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.     

高岭石/甲醇复合物结构及其脱嵌动力学研究

目前对高岭石/二甲基亚砜(Kaol-DMSO)和高岭石/甲醇(Kaol-Me)复合物的研究大多局限于对其表面特征分析,鲜有对其脱嵌动力学特征研究的报道.本文在综合分析Kaol-DMSO和Kaol-Me复合物结构的基础上,重点针对其脱嵌动力学特征进行分析.结果表明:与二甲基亚砜(DMSO)分子依靠氢键结合在高岭石晶层间不同,甲醇(Me)分子是取代高岭石晶层八面体结构中Al-OH的-H形成甲氧基嫁接在晶层中.由于DMSO和Me在高岭石层间有着两种不同的存在状态,所以Kaol-Me复合物的活化能大于Kaol-DMSO插层复合物的活化能.活化能的大小反映了其结构的稳定性,据其活化能值推断Kaol-Me复合物的稳定性大于Kaol-DMSO插层复合物.     

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。     

TiO_2/氧化石墨烯纳米复合物的制备及结构变化

为了探讨TiO2/氧化石墨烯纳米复合物的制备技术及产物结构的变化规律,采用微波法将钛酸丁酯引入季铵盐/氧化石墨插层复合物的层间域内,钛酸丁酯经原位水解在氧化石墨层间生成Ti(OH)4,再经焙烧处理制备TiO2/氧化石墨烯纳米复合物。采用XRD、SEM、FTIR和XPS对原料和不同阶段生成的产物的结构及变化、微观形貌、氧化官能团特征和化学键特点进行表征。结果表明,钛酸丁酯在原位水解过程中将氧化石墨剥离为氧化石墨烯;TiO2/氧化石墨烯纳米复合物中锐钛矿型TiO2的形成温度比纯TiO2的提高了约100℃;TiO2/氧化石墨烯纳米复合物中的TiO2和纯TiO2的平均晶粒尺寸都随焙烧温度的升高而增大,但前者的平均晶粒尺寸均小于相同温度焙烧处理的纯TiO2的;在TiO2/氧化石墨烯纳米复合物中氧化石墨烯与TiO2之间形成Ti-O-C键,并抑制了锐钛矿型TiO2的形成,而氧化石墨烯作为阻隔层则阻碍了锐钛矿晶粒的长大。     

CdS/沸石分子筛复合光催化剂的制备及光催化性能

以煤矸石为原料,经Na2CO3碱熔活化和水热合成获得了沸石分子筛;利用Cd2+对沸石分子筛进行离子交换并通过沉淀过程制得了CdS/沸石分子筛复合粉体.采用X射线粉末衍射(XRD)和扫描电子显微镜(SEM)对所得样品进行表征,并以模拟太阳光为光源,罗丹明B (RhB)为目标降解物,对其光催化活性进行了研究.结果显示:沸石分子筛上负载的CdS的晶相为立方相,制得的CdS/沸石分子筛复合粉体具有较好的光催化活性,且三次循环利用后仍具有较好的催化活性,在模拟太阳光辐照下,CdS/zeolite(0.5 M)复合粉体重复利用3次后,处理260 min对RhB的降解率仍可达91.3;.所得粉体对RhB的光催化过程符合一级动力学方程式,光催化过程中,RhB 紫外可见光谱的蓝移现象揭示所得CdS/沸石分子筛可通过脱乙基-共轭显色基团断裂途径降解RhB.     

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.     

粉煤灰基地质聚合物水热转化FAU型分子筛的工艺与表征

以粉煤灰基地质聚合物为基本骨架,通过水热合成法将其原位转化为自支撑FAU型沸石分子筛.研究水热过程中NaOH浓度、NaOH体积、水热温度和水热时间对FAU型沸石分子筛结晶程度的影响,得到粉煤灰基地质聚合物原位转化FAU型沸石分子筛型体的适宜条件:水热温度100℃,NaOH浓度2.0 mol/L,NaOH体积50 mL,水热时间18 h.XRD、SEM和FTIR分析表明,所得FAU型分子筛结晶纯度高,具有致密又规则的八面体形貌,基本继承了地质聚合物的主要骨架结构,其抗压强度为18.8 MPa,BET比表面积为175.31 m2/g.该法工艺简单,环境友好.在此方法的基础上通过改变原料配比和反应条件,可以合成其他类型的沸石分子筛型体.     

醋酸根型层状双氢氧化物与蒙脱石的插层组装作用研究

在水热法合成硝酸根型层状双氢氧化物(NO3-LDH)的基础上,用离子交换法制备醋酸根离子插层层状双氢氧化物(Aco-LDH).在超声作用下,利用水分子对Aco-LDH层间域内氢键网络的破坏作用实现了Aco-LDH的剥离.利用蒙脱石在水中的溶胀特性实现了其片层的分散剥离.将剥离后的LDH片层与剥离蒙脱石(MMT)进行插层组装获得了LDH/MMT层状复合材料.用XRD、FFIR、TEM、AFM、N2吸附-脱附等手段对样品进行了表征.结果表明,当Aco-LDH浓度为1 mg/mL时,在水中超声处理获得厚度为5～20 nm的LDH片层.蒙脱石分散后其层间距扩大,结晶程度降低.插层组装作用获得的LDH/M MT层状复合材料的主体为蒙脱石,LDH与MMT之间形成片-片组装结构,复合物的层间距为1.50 nm,接近单元LDH片层与单元MMT片层的堆叠结构厚度,比表面积达105.89 m2/g.     

高炉渣基A型沸石的合成及对Pb2+离子的吸附

以内蒙古包钢高炉渣为前驱体,采用水热法成功合成了高炉渣基A型沸石,通过XRD、SEM表征其微观结构,并研究其对Pb2离子的吸附性能.研究结果表明,提取高炉渣中的SiO2和Al2O3分别为硅源和铝源,再外加一定比例铝源能够合成高炉渣基A型沸石,最佳合成条件为:n(SiO2)/n(Al2O3)=0.24、nH2O/n(SiO2)=98、水热时间为12 h和水热温度为100℃.所合成的高炉渣基A型沸石对Pb2离子具有较强的吸附性能,吸附率高达94.82;,符合拟二级动力学模型,属于多分子层的吸附,吸附容易进行,平衡吸附量为39.37 mg/g.     

Iodine Intercalation of Bi2Sr2Ca(n−1)CunOy(N=2,3) Superconductors by Using Reactants I2 or FeI2

Abstract

The change of superconductivity induced by intercalation is very interesting We have investigated on intercalation into Bi2212 single crystal and Bi2223 polycrystalline superconductors using FeI₂ or I₂ as reactant. The iodine intercalation by using FeI₂ as a reactant into Bi2223 phase is reported for first time as long as we know. In iodine intercalation into Bi2212 by using FeI₂ as reactant, the critical tem T_Conset in out-of-plane measurement has suddenly decreased on X=0.95. Similar changes of T_Conset with higher X have been observed independent of directions and reactants. T_Conset of I_xBi₂Sr₂CaCu₂O_y intercalated by FeI₂ is a little lower than one of I_xBi₂Sr₂CaCu₂O_y intercalated by I₂. This is likely due to the change of hall concentration induced by reduction of host In iodine intercalation into Bi2223, the smaller change of T_Conset with increasing amount of intercalant is likely due to the number of CuO₂ planes between ntercalant layers.     

Raman Scattering and X-Ray Diffraction Studies on Alkali-Metal Intercalated Clays

Abstract

Vermiculite and fluor-tetrasilicic mica were intercalated with alkali metals (Na, K and Rb) by vapor transport. X-ray and Raman scattering experiments were conducted to study the structure and lattice dynamics of the new clay compounds. When Rb and K atoms were intercalated to the host materials, superlattices were formed. In Na intercalated compounds, however, no superlattice x-ray diffraction peaks were found. Raman spectra exhibited drastic changes after alkali-metal intercalation, reflecting the structural changes found by our x-ray diffraction.     

Technology of Intercalation and New Effects in PbI2 Single Crystals Intercalated by Hydrazine

Abstract

The hydrazine intercalated lead iodide single crystal technology was developed. A new type of excitons named as interlayer excitons is described. The amplification of polariton emission (Sugakov's phenomenon) and the structure phase transition under intercalation are found and studied.     

Synthesis and morphology of nanosized zeolite L

AFM is a powerful tool for imaging nanoscale surface features; it provides two and three dimensional crystal structure images and other information about actual surface of zeolite crystallites. In this paper, nanosized zeolite L is synthesized in different crystallization times and a study of crystal growth of zeolite L is reported using atomic force microscopy (AFM). X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques are used for characterization of the as synthesized samples. TEM and two‐dimensional AFM images indicate that the zeolite particles are in a nano‐range and they have hexagonal structure. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and Electrochemical Properties of Carbon Nanotube Intercalation Compounds

Abstract

This article summarizes the current status of carbon nanotube intercalation compounds. It focuses on the structure and electrochemical properties of intercalated single-walled carbon nanotubes (SWNTs). Materials synthesis, purification and characterization methods are also discussed. This article draws mostly from works performed at UNC.     

循环流化床粉煤灰可控制备高纯F型八面沸石研究

利用粉煤灰制备沸石分子筛是其高值化利用的重要方向之一.以循环流化床粉煤灰为原料,采用酸浸预处理-氢氧化钠碱熔活化-水热晶化法制备F型八面沸石,并用于吸附亚甲基蓝.考察酸浸温度、碱熔温度及碱灰质量比对粉煤灰结构的影响及碱熔温度、碱灰质量比、液固比及晶化时间对沸石的结构和形貌的影响.通过XRD和SEM对粉煤灰沸石的晶体结构和形貌进行表征.结果表明,利用循环流化床粉煤灰制备高纯F型八面沸石适宜条件为碱熔温度550℃,碱灰质量比1.5:1,液固比12 mL/g,晶体导向剂用量10;,晶化温度100℃,晶化时间20 h.其比表面积高达357 m2/g,且对亚甲基蓝的饱和吸附量高达178 mg/g.     

The Effect of Li on Structure of Supported Rh Particles in Zeolite

Abstract

We prepared Rh ion exchanged Y-type zeolite (RhY) and Li-doped RhY (Li/RhY) catalysts and studied the structure transformation of Rh intercalated species during CO adsorption and CO₂ hydrogenation by EXAFS and TEM. We found that Rh particles in RhY initially supported inside the zeolite cage as 1.3 nm spherical or hemispherical particles. CO exposure of the fresh RhY caused formation of atomically dispersed Rh species. After CO₂ hydrogenation and following reduction, the Rh particles aggregated to form 3.3 nm particles on the outer surface. Meanwhile, Rh particles in Li/RhY were embedded in the zeolite cages, which were narrowed by Li deposition on the wall. The size of the Rh particles was 0.8 nm in diameter. The Rh particles in Li/RhY were stable under reduction, CO adsorption, and CO₂ hydrogenation conditions. We concluded Li additive changed the stability of Rh particles in the supercage by modifying surface hydroxyl group concentration.     

固相法合成NaA型粉煤灰沸石对染料废水的吸附性能研究

以粉煤灰为原料,采用固相法合成NaA型粉煤灰沸石.通过静态吸附实验,研究了吸附时间、pH值、溶液浓度以及吸附温度对粉煤灰沸石吸附脱除亚甲蓝性能的影响.通过SME、XRD对产品进行表征,探讨了亚甲蓝在粉煤灰沸石上的吸附行为.结果表明:经XRD分析,合成产物主要为NaA型沸石.SEM分析表明,产物分别具有纺锤体及NaA型沸石立方体骨架结构;在吸附温度25 ℃,pH值>5,粉煤灰沸石投加量8 g·L-1,吸附30 min时,NaA型沸石对初始浓度为50~100 mg·L-1的亚甲蓝去除率均可达90;以上,较粉煤灰提高了45;;与商品沸石的吸附性能相当.合成的粉煤灰沸石吸附亚甲蓝过程符合Langmuir模型,其为单分子层吸附.     

Doping of Carbon Nanotubes by Heavy Alkali Metals

Abstract

Multiwall (MWNT) and single wall (SWNT) carbon nanotubes were intercalated with heavy alkali metals. From the point of view of their composition, alkali 2D superlattice, EPR and ¹³C NMR characteristics, the intercalation compounds of MWNT (1^st and ^2nd stage) are close to their parent GIC. An expansion of the 2D triangular lattice of SWNT bundles was clearly detected, showing that the alkali atoms are intercalated in the free space between the tubes.     

Structural and Thermal Characterization of Zeolite Type X Modified by Successive Ion Exchange with Cobalt and Manganese Cations

The successive exchange of Co²⁺ and Mn²⁺ with NaX zeolite has been studied. Influence of the above cations on crystalline structure of zeolite type X and its thermal stability has been shown on the grounds of X-ray diffraction, differential thermal analysis, and infrared spectroscopic measurements.