XRD study of the dehydration and rehydration behaviour of Al-pillared smectites differing in source of charge

The swelling properties of Al-pillared clays, obtained from five different smectites, were studied using X-ray diffraction. These clays, the dioctahedral beidellite and montmorillonite and the trioctahedral saponite, hectorite and laponite differ in source of isomorphic substitution and represent a series of decreasing basicity along the siloxane plane. An Al oxyhydroxy cation was inserted between the layers to form the respective pillared clays and these clays were heated incrementally to 600°C. The XRD peaks at each stage of heating were recorded as well as the same samples subsequently wetted. Basal spacings of each clay at each stage of dehydration d rehydration indicated that the swelling of tetrahedrally substituted saponite and beidellite was indeed restricted, compared with the other three clays. This was attributed to greater basicity of the oxygen plane of beidellite and saponite due to tetrahedral substitution of Si by Al, resulting in an increase in the strength of hydrogen bonds between either water or the interlayer polyhydroxy cation and the clay.The data from the XRD analyses helped in addition, to clarify the thermal transformations of the Keggin ion itself. According to the changes in thed-spacings of the pillared clays it was concluded that the Keggin ion lost its structural water at 200°C and dehydroxylated in a range beginning at 350°C. Between 500 to 600°C this polymer cation, which is thought to form the Al₂O₃ oxide, did not rehydrate.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthdayThe authors wish to thank Laporte Industries, Inc., U.K. for the laponite sample.     

羟基铝离子柱撑蒙脱石材料的制备与结构表征

采用水洗过滤提纯蒙脱石原矿,以NaCl作为钠化改型剂对提纯后的蒙脱石原矿进行了钠化改型,以NaOH水解AlC13溶液制备了铝柱化剂,并采用离子交换法使铝柱化剂柱撑进入钠基蒙脱石层间得到羟基铝离子柱撑蒙脱石。采用XRF,XRD,SEM等方法对铝柱撑蒙脱石载体的结构进行了表征。柱撑前后样品的测试结果表明,羟基铝离子通过离子交换反应进入蒙脱石层间。     

氯掺杂二氧化钛柱撑蒙脱土的合成及光催化性能

采用溶胶 凝胶法制备了氯掺杂二氧化钛柱撑蒙脱土催化剂。 利用XRD、SEM、UV-Vis-DRS、光致发光谱(PLS)、N2吸附-脱附和XPS等测试技术对其进行了表征。 结果表明,该催化剂具有明显的锐钛矿相结构,且氯掺杂与二氧化钛柱撑后,蒙脱土的层间结构没有完全被破坏;氯掺杂拓宽了其光吸收范围,在可见光区吸收增强;其带隙能由3.19 eV减小至3.14 eV;氯以阴离子形式存在于TiO2晶格中。 对硝基苯胺降解实验表明,氯掺杂可显著提高二氧化钛柱撑蒙脱土的光催化活性,氯掺杂量为6%(与钛的摩尔比)的催化剂具有较好光催化活性。     

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．     

新型无机/有机复合柱撑粘土材料的合成与表征

以无机TiCl4／HCl制成的钛基柱撑液和十六烷基三甲基溴化胺(CTAB)为有机改性液,通过控制两种柱撑液的加入顺序以及相对含量,利用蒙脱石粘土矿物层间域的特殊化学反应场所的特性,合成得到三类复合柱撑蒙脱石材料．X射线衍射结果表明,d001晶面由于CTAB与钛基水合离子的相互作用形成粒度不同的柱撑空间而表现为两个峰值．与FT-IR光谱相比,FT-Raman光谱能够更加有效地表征和鉴定复合柱撑粘土的结构差别．采用原土无机柱撑后再有机柱撑,可以合成层间距更大的复合柱撑粘土材料．经热处理后得到锐钛型氧化钛的改性粘土材料,并且可以重新合成得到无机／有机复合柱撑的新型改性粘土材料．这些合成手段为制备新型改性粘土材料应用于环保以及化工等方面提供了借鉴．     

锆钇柱撑蒙脱土负载Pd催化剂的催化性能研究

合成了锆钇柱撑蒙脱土(Zr-Y-MMT)载体,并用于丙酮、甲苯和乙酸乙酯的催化氧化。通过XRD、TEM及N₂吸附-脱附技术对Zr-Y-MMT载体和负载Pd催化剂(Pd/Zr-Y-MMT)进行了表征。XRD结果显示,经锆钇柱撑后蒙脱土的层间距由1.27 nm增大至1.78 nm;N₂吸脱附结果表明,经锆钇柱撑后,其比表面积有了很大的增加,由62 m²·g^-1增大至395 m²·g^-1。活性评价结果发现,Zr-Y-MMT载体比Na-MMT有更好的催化活性,其完全氧化丙酮、甲苯和乙酸乙酯的温度分别为320 ℃、350 ℃和290 ℃。此外,当此载体上负载0.1wt%Pd时,其用于完全氧化甲苯的活性有了明显的改进。     

铝柱撑蒙脱石负载纳米金催化剂的结构表征及其CO催化活性研究

以铝柱撑蒙脱石为载体,用沉积沉淀法在其表面负载金属Au后制备了Au负载铝柱撑蒙脱石高效负载型催化剂。以XRD,TEM,XPS等手段对催化剂的结构进行了表征,并研究了铝柱撑蒙脱石负载前后CO催化氧化活性的变化规律。结果证明,Au是以高度分散的状态均匀分布在铝柱撑蒙脱石载体表面,且以Au0和Au3+的混合价态形式存在。CO催化氧化活性表征结果表明,负载后催化剂的催化活性有了显著提高,且其催化活性随着负载量的增加而不断增强,但当负载量增大到一定程度后,其催化活性不再继续增加,且有所下降。     

Influence of Drying and Calcination on Remaining Amount and Immobile Character of Titanium on Titanium‐pillared Montmorillonite

Remove of titanium (Ti) from titanium‐pillared montmorillont (TIPM) is not expected during its application as adsorbent and photocatalyst, etc. But studies on immobilization of Ti on TIPM are seldom reported. In this work, TIPM was synthesized from TiCl₄ and Na⁺‐montmorillont (Na⁺‐MMT). Then the prepared TIPM was heated at different temperatures (100, 240 and 450°C) to yield three TIPM samples (TIPM1, TIPM2, and TIPM3). Inductively coupled plasma optical emission spectrometer (ICP‐OES) was used to determine the effect of heating temperature on the remaining amount of Ti on TIPMs. A two‐step treatment method which is often used in the pretreatment and application of TIPM was developed to investigate the immobile character of Ti on TIPMs. X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), N₂ adsorption/desorption isotherm, thermogravimetric analysis and differential scanning calorimetry (TG‐DSC) were also used to characterize TIPMs before and after the treatment. The results show that with an increase in heating temperature, the amount of Ti species remained on TIPM decreases gradually and Ti immobilization is strengthened on TIPM. For TIPM3, less than 2% Ti is removed from TIPM3 after the treatment required to simulate the practical conditions of TIPM in its application, while those of TIPM1 and TIPM2 are 6.6% and 8.4%, respectively. The reason may be that when TIPM is heated, Ti species intercalated into MMT become chemically bonded with the framework of MMT and partially migrate into the layer structure, which make Ti immobile on TIPM firmly during the treatment process.     

Simultaneous DTA-TG Study of Montmorillonite Mechanochemically Treated with Crystal-violet

The mechanochemical solid-state adsorption of the cationic dye crystal violet (CV) by montmorillonite was investigated by XRD and simultaneous DTA-TG. Solid CV was ground with the clay for 5 min and four different varieties of CV mechanochemically treated clay were investigated. X-ray and DTA data were compared with those of CV-montmorillonite obtained from an aqueous suspension. X-ray and DTA studies of a ground mixture and a ground mixture heated at 110°C suggest that the mechanochemical adsorption of organic cations takes place on the external surfaces of the clay. The study of a ground mixture washed with water, and washed with water and acetone reveal that water is essential for the penetration of CV into the interlayer space.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal Stability of Clay/organic Intercalation Complexes

The comparison of thermal stabilities of different organoclay intercalation complexes is presented in this work. Montmorillonite/monomer and montmorillonite/polymer intercalation complexes with similar basal spacings show a pronounced difference in changes of d ₀₀₁ values after 30 min heating. The hydrophilic and/or organophilic surface modification of the starting montmorillonite is an important factor affecting the intercalated amount of organic material and thus the expansion of the sheet silicate structure.This revised version was published online in November 2005 with corrections to the Cover Date.     

Comparative Studies of the Micropore Size Distributions of an Alumina Pillared Montmorillonite and a Molecular Sieve Carbon

The aim of this work is to applicate and to compare various analysis methods for the characterization of the microporous structure from nitrogen adsorption at 77 K of an alumina pillared montmorillonite and a molecular sieve carbon. The adsorption potential distribution (X(A)), the Horvath-Kawazoe (HK) method, the Jaroniec-Gadkare-Choma (JGC) one and a numerical algorithm for the reconstruction of the micropore size distribution (MPSD) from the adsorption equilibrium isotherm have been applied. Comparison of all distributions revealed that the molecular sieve carbon shows smaller micropores and smaller structural hetereogeneity than the alumina pillared montmorillonite.     

Montmorillonite treated with Rhodamine-6G mechanochemically and in aqueous suspensions

The mechanochemical solid-state adsorption of the cationic dye rhodamine-6G (R6G) by montmorillonite was investigated by XRD and simultaneous DTA-TG. Five different mixtures of R6G and montmorillonite were investigated. They contained 10, 20, 35, 50 and 100 mmol R6G per 100 g clay. The solid R6G was ground with the clay for five minutes. Mixtures were ground both in the absence of water (dry grinding) and with the adding of drops of water periodically, (wet grinding). There were no differences between samples obtained by wet or dry grinding. X-ray and DTA data were compared with those of R6G-montmorillonite obtained from aqueous suspensions. The mechanochemical products were different from those obtained from aqueous suspensions. The X-ray and DTA studies suggest that the mechanochemical adsorption of organic cations takes place on the external surfaces of the clay whereas in suspensions the adsorption takes place into the interlayer space. In the latter case the final stages of oxidation occur in temperatures higher than those of the neat dye whereas in the former they occur at lower temperatures. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dehalogenation of Aryl Halides Catalyzed by Montmorillonite Immobilized Bimetal Catalyst in Aqueous System

A novel bisupported bimetal catalyst PVP-PdCl2-FeSO4/Al-Mont-PEG600 was prepared by immobilization of PVP (poly (N-vinyl-2-pyrrolidone)) supported bimetallic catalyst using alumina pillared inartificial montmorillonite as the carrier. This catalyst has good dehalogenation activity and selectivity to aryl halides-o-chlorotoluene in aqueous system in the presence of phase transfer catalyst (PEG) and sodium formate as hydrogen source. The catalyst also shows good reusability.     

Thermal Analysis and X-ray Diffraction of Synthesis of Scheelite

Scheelite (calcium tungstate)is the product of one of the processing methods of wolframite by its roasting with calcium oxide or limestone or its fusion with calcium chloride, followed by acid processing of calcium tungstate with the formation of tungstic acid. Scheelite occurs in contact metamorphic deposits, hydrothermal veins and pegmatites. The present work illustrates a thermal analysis study of synthesis of scheelite by sintering of wolframite with calcite and sintering of tungsten oxide with calcite or calcium oxide using a derivatograph. The reaction products were identified microscopically and by using a Siemens Crystalloflex diffractometer. The DTA curve of sintering of wolframite with calcite shows the beginning of the reaction at 560°C with the formation of scheelite. The intensive formation of scheelite is represented by the medium and wide endothermic peak at 740°C. This is followed directly by a large and sharp endothermic peak at 860°C, representing the dissociation of unreacted calcite. The DTA curve of tungsten trioxide shows three thermal effects. The sharp exothermic peak at 320°C represents the oxidation of tungsten oxide content of lower valency. The endothermic peaks at 750 and 1090°C are related to polymorphic changes of tungsten trioxide. The beginning of its sublimation is observed at temperature higher than 800°C. The DTA curves of sintering of tungsten trioxide with calcite or calcium oxide indicate that the intensive formation of scheelite takes place by endothermic reactions at 660 and 545°C respectively. The medium and small endothermic peaks at 520 and 730°Con the DTA curve of tungsten trioxide with calcium oxide represent the dehydration of calcium oxide and the loss of carbon dioxide due to some carbonatization of calcium oxide with carbon dioxide from air, respectively. The produced scheelite is colorless in thin sections, has distinct cleavage (101), crystallizes in the tetragonal system in the form of tabular crystals and is optically positive. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and characterization of manganese- and samarium-manganese-alumina pillared montmorillonites

A Na-montmorillonite was intercalated with manganese- and samarium-manganese-aluminium solutions. The pillared montmorillonites were characterized by X-ray diffraction and nitrogen adsorption. The presence of manganese and samarium-manganese citrates in the intercalation process modify the distance between the clay sheets and the microporous structure of the pillared montmorillonites.     

蒙脱土改性研究进展

概括了蒙脱土的结构和基本性质,综述了近年来国内外蒙脱土改性方面的研究进展,从无机改性、有机改性和有机-无机复合改性三方面对其改性方法和机理分别进行了讨论,并展望了其应用前景.     

铕掺杂硅钛柱撑蒙脱土的合成及发光性能研究

采用溶胶凝胶法制备了Eu3+掺杂的硅钛柱撑蒙脱土(Si-Ti-MT),运用XRD,SEM-EDX和FT-IR对其结构进行了表征。结果表明,Eu3+掺杂的硅钛柱撑剂插入蒙脱土层之间,保持了蒙脱土层状结构。经荧光发射光谱和激发光谱分析可知,Si-Ti-MT是Eu3+发光的有效基体,其发射能级主要为Eu3+613 nm(5D0→7F2);激发光谱中表现了Eu3+的5个特征激发带,分别为363 nm(7F0→5D4),382 nm(7F0→5G2),395 nm(7F0→5L6),415 nm(7F0→5D1)和465 nm(7F0→5D2);热处理促进了Eu3+掺杂的硅钛柱撑蒙脱土的发光,且样品的荧光强度随着Eu3+掺杂量的增加而增强,不会发生浓度猝灭现象。     

The Characterization of Organic Modified Montmorillonite and Its Filled PMMA Nanocomposite

Thermogravimetric analysis (TG) and Fourier transform infrared (FTIR)results of commercial montmorillonite were compared to that exchanged with trimethyloctadecyl quaternary ammonium chloride (SCPX2048), both were treated up to500°C. The time-of-flight mass spectrometer (TOF/MS) results of SCPX2048 trapped under300 and 500°C were compared with that of N,N,Ntrimethyl-1-dodecanammonium chloride(A 18-50) trapped under 200 and 300°C. The degradation mechanism of organic modified montmorillonite was proposed. PMMA-clay nanocomposite was synthesized through intercalation method and its properties were examined by both TG and DSC techniques. The thermal stability and glass transition temperature of montmorillonite filled PMMA increase comparing with that of the pure PMMA. This revised version was published online in July 2006 with corrections to the Cover Date.     

镧改性铜基铝铈交联蒙脱土的制备及其对丙烯选择性还原NO的催化性能

 制备了镧改性铜基铝铈交联蒙脱土催化剂La/Cu/SO2-4/AlCe-PILM,研究了它在富氧条件下对丙烯选择还原NO的催化性能,考察了镧的添加方法、添加量及催化剂焙烧温度对La/Cu/SO2-4/AlCe-PILM催化性能的影响. 结果表明,采用分步浸渍法引入镧能显著提高催化剂对NO选择还原反应的催化活性和高温稳定性,镧的添加量为1.0%时,经500 ℃焙烧制得的La/Cu/SO2-4/AlCe-PILM催化剂性能较佳,NO最大转化率由未加镧时的49.1%提高到加镧时的57.2%,在650 ℃反应时La/Cu/SO2-4/AlCe-PILM上的NO转化率仍高达20%. XRD,TPR和XPS表征分析结果表明,镧物种和铜物种均呈分散状态,镧的引入可能促进了活性中心Cu2+的氧化还原催化循环过程,从而提高了催化剂对丙烯选择还原NO反应的催化活性.     

酸化交联蒙脱土催化合成乙酸苄酯

酸化交联蒙脱土催化合成乙酸苄酯;酸化交联蒙脱土;催化;乙酸苄酯