Synthesis of Zeolite L. Tuning Size and Morphology

A convenient synthesis of zeolite L is presented. The size of the crystals can be tuned between 30 and 6000nm, spanning a volume range of seven orders of magnitude. The zeolite L crystals, which typically feature a cylindrical morphology, are synthesized with various aspect ratios ranging from elongated to disc-shaped. The importance of obtaining zeolite crystals with well-defined size and morphology is discussed in view of potential applications of zeolite L containing organic dye molecules as guests.     

Effect of aging temperature of alkaline aluminosilicate and silicate gels on the kinetics of crystallization of zeolite ZSM-5 and silicalite-1

The temperature dependences of nucleation of zeolite ZSM-5 and silicalite-I pass through extrema in the range from 110 °C to 120 °C. Despite having the same crystalline structures, zeolite ZSM-5 has a maximum and silicalite-1 has a minimum of nucleation in the temperature range mentioned. A method for preparation of single crystals of silicalite-1 up to 150 m in size has been developed. The comparison of the curves of the temperature dependences of nucleation for zeolites Na-X, Na-A, and ZSM-5 shows that the positions of the maxima on these curves are determined by the type of the crystal structure of zeolite.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1091–1095, May, 1996.     

A facile method to tune zeolite L crystals with low aspect ratio

We demonstrate an alternative route to tune the morphology of zeolite L crystals using C(2)H(5)OH as the co-solvent in the synthesis gel. A low aspect ratio (0.2 to 0.4) of zeolite L crystals was obtained at lower synthesis temperature (150 °C) and shorter synthesis duration (3 days).     

Encapsulation of Metalloporphyrins in Nanometer-sized Zeolites:Synthesis,Characterization and Catalysis

The lasting extensive interest in zeolite molecular sieves, a class of nanoporous aluminosilicate oxidic crystals, lies in their three special properties:(a) the nanoscale porous cage that can serve as size- and/or shape-based host to recognize, select, and discriminate among the molecules, (b) the well-defined and controllable charge environment and charge strength inside pores that can facilitate or inhibit certain chemical processes, and (c) the well-organized pores/channels that can host the organization and assembly of molecules to display novel optical or electrochemical properties. Zeolitic materials possess yet another very important property, namely, their huge surface-to-volume ratio. Conventionally synthesized zeolites are quite large crystals with grain size at micrometer scale. This implies that the dominant portion of the "overall surface area" is attributable to the " interior surface" of nanopores/nanochannels instead of the "exterior surfaces" of the crystal powders. In many situations, this has limited the efficacy of zeolite materials, particularly in many catalysis-related applications. In order to improve the efficiency of catalysis of zeolite materials, it is often desirable to achieve a balanced ratio (~1) between interior-surface-area and exterior-surface-area, namely, to significantly reduce the size of zeolite crystals.     

Model Studies in Heterogeneous Catalysis. From Structure to Kinetics

Summary. Heterogeneous catalysis is one of the fields of modern technology, where the application of complex inorganic materials is of enormous economical importance. For a long time, the chemical and structural complexity of catalyst materials has precluded detailed insights into chemical processes on catalyst surfaces. In the last decades, however, substantial progress has been made toward a microscopic-level understanding of reaction mechanisms and kinetics, mainly based on the development of new well-defined model systems and on advances in experimental technology and theory. Scrutinizing the example of supported model catalysts, we review some of these innovations in model catalysis. As a particular challenging aspect of todays work, we discuss the question how detailed structural information on the model systems can be linked to catalytic reaction kinetics at the microscopic level.This revised version was published online in February 2005. In the previous version the issue was not marked as a special issue, and the issue title and the editor was missing     

High Selective Alkylation of Aniline with Methanol to N-Methylaniline over [Fe]-KL Molecular Sieves

In the alkylation of aniline with methanol, [Al]-KL zeolite exhibits a much higher NMA (N-methylaniline) selectivity (>95%) and more stable activity with time on stream than NaX, NaY and Na under the same experimental conditions. Incorporation of an appropriate amount of Fe into the framework of zeolite L can enhance the reaction activity without loss of high NMA selectivity. This improvement is attributed to an increase in the basicity of the zeolite as shown by pyrrole-IR spectra. The high NMA selectivity of zeolite L may be due to its one-dimensional channel structure with no large cavities and its lower number of accessible acid sites.     

Derivative Enthalpies of Adsorption of p-Xylene and m-xylene onto NaY and BaY Zeolites at 150°C: Contribution to the prediction of adsorption selectivity

The derivative enthalpies of adsorption of m-xylene and p-xylene onto the NaY and BaY zeolites were measured at 150°C, then compared with those obtained at 25°C, and finally used to predict the selectivity of adsorption of xylene mixtures. Significant differences were observed as the temperature was elevated: for the NaY zeolite, the adsorbate-adsorbate interactions became prevalent, in contrast with the BaY zeolite, between zeolite and derivative interactions were stronger. The difference between the adsorption derivative enthalpies of the two xylenes displayed an abrupt variation from 2 molec. ^–1 for both zeolites, the filling from which selectivity towards m-xylene for the NaY zeolite and towards p-xylene for the BaY zeolite appeared. The preferentially adsorbed xylene was closely connected with the sense of this difference, which changed with the zeolite.This revised version was published online in November 2005 with corrections to the Cover Date.     

Facile synthesis of 5A zeolite from attapulgite clay for adsorption of <Emphasis Type="Italic">n</Emphasis>-paraffins

5A zeolites were facilely synthesized from attapulgite clay and sodium aluminate precursors. The optimum synthesis condition for 4A zeolite (Na-form) were H₂O/attapulgite ratio of 40:1 volume/mass, NaOH/attapulgite mass ratio of 2.35:1, the crystallization time was 4 h at 80–85 °C. The 4A zeolite was converted to related 5A zeolite (Ca-form) through ionic exchanges using calcium chloride solution with the Si/Al mole ratio of 1.3. SEM images demonstrated that as-synthesized 5A zeolites are ordered cubic crystals, average crystals length dimension is 1–2 μm. And the zeolites product had a specific surface area of 482 m² g^?1 and total pore volume of 0.274 cm³ g^?1. The static adsorption experiments showed that the equilibrium adsorption capacities of n-decane and n-pentadecane on produced 5A zeolite were 0.253 and 0.510 g g^?1, respectively. And the adsorption equilibrium time of n-decane and n-pentadecane on 5A zeolite were 45 and 60 min, respectively. The experimental adsorption data of n-decane and n-pentadecane on three zeolites could be properly fitted by the Langmuir–Freundlich isotherm model.     

Cover Picture: Microcontainers with Fluorescent Anisotropic Zeolite L Cores and Isotropic Silica Shells (Angew. Chem. Int. Ed. 7/2009)

Nanocontainers composed of zeolite L crystals were filled with fluorescent dyes and used as the core of a silica “box‐in‐a‐box” construction as in Russian matryoshka dolls, as described by A. Guerrero‐Martínez, L. de Cola, and co‐workers in their Communication on page 1266 ff. The anisotropic cores and isotropic shells of the multicolor emitting systems are separated by a polyelectrolyte layer and can be addressed independently. This approach opens fascinating routes for the construction of multifunctional nanosystems.

     

Uranium sorption from aqueous solutions on sodium-form of HEU-type zeolite crystals

The uranium sorption from aqueous solutions (concentration range 50–20.000 mg/l) by the sodium-form (Na-form) of HEU-type zeolite crystals (particle-size <20 m) has been investigated by means of a batch-type method. The INAA, RI-XRF, powder-XRF, SEM-EDS and FT-IR techniques were used for the study of the experimental products. The absolute uranium uptake by the material reached the value of 11.68 mg/g in the case of initial concentraton 20,000 mg/l. On the other hand theK _d -values indicated that the relative uranium uptake, and consequently the percentage of removal, is higher for concentrations below 100 mg/l. The uranium uptake by the zeolite is attributed to different sorption processes such as ion-exchange, adsorption and surface precipitation, taking place both to the interior and the surface of the crystals and strongly depending on the pH of the solutions. The investigated zeolitic material was sufficiently resistant at the low initial pH of the solutions with dealumination phaenomena only observed in the case of the most acidic solution used.     

键阻断原理构建中孔A型沸石

采用不同类型的有机硅烷化SiO₂作为基本合成单元, 制备了具有晶内中孔的A型沸石。考察了反应碱度、Si/Al比、晶化时间等合成条件对产品的影响。结果表明, 甲氨基丙基三甲氧基硅烷是合成中孔A型沸石的最佳硅烷化试剂;硅烷化试剂的应用, 使中孔沸石晶化过程可以通过“键阻断原理”有效控制;沸石的中孔尺寸可以通过不同类型的有机硅烷化试剂进行调控; 一定范围内, 其外比表面积、中孔体积随SiO₂表面硅烷化度的增加而增加。通过沸石晶化过程中的“键阻断”, 可以制备具有晶内中孔的A型沸石。     

键阻断原理构建中孔A型沸石

采用不同类型的有机硅烷化SiO2作为基本合成单元,制备了具有晶内中孔的A型沸石。考察了反应碱度、Si/Al比、晶化时间等合成条件对产品的影响。结果表明,苯胺基丙基三甲氧基硅烷是合成中孔A型沸石的最佳硅烷化试剂;硅烷化试剂的应用,使中孔沸石晶化过程可以通过"键阻断原理"有效控制;沸石的中孔尺寸可以通过不同类型的有机硅烷化试剂进行调控;一定范围内,其外比表面积、中孔体积随SiO2表面硅烷化度的增加而增加。通过沸石晶化过程中的"键阻断",可以制备具有晶内中孔的A型沸石。     

Novel Immobilized Hydrosilylation Catalysts Based on Rhodium 1,3-Bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidenes

Summary. The reactivity of a well defined Rh (I) complex, i.e. Rh(CF₃COO)(NHC)(COD) (1, NHC=1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene, COD=⁴-cycloocta-1,5-diene) in the hydrosilylation of 1-alkenes, alkynes, and ,-unsaturated carbonyl compounds, respectively, is described. With this complex, excellent reactivity was observed and turn-over numbers (TONs) up to 1000 were reached. A supported version of 1 was realized by reaction of RhCl(NHC)(COD) with PS-DVB–CH₂–O–CO–CF₂–CF₂–CF₂–COOAg (PS-DVB=poly(styrene-co-divinylbenzene) to yield PS-DVB–CH₂–O–CO–CF₂–CF₂–CF₂–COORh(NHC)(COD). This supported version of 1 exhibited at least comparable, in some cases increased reactivity compared to 1 and allowed the rapid removal of the catalyst from the reaction mixture. Due to reduced catalyst bleeding, the synthesis of target compounds with a Rh-content of less than 130ppm was accomplished.This revised version was published online in February 2005. In the previous version the issue was not marked as a special issue, and the issue title and the editor was missing     

Effect of Sodium Concentration on the Synthesis of Faujasite by Two-step Synthesis Procedure

The relationship between the concentration of sodium cations and the properties of faujasite(FAU) zeolite was investigated using a two-step synthesis procedure including (1) formation of amorphous aluminosilicate precursors and separation of amorphous nanoparticles, and (2) transformation of these amorphous particles into zeolite crystals by treatment with alkali solutions(NaOH). Three representative samples including two nano-sized zeolites and one micron-sized zeolite were prepared using different concentrations of sodium hydroxide. The crystallization process of these zeolites was studied in detail by Fourier transform infrared(FTIR) spectrometry, nuclear magnetic resonance spectroscopy(NMR), X-ray diffraction(XRD), scanning electron microscopy (SEM), transmission electron microscopy(TEM), and N₂ adsorption. The results indicated that minor changes in the concertation of inorganic cations can significantly shorten the induction period and crystallization time and thus affect the morphology, size and chemical composition of the zeolite crystals.     

高性能AlPO4-14分子筛膜的制备及气体分离性能

制备了高性能的AlPO₄-14分子筛膜. 首先通过控制反应溶胶中水和模板剂的含量制备了形貌均一的AlPO₄-14分子筛, 分子筛的尺寸为15~18 mm; 然后采用晶种法即在反应凝胶中加入分子筛作为晶种进一步调控分子筛的大小, 使得AlPO₄-14分子筛的尺寸从15~18 mm减小到2~3 mm, 得到形貌均一的纯相片状晶体, 同时有效缩短了制备时间; 最后以多孔管状莫来石为支撑体, 采用二次生长法制备AlPO₄-14分子筛膜. 考察了2种不同大小的晶种对膜形貌和性能的影响, 发现以大尺寸的分子筛(15~18 mm)作为晶种制备的分子筛膜的分离层存在较多缺陷, 而采用小尺寸的晶种(2~3 mm)制备的膜层较均一致密. AlPO₄-14分子筛膜经高温脱除模板剂后仍然保持着纯相的AlPO₄-14晶型, 表明二次生长法促进了AlPO₄-14晶体在膜层中的生长且使其具有更高的结晶度和热稳定性. 在25 ℃, 100 kPa下, AlPO₄-14分子筛膜对H₂/CH₄, CO₂/CH₄和H₂/CF₄的理想分离因子分别为28, 40和1047, 且H₂和CO₂的渗透速率分别为6.3×10 ^-7和9×10 ^-7 mol·(m ²·s·Pa) ^-1; 对等摩尔CO₂/CH₄混合气体的分离因子为81.5, 且CO₂的渗透速率为8.8×10 ^-7 mol·(m ²·s·Pa) ^-1.     

Thermal and Dynamic-Mechanical Characterization of Uni- and Biaxially Oriented Polypropylene Films

The effect of uni- and biaxial orientation in the morphology of polypropylene films has been investigated by thermal, dynamic-mechanical, X-ray pole figure and diffraction patterns. In uniaxial oriented films the level of damping is roughly three times higher in the MD direction than it is in the TD direction. The stretching always produces crystals of the form independently of the starting type. Fast DSC scans show two melting peaks indicative of two crystalline species. The Fujiyama et al. model for the crystalline structure can be also applied to the uniaxially stretched films. Upon biaxially orienting, the folded lamellae crystals (kebabs) are the ones to support all the force applied, and when their maximum level of stress slippage is reached they deform following the Peterlin's model, forming a new shish structure. These new shishes are aligned to the TD direction and by linking the original shishes in the MD direction produce a planar orthogonal net of linked shish structures. The space among the shishes is filled with small and imperfect folded lamellae with c-axis in the film plane and preferentially oriented in the MD and TD directions, keeping constant crystallinity density throughout.This revised version was published online in November 2005 with corrections to the Cover Date.     

Preparation of a Completely Oriented Molecular Sieve Membrane

Growth of oriented seed crystals on a substrate led to a completely oriented and continuous membrane of LTA-type zeolite. The seed crystals of cubic morphology were dip-coated onto a tilted substrate (see schematic diagram) with the zeolite channels normal to the surface. The substrate was hydrothermally treated in a reaction mixture containing the organic ligand 2,2-bis(hydroxymethyl)-2,2',2"-nitrilotriethanol, which lowers the degree of supersaturation of [Al(OH)(4)](-) ions and preferentially facilitates the intergrowth of the seed crystals.     

一种新型共生沸石(T-L)的合成与表征

在Na₂O-K₂O-Al₂O₃-SiO₂-H₂O体系中水热合成了一种新型的共生沸石, 它由L型沸石生长在T型沸石的一端而形成, 称之为T-L型沸石. 通过XRD, SEM, TEM, EDX, IR等手段对其进行了初步的表征. SEM相片表明这种沸石具有特殊的铆钉状外形; 在TEM相片上可以清楚地看到L型沸石的大孔道, 此孔道与L型沸石的表面垂直. 通过EDX的数据计算发现共生沸石的两相有不同的骨架硅铝比: T型沸石部分Si/Al＝3.71, L型沸石部分Si/Al＝3.41. 在该样品中B酸大于L酸.     

A new strategy for the controlled deposition of gold nanoparticle aggregates on two-dimensional polystyrene arrays and its application in glucose oxidase immobilization

Zeolite 4A (LTA) has been successfully synthesized by a hydrothermal method, where kaolin was used as silica and alumina source. The synthesized zeolite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), laser granulometry, and FTIR spectroscopy. XRD data from the Rietveld refinement method confirmed only one crystallographic phase. Zeolite A morphology was observed by SEM analysis, and it showed well-defined crystals with slightly different sizes but with the same cubic shape. Particle size distribution of the crystals was confirmed by laser granulometry, whereas FTIR spectroscopy revealed significant structural differences between the starting material and the final zeolite product used as water softener.     

Removal of heavy metals and bacteria from aqueous solution by novel hydroxyapatite/zeolite nanocomposite,preparation, and characterization

In this study, a HAp/NaP nanocomposite was prepared by adding a synthesized nano-hydroxyapatite to zeolite NaP gel in the hydrothermal condition and used for the removal of lead(II) and cadmium(II) ions from aqueous solution. HAp/zeolite nanocomposite was then characterized by Fourier transform infrared spectroscopy, X-ray diffraction and Rietveld method, scanning electron microscope, energy-dispersive X-ray analysis, and surface area and thermal analyses. Results suggested that the nanocomposite crystals of HAp were dispersed onto the zeolite external surface and/or encapsulated within the zeolite channels and pores. The potential of the composite in adsorption of heavy metals was investigated by using batch experiment. The metal concentration in the equilibrium C _e (mg/g) after adsorption with nanocomposite of HAp/NaP was analyzed using flame atomic adsorption spectrometry. The adsorption experiments were carried out at pH of 3–9. The influences of contact time, initial concentration, dose, and temperature on the adsorption of lead and cadmium ions were also studied. Results show that these nanocomposites have further adsorption related to NaP and HAp. They have great potential (about 95 %) for Pb(II) and Cd(II) adsorption at room temperature. The equilibrium process was described by Frendlich, Langmuir, Temkin, and Dubinin–Radushkevich (D-R) models. The kinetics data were successfully fitted by a pseudo-second-order model. The in vitro antibacterial activity of these composites was evaluated against Bacillus subtilis (as Gram-positive bacteria) and Pseudomonas aeruginosa (as Gram-negative bacteria) and compared with standard drugs that show inhibition on bacterial growth.