的活性和良好的规范性,因而适合对其进行化学修饰,在催化剂负载方面值得深入研究.本文以甲氧基嫁接的高岭石为前躯体,采用置换插层法制备出高岭石/三聚氰胺插层复合物,进一步在550 ℃煅烧获得g-C3N4/高岭石复合光催化剂.利用X射线衍射、傅里叶红外和热重-差热分析等手段对复合光催化材料进行表征,并对其光催化性能进行研究.结果表明,当高岭石与光催化剂前驱体三聚氰胺质量比为1∶1和1∶2时,较难缩聚得到g-C3N4;然而,当高岭石与三聚氰胺质量比为1∶3、1∶4、1∶5时,可获得不同g-C3N4占比的复合材料,其整体分散状况因高岭石的加入而有效改善,这表明高岭石的加入能有效避免g-C3N4的团聚.所制备的高岭石负载石墨相氮化碳光催化材料具有较好的光学性能,在探索经济、高效、绿色矿物基复合光催化剂方面研究具有重要意义.     

煤系高岭石插层合成X型沸石分子筛及其结构中钾的占位

归属于八面沸石结构(FAU)的X型沸石分子筛是一种重要的催化剂,在石油化工及吸附剂领域具有广泛应用前景,目前利用传统工艺生产的沸石分子筛价格昂贵.我国煤系高岭石资源丰富、品质优良,经过醋酸钾插层处理后,是合成X型分子筛的理想原料.本文应用X射线衍射、红外光谱、热重等多种表征技术,对高温焙烧后的高岭石/醋酸钾插层复合物进行了表征.结果表明,焙烧高岭石/醋酸钾插层复合物合成X型沸石的最佳温度为800℃,最佳浓度为30;.并进一步探讨了高岭石/醋酸钾插层复合物合成X型沸石分子筛的机理、结构以及钾离子在沸石分子筛骨架外的分布位置.     

TiO2/蛭石纳米复合物的制备及产物结构变化研究

以TiOSO4为钛源,采用阳离子交换、原位水解、原位脱羟技术制备了TiO2/蛭石纳米复合物.采用XRD、FTIR、FSEM等对TiO2/蛭石纳米复合物制备过程产物包括聚合羟基钛离子-蛭石、水合氧化钛/蛭石复合物以及TiO2/蛭石纳米复合物的结构、微观形貌等进行了表征和研究.结果表明:在pH值较低时,TiOSO4溶液中的聚合羟基钛离子通过阳离子交换作用进入蛭石层间域中,随着pH值逐渐升高,进入层间域中的聚合羟基钛离子水解聚合形成水合氧化钛,蛭石的层间域被撑大,有序性结构被破坏;经900℃热处理后水合氧化钛脱水形成TiO2/蛭石纳米复合物;样品中TiO2含量随结束pH值的升高而增加,并均匀地插入蛭石的层间域中或分布在蛭石片层的表面;与纯TiO2纳米粉体相比较,TiO2/蛭石纳米复合物结构中TiO2在900℃焙烧后仍未出现金红石相,表明蛭石结构层对TiO2的晶相转变具有明显的阻滞作用.     

溶胶-凝胶合成NiO-ZnO复合物及其乙醇敏感特性研究

以Zn(NO3)2·6H2O和Ni(NO3)2·6H2O为原料,采用柠檬酸溶胶-凝胶法合成了NiO-ZnO系列复合物.利用X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)等对系列复合物的物相及形貌进行表征,利用静态配气法对其气敏性能进行测试.研究了煅烧温度对复合物乙醇敏感特性的影响.结果表明,600℃下煅烧得到的NiO-ZnO复合物对乙醇在较低的工作温度125℃下具有良好的敏感性能,如对50 ppm乙醇的灵敏度为29.8,响应和恢复时间很短仅为8s和14 s,且对于汽油、丙酮、乙醚等其余7种测试气体有较高的选择性,经1个月的稳定性测试该复合物对乙醇敏感特性基本保持不变.     

Bi2O3/g-C3N4/TiO2三元复合物的制备及其可见光催化活性研究

以工业纳米TiO2,三聚氰胺(C3H6 N6)和硝酸铋(Bi(NO3)3·5H2O)为原料,通过高温煅烧制备Bi2O3/g-C3 N4/TiO2三元复合物,采用XRD、XPS、FT-IR、UV-vis、PL光谱等对其结构进行了表征.结果表明g-C3 N4和Bi2O3分散覆盖在TiO2表面,形成具有异质结结构的Bi2O3/g-C3N4/TiO2三元复合物,其带隙降低,对可见光的吸收增强,电子和空穴通过在Bi2O3、g-C3N4和TiO2三者界面间的转移有效延长了光生载流子的寿命,从而提高光催化效率.以亚甲基蓝为目标污染物评价其光催化活性.结果表明,当TiO2与C3H6N6质量比为1∶2.5,Bi(NO3)3·5H2O含量为0.35;,煅烧温度为520℃,煅烧时间为5h时制得的Bi2O3/g-C3 N4/TiO2三元复合物(即0.35Bi/C/T)活性最高,LED灯(12 W)光照180 min后对10mg/L亚甲基蓝溶液降解率达98.1;.     

不同结构Al/Fe2O3纳米复合物的对比研究

采用三种工艺合成出不同结构的Al/Fe2O3纳米复合物.运用扫描电镜、X射线衍射仪、差示扫描量热仪等对产物进行对比表征,结果表明采用溶胶-凝胶法制备的纳米Al/Fe2O3颗粒粒径均在100 nm以内,而传统混合或简单复合工艺制备的Al/Fe2O3颗粒尺度在微米或亚微米级;XRD证实合成产物纯度高;热分析数据显示纳米Al/Fe2O3初始分解峰温较低,而放热焓值偏高,说明材料纳米化在改善安全性的同时显著提高了能量释放速率.     

低温水热制备BaZrO3微晶及其结晶动力学研究

在碱性条件下([NaOH] =0.008 mol/mL),以氯化钡(BaCl2·2H2O)和氧氯化锆(ZrOCl2·8H2O)为原料,采用传统水热法在低温下制备了锆酸钡(BaZrO3)微晶.利用XRD和SEM分别对产物进行了物相组成及微晶形貌的测试与表征.研究了反应温度为135℃时不同反应时间对产物微观结构及形貌变化的影响.结果表明:在135℃下反应2h即可合成纯相的BaZrO3粉体,且随着水热温度的升高,产物由无定形态变为类球状结构最终变为棱角分明的菱形十二面体结构,结晶程度提高,晶粒尺寸增大.通过对其结晶动力学研究,计算得到BagrO3微晶的表观成核活化能为24.36 kJ/mol.     

V2O5/g-C3N4复合物的制备及可见光催化性能研究

以偏钒酸铵和尿素混合物为前驱体,混合煅烧制备了V2O5/g-C3N4复合物催化剂.用X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见光漫反射吸收光谱(UV-vis)、比表面积测试(BET)、光致发光谱(PL)等对其结构进行了表征.结果表明复合物中存在V2O5和g-C3N4形成异质结构,其禁带宽度减小、吸收带边红移,光催化效率有显著提高.以亚甲基蓝(MB)为目标化合物,评价了样品的光催化活性,当前躯体中尿素与NH4VO3质量比为10∶1,煅烧温度为500℃,煅烧时间为0.5h,催化剂活性最高.在60W日光灯照射40 min,对亚甲基蓝得降解率达到97.52;.     

Structure of the Antiplasmodial Compound 7,9-Dinitrocryptolepine Hydrochloride Methanol Solvate

Abstract  The structure of C₁₆H₁₀N₄O₄[HCl,1.5CH₃OH], M_r = 406.80, has been determined from X-ray diffraction data. The crystals are monoclinic, space group C2/c, with eight molecules per unit cell and a = 21.482(4), b = 7.131(1), c = 24.495(5) ?, β = 111.01(3)°, crystal density D_c = 1.546 g/cm³. The material was difficult to crystallize and crystals produced were found to be poor diffractors. Intensity data were measured at liquid nitrogen temperature using a weakly diffracting crystal typical of the batch. However the X-ray analysis has finally enabled the chemical constitution of this cryptolepine derivative, which was previously incorrectly assigned, to be unequivocally established. Direct methods were used to solve the structure which was refined by full-matrix least squares to a conventional R-index of 0.0798 for 2,861 reflections and 268 parameters. The 7,9-dinitrocryptolepine molecule is highly planar with a strong intramolecular hydrogen bond between N(10) in ring C and O(92) of a nitro group. There are a number of intermolecular hydrogen bonds involving the cryptolepine derivative the hydrochloride and both solvated methanols. One of the methanol solvate molecules (methanol 2) is unusually disordered with its C atom lying exactly on a crystallographic twofold axis. Consequently the methanol OH and H₃ groups are at 0.5 occupancy and repeated by the twofold symmetry. Graphical Abstract  Cryptolepine (5-methyl, 10H-indolo[3,2-b]quinoline) the principal constituent of Cryptolepis sanguinolenta (Periplocaceae) is currently of interest as a lead compound for the development of both antimalarial and anticancer agents. Cryptolepine has potent activity against malaria parasites in vitro, but it is also cytotoxic on account of its abilities to intercalate into DNA, inhibit DNA synthesis and inhibit topoisomerase II. The 7,9-dinitroanalogue of cryptolepine was synthesised as part of a program designed to discover new antimalarial and anticancer agents. The X-ray structure of this compound will help to determine whether or not 7,9-dinitrocryptolepine is able to intercalate into DNA and facilitate the design of new cryptolepine analogues with DNA binding properties appropriate for antimalarial (with no DNA intercalation) or anticancer (sequence-specific binding) applications.      

Crystal Structure and Thermodecomposition Kinetics of Mn(II) Complex with 1-Phenyl-3-Methyl-4-Benzoyl-5-Pyrazolone

Abstract  

The complex [Mn(PMBP)₂(CH₃OH)₂] of manganese(II) with 1-phenyl-3-methyl- 4-benzoyl-5-pyrazolone (PMBP) was prepared and characterized by elemental analysis, thermal analysis, IR. The crystal structure of the complex determined by single crystal X-ray analysis, indicates that PMBP is a bidentate ligand in the complex and Mn(II) atom is six-coordinated and is in a meridional octahedral environment. The compound crystallizes in the monoclinic system, space group P ₂(1)/c, with a = 11.038(10) ?, b = 16.254(15) ?, c = 9.540(9) ?, α = 90.00°, β = 105.112(10)°, γ = 90.00°, V = 1,652(3) ?³, D _x  = 1.354 g cm⁻³ and Z = 2. The thermal decomposition kinetics of the complex was investigated under nonisothermal conditions using the Achar differential method and the Coats–Redfern integral method.     

硬脂酸/插层高岭石复合相变材料的制备和热性能研究

高岭石(K)是一种常见的黏土矿物,具有低成本、阻燃、多层结构等固有优点。本文采用真空浸渍法将硬脂酸(SA)吸附到插层高岭石(IKL)和二甲基亚砜(DMSO)复合物的孔隙中来制备用于储热的复合相变材料。通过X射线衍射(XRD)、红外光谱(FT-IR)、热重分析(TG)、差示扫描量热法(DSC)、扫描电子显微镜(SEM)和比表面积分析仪(BET)表征了复合材料的热性能、结构和主要组分。由于插层复合物形成后高岭石层间距增大,对SA的吸附率达到32.3%,熔化和凝固潜热值分别为43.36 J/g和43.16 J/g,熔化和凝固温度分别为51.9℃和51.7℃。此外,该复合相变材料具有较好的热稳定性。由于SA/IKL复合相变材料具有高吸附量、高潜热、良好的热稳定和低成本等优点,因此,其在实际的应用中具有潜在的价值。     

Kinetics of Desolvation and Structure of Bulky Xanthenol Inclusion Compounds

Abstract  The inclusion compounds of 14-hydroxy-14-toluenyldibenzo[a:j]xanthene (H) with the guests acetone (H·ACE), pyridine (H·PYR) and N,N-dimethylformamide (H·DMF) were all successfully solved in the triclinic spacegroup P-1 with unit cell dimensions for H·ACE: a = 9.415(2) ?, b = 9.730(2) ?, c = 12.994(3) ?, α = 82.65(3), β = 76.69(3), γ = 88.67(3), Z = 2; for H·PYR: a = 9.482(2) ?, b = 10.169(2) ?, c = 13.089(3) ?, α = 106.59(3), β = 95.91(3), γ = 90.35(3), Z = 2 and for H·DMF: a = 9.537(19) ?, b = 10.055(2) ?, c = 13.129(3) ?, α = 79.18(3), β = 74.42(3), γ = 86.46(3), Z = 2. The thermal stabilities for all compounds were investigated and in particular the kinetics of desolvation for the DMF compound was determined using both isothermal and non-isothermal methods. Index Abstract  The host compound 14-hydroxy-14-toluenyldibenzo[a:j]xanthene forms inclusion compounds with the guests acetone, pyridine and N,N-dimethylformamide. The crystal structures were determined and their thermal stabilities investigated. The kinetics of desolvation for the DMF compound was determined using both isothermal and non-isothermal methods.      

Optical Properties,Conductivity and Structure of the DTT-TCNQ CT Complex

Abstract

The crystal structure, the optical spectra and electrical conductivity of dithieno(3,2-b; 2′,3′-d)thiophene-tetracyanoquinodimethane (DTT-TCNQ) charge-transfer complex have been measured. DTT-TCNQ crystallizes in the monoclinic space group P2₁/c with a = 7.206(2), b = 7.574(2), c = 32.324(9), β - 92.18(4)°, Z - 4, and the donor and acceptor molecules are arranged in alternated stacks.

The low conductivity (a = 10^?2 S cm^?1 for the single crystal, along the stacking axis a) is characteristic of a semiconductor with activation energy of .61-.76 eV, and is related to the alternate stack structure.

Despite the poor condctivity of the DTT-TCNQ CT complex we estimated, from structure and IR data, a low degree of ionicity (p = .2–.3) which characterizes the DTT molecule as an interestign donor.

The polarized IR spectra shows the effect of vibronic activation of some of the a_g modes of TCNQ.     

奥沙拉秦钙配合物的合成、结构及表征

本文通过CaCl2·2H2O与药物奥沙拉秦及辅助配体邻菲罗啉在水热条件下得到了一个新的奥沙拉秦配合物[ Ca(L) (Phen)·4(H2O)]n(H2L=奥沙拉秦=3,3-azo-bis-6-hydroxybenzoic acid)(1).通过元素分析、红外对配合物进行了表征,并利用X单晶射线衍射仪测定了其结构.结构解析表明,配合物1属三斜晶系,空间群P-1,晶胞参数a=0.8001 (3) nm,b=1.1245(4) nm,c=1.5129(6) nm,α=89.450(6)°,β=86.297(6)°,γ=77.633(6)°,V=1.3268(9) nm3,Z=2,F(000) =636,最终偏差因子(对Ⅰ＞2σ(Ⅰ)的衍射点),R1=0.0521,wR2 =0.1538,S=1.045.在该结构中,中心Ca(Ⅱ)离子周围形成了一个稍微扭曲的五角双锥体,分别与一个来自奥沙拉秦配体的羧基氧原子(单齿)、两个邻菲罗啉中的两个N原子和四个水分子配位.     

Synthesis and Crystal Structure of Isobutyl-substituted Tetramethylcyclopentadienyl Tetracarbonyldiiron Complex

Abstract  The synthesis of the new ligand, (C₅Me₄ ⁱ Bu)H was described and its reaction with Fe(CO)₅ to prepare (C₅Me₄ ⁱ Bu)₂Fe₂(CO)₄ was presented. The structure of complex was characterized by IR, ¹H NMR, elemental analysis and single crystal X-ray diffraction. It confirms the complex is a dimer with bridging and terminal CO groups. The Fe–Fe bond distance is 2.5508(9) ?. (C₅Me₄ ⁱ Bu)₂Fe₂(CO)₄ belongs to triclinic: space group P ī, with a = 8.5468(17) ?, b = 8.8997(18) ?, c = 9.4044(19) ?, α = 89.52(3)°, β = 74.11(3)°, γ = 86.42(3)°, V = 686.6(2) ?³, Z = 2, Dc = 1.399 g cm⁻³, μ (MoKα) = 1.090 mm⁻¹, F(000) = 306, and final R ₁ = 0.0324, wR ₂ = 0.0852 for observed reflections 2,396 (I > 2σ(I)). Graphical Abstract  The synthesis of the new ligand, (C₅Me₄ ⁱ Bu)H was described and its reaction with Fe(CO)₅ to prepare (C₅Me₄ ⁱ Bu)₂Fe₂(CO)₄ was presented. Single crystal X-ray diffraction analysis reveals that the molecular structure of this complex is a dimmer.      

不同结晶度高岭石的带电性研究

本文采用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)和热分析(TG-DSC)等三种表征手段,对四个不同地区高岭石样品的结构特征进行了研究.结果表明,高岭石结晶度高低顺序为:淮北>大同>龙岩>清远,Hinckley结晶度指数与脱羟基温度具有较好的相关性.利用电泳仪测定了高岭石颗粒在不同pH条件下的表面电位,并且通过线性拟合pH值-电位图得到了不同结晶度高岭石的零电荷点(PZC).进一步研究得出4种高岭石具有相近的PZC,其范围为3.2～4.3.在pH=7条件下,高岭石的表面电位与Hinckley结晶度指数呈现正相关,而PZC受结晶度指数的影响不强烈.