Thickness-controlled Growth of Silicalite Membranes on Cerium Oxide Supports

Layers of silicalite crystals with controlled thicknesses were deposited on cerium oxide porous disks by hydrothermal synthesis. The morphology and structure of the ceramic composites were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and (scanning) transmission electron microscopy ((S)TEM) and compared to zeolite layers on aluminum oxide supports. The elemental distribution, as visualized in elemental mappings by energy-dispersive X-ray spectroscopy (EDXS), confirm the formation of the zeolite layer and reveal the incorporation of zeolite crystals inside the pores of the supporting oxide. Zeolite layer integrity was assessed by gas permeation tests. These composites can be utilized as gas separators and can increase the selectivity of gas sensors or applied in catalysis.     

Y沸石的高温合成

采用甲基三乙氧基硅烷(MTS)为添加剂, 在高温(140 °C)条件下水热合成出具有六方片状形貌的Y型沸石. 相比于100 °C左右合成的Y型沸石, 高温合成的Y沸石具有更高的硅铝比值、更大的晶体宽厚比值以及对有机挥发物具有优异的吸附性能. 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、²⁹Si固体核磁共振(NMR)、傅里叶变换红外(FTIR)光谱、碳氢氮元素分析(CHN)、水接触角等表征, 证明了所合成的新型Y沸石具有甲基基团, 它们的存在增强了疏水性能, 提高了对有机挥发物的吸附能力.     

纳米晶簇多级孔道L沸石的合成及其脱硫性能

采用晶化培育法制备了L沸石纳米晶簇,以其作为前驱体,并以3-三甲基甲硅烷基丙基十六烷基二甲基氯化铵(TPHAC)为模板剂,合成了微孔-介孔多级孔道L沸石(MeLTL沸石).通过X射线衍射(XRD)、氮气吸附-脱附、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、27Al固体魔角核磁(27AlMASNMR)和吡啶傅立叶变换红外(Py-FTIR)等方法对MeLTL沸石进行了表征.研究结果表明,MeLTL沸石是由L沸石纳米晶簇自组装形成的,并具有介孔孔道和L沸石的微孔结构以及适宜的酸量与酸强度,其比表面积和孔体积分别高达611m2.g-1和0.696cm.3g-1.将MeLTL沸石作为添加剂引入柴油加氢脱硫催化剂载体中,并与添加L沸石、Al-MCM-41和仅以γ-Al2O3为载体的催化剂进行比较,其脱硫性能为最佳,经加氢后的柴油硫含量仅为9.3μg.g-1,脱硫率达99.3%.     

Synthesis and Catalytic Properties of ZSM-5 Zeolite with Alkyl-polyamine Triethylene-tetramine as Directing Agent

With alkyl-polyamine triethylene-tetramine as the structure-directing agent,aluminosilicate zeolite ZSM-5(MFI) crystals were synthesized and characterized by XRD,SEM,FTIR,and TG-DTA. The results indicate that the organic amine has a certain influence on the crystal shape and size. The alkaline condition was in favor of the crystallization of ZSM-5 zeolite in the triethylene-tetramine system. The catalytic activity of as-synthesized crystals was examined for the aqueous hydroxylation of phenol with hydrogen ...     

Synthesis of zeolite nanocrystals at room temperature

Zeolite A nanoparticles were synthesized under room-temperature conditions from a very reactive organic-template-free gel system. The optimization of the syntheses parameters, namely, the composition of the initial system and the careful choice of the reactants, allowed the crystallization to be accomplished within 3 days. At this stage the individual zeolite crystals were in the range of 100-300 nm without well-developed crystal faces. The prolongation of the synthesis time up to 10 days led to formation of larger well-faceted cubic crystals averaging about 400-500 nm in size. The high-resolution transmission electron microscopy (HRTEM) study revealed that a thin layer of amorphous material covers the zeolite particles acting as a binder between individual zeolite crystals. The postsynthesis treatment of the product in NH(3) media under ultrasonic radiation disintegrated the loosely attached zeolite particles and decreased the fraction of zeolite A particles with low colloidal stability. The employed approach, however, did not result in complete disintegration of aggregated crystals. The zeolite crystals obtained under ambient conditions were characterized by XRD, SEM, dynamic light scattering, and N(2) adsorption measurements.     

基于压电陶瓷的A型分子筛膜合成与吸附性能

无铅压电陶瓷0.8Na0.5Bi0.5TiO3-0.2K0.5Bi0.5TiO3表面采用化学改性预涂晶种作为基底,分别以微乳和澄清溶液法在基底上水热晶化合成了A型分子筛膜。通过XRD、SEM和FTIR对晶种及分子筛膜进行了表征,通过压电谐振法测量甲烷吸附性能。结果表明:微乳和澄清溶液法均合成单一A型分子筛相,1次合成分子筛膜的时间分别为6、9h,通过不同镀膜次数生成A型分子筛膜的形貌、膜厚不同。经A型分子筛膜修饰压电振子后,其对甲烷气体的灵敏度可分别达到59Hz/1%CH4、68Hz/1%CH4。     

Incorporation of CoS nanoparticles into ZSM-5 zeolite by hydrothermal and ion exchange methods

Cobalt sulfide nanoparticles were introduced into the medium-pore zeolite ZSM-5 (Zeolite Scony Mobil Five) by ion exchange in aqueous suspension and also by the addition of cobalt sulfate to the synthesis gel in hydrothermal zeolite synthesis. The latter method was systematically studied in the presence of tetraethylammonium ions as organic agents. The materials were characterized by chemical analysis, x-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM), energy dispersion x-ray (EDX), IR, BET and diffuse reflectance spectroscopy (DRS). SEM picture and BET were used to discriminate between CoS nanoparticles in the zeolite pores and on the outer crystal surface. Their crystalline structure and morphology were studied by XRD and scanning electron microscopy. The results showed that in hydrothermal method zeolite acts as a template. CoS nanoparticles with an approximate size of 22 nm grow on the surface of zeolite. In ion exchange method, however, the majority of CoS nanoparticles are about 6 nm in diameter, located on the surface of the MFI (type materials ZSM-5) structure. Exciton absorption peaks at higher energy than the fundamental absorption edge of bulk CoS indicate quantum confinement effect in nanoparticles as a consequence of their small size. The absorption spectra show that the optical band gap for CoS nanoparticles produced by hydrothermal and ion exchange methods is 3.68 and 4.1 eV, respectively.     

Preparation of Zeolite X Membranes on Porous Ceramic Substrates with Zeolite Seeds

Zeolite X membranes were investigated by in-situ hydrothermal synthesis on porous ceramic tubes precoated with zeolite X seeds or precursor amorphous aluminosilicate, and porous α-Al2O3 ceramic tubes with a pore size of 50 200 nm were employed as supports. Zeolite X crystals were synthesized by the classic method and mixed into deionized water as a slurry with a concentration of 0.2 0.5wt%, having a range of crystal sizes from 0.2 to 2μm. Crystal seeds were pressed into the pores near the inner surface of the ceramic tubes, and crystallization took place at 95℃ for 24-96 h. It was also investigated that Boehmite sol added with zeolite X seeds was precoated on ceramic supports to form a layer of γ-Al2O3 by heating, and hydrothermal crystallization could then take place to prepare the zeolite membranes on the composite ceramic tubes. The crystal species were characterized by XRD, and the morphology of the supports subjected to crystallization was characterized by SEM. The composite zeolite membranes have zeolitic top-layers with a thickness of 10-25 μm, and zeolite crystals can be intruded into pores of the supports as deeply as 100μm. The experimental results indicate that the precoating of zeolitic seeds on supports is beneficial to crystallization by shortening the synthesis time and improving the membrane strength. The resulting zeolite X membrane shows permselectivity to tri-n-butylamine((C4H9)3N) over perfluro-tributyl-amine ((C4Fg)3N), and a permeance ratio of 57 for ((C4Hg)3N to (C4F9)3N could be reached at 350℃. Permeances of BZ, EB and TIPB through the zeolite membrane were also measured and were found to slightly increase with temperature.     

基于压电陶瓷的A型分子筛膜合成与吸附性能

无铅压电陶瓷0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃表面采用化学改性预涂晶种作为基底,分别以微乳和澄清溶液法在基底上水热晶化合成了A型分子筛膜.通过XRD、SEM和FTIR对晶种及分子筛膜进行了表征,通过压电谐振法测量甲烷吸附性能.结果表明:微乳和澄清溶液法均合成单一A型分子筛相,1次合成分子筛膜的时间分别为6、9 h,通过不同镀膜次数生成A型分子筛膜的形貌、膜厚不同.经A型分子筛膜修饰压电振子后,其对甲烷气体的灵敏度可分别达到59 Hz/1%CH₄、68 Hz/1%CH₄.     

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.     

超细4A分子筛的超声波低温快速合成

在低温条件下用超声波快速合成了4A分子筛.产物分别用XRD,IR,SEM和DSC等进行了表征.结果表明,用超声波法合成4A分子筛的速度是常规法的24倍.合成产物的白度为95%,钙离子交换容量为335mgCaCO₃/g4A分子筛,平均粒径为280nm.与采用常规方法合成的产物相比,超声波法合成的产物热稳定性有所下降.     

低温加氢裂解脱除高硅ZSM-5分子筛内TPAOH模板剂

分子筛膜的合成和应用是近年来的研究热点, 特别是具有独特孔道结构的MFI 型分子筛膜. 但由于膜内有机模板剂在高温脱除时会导致膜产生缺陷, 进而影响分子筛膜的应用. 所以分子筛膜及分子筛晶体中有机模板剂的低温脱除工艺一直是研究者们致力解决的问题之一. 本文系统考察了高硅ZSM-5分子筛晶体内有机模板剂(四丙基氢氧化铵, TPAOH)在H₂/N₂气氛下的低温裂解脱除规律, 采用低温加氢裂解工艺, 在350 ℃以下可有效脱除分子筛晶体孔道内的有机模板剂. 通过对裂解后分子筛晶体的比表面积(BET)、热失重(TG)、傅里叶变换红外(FTIR)光谱和拉曼光谱表征证实, 相比于空气和氮气气氛, 含氢还原性气氛更有利于模板剂的低温脱除, 脱除率随温度的升高而增加; 280 ℃时, 加氢裂解后晶体的BET比表面积已达到252 m²·g^-1, 仍有少量有机残余物; 350 ℃时, 加氢裂解后晶体的BET比表面积可达到399 m²·g^-1, 仅有微量无机碳残余物. 此外, 低温加氢裂解后的分子筛表面相对洁净, 且氨气程序升温脱附(NH₃-TPD)结果表明低温加氢裂解后的ZSM-5 分子筛晶体具有相对较多的酸性位.     

Activity and selectivity of zeolite MCM-22 catalysts in the disproportionation of toluene

Zeolite precursor MCM-22 samples were prepared by hydrothermal synthesis. The H-zeolites, obtained from the precursors, were characterized by scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, and by their activity in the title reaction. Despite of the lower Br?nsted acid site concentration of the zeolite having smaller crystallites, showed higher activity, while the zeolite, having larger crystals were more selective for p-xylene formation.     

两种杂原子复配对Y型分子筛结晶性能的影响

分子筛作为催化剂或催化剂的载体材料广泛应用于各种催化反应过程中,将杂原子引人分子筛骨架中形成杂原子分子筛,可在较大的范围内调节分子筛表面的酸性中心和氧化还原催化活性中心.     

正交试验法优化合成沸石对水中Cr(Ⅲ)的去除条件研究

以粉煤灰为原料,采用水热晶化一步法合成沸石,通过XRD和SEM对合成产品进行表征,L9(34)型正交试验研究Cr(Ⅲ)的优化去除条件,对沸石解吸及循环利用的可能性进行评价。结果表明,合成产品为规则的菱形或多面体形NaP1型沸石,直径约为6μm。正交试验表明水中沸石对Cr(Ⅲ)去除影响的主次顺序为Cr(Ⅲ)浓度、反应时间、溶液pH值和沸石加入量,较优水平组合为Cr(Ⅲ)浓度10mg/L、反应时间15min、溶液pH值2和沸石加入量1.5g/L,Cr(Ⅲ)的平均去除率为95.51%。可以使用蒸馏水和HCl洗脱沸石,达到沸石循环利用及洗脱液回用的目的。     

沸石合成过程中的溶剂效应

沸石合成过程中的溶剂效应窦涛，冯芳霞，王晓钟，萧墉壮，曹景慧（太原工业大学精细化工研究所，太原０３００２４）刘建宇钟炳（山西省化工设计院，太原０３００２４）（中国科学院山西煤炭化学研究所，太原０３０００１）关键词ＺＳＭ－５，ＺＳＭ－３５，方钠石，溶剂...     

PS-b-PNIPAM/Ag复合微粒的制备与表征

采用原子转移自由基聚合(ATRP)法合成了聚苯乙烯-b-聚(N-异丙基丙烯酰胺)(PS-b-PNIPAM)两亲性嵌段共聚物, 并以其为模板, 聚乙烯亚胺(PEI)作为银离子和嵌段共聚物PS-b-PNIPAM的交联剂以及还原剂, 制备了PS-b-PNIPAM/Ag复合纳米微粒. 利用透射电子显微镜(TEM)、X射线衍射(XRD)和傅里叶变换红外(FTIR)光谱对复合纳米微粒的形貌及其成分进行了表征. X射线衍射和电子衍射证明银纳米微粒具有良好的面心立方体单晶结构. 研究结果表明, 不同浓度的两亲性嵌段共聚物PS-b-PNIPAM在丙酮中形成的胶束模板对银纳米粒子的尺寸及其分布有重要的影响.     

Mg掺杂GaN纳米线的结构及其特性

利用类似Delta掺杂技术在硅衬底上沉积Mg:Ga2O3薄膜, 然后在850 ℃下对薄膜进行氨化, 反应后制备出大量Mg掺杂GaN纳米线. 采用扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱和高分辨透射电子显微镜(HRTEM)对样品进行分析.结果表明, Mg掺杂GaN纳米线具有六方纤锌矿单晶结构, 纳米线的直径在30-50 nm范围内, 长度为几十微米.     

Anionic emulsion-directed synthesis of zeolite ZSM-5 with tunable morphology and Si/Al ratio

Zeolite ZSM-5 was synthesized for the first time in an anionic emulsion system composed of sodium dodecylbenzene sulfonate, pentanol, cyclohexane and zeolite synthesis mixture, and subsequently characterized by XRD, SEM, FTIR, TG and N₂ adsorption techniques. It is found that altering emulsion composition and adding electrolyte can effectively change the morphologies and/or Si/Al ratios of the ZSM-5 samples. Besides the commonly seen coffin morphology, ZSM-5 particles with rare elliptic cylinder, column and ellipsoid morphologies are also obtained. Depending on the weight ratios of anionic surfactant and zeolite reaction mixture, the framework Si/Al ratios of ZSM-5 samples vary slightly. Investigations on the crystallization process further show the emulsion system can induce rapid crystallization by virtue of shortening the induction time. The ways that the emulsion system affects zeolite crystallization, framework Si/Al ratio and particle morphology are tentatively discussed.     

Fabrication of flowerlike polymer superstructures using polymer/zeolite composites prepared with supercritical CO2

We report a route to the fabrication of unique flowerlike polymer superstructures with uniform petals at the nanoscale. In this method, polymer/zeolite composite is first prepared by loading corresponding monomer and initiator into the channels of the host zeolite with the aid of supercritical (SC) CO2, followed by thermal polymerization of monomers in the channels of the zeolite. The resultant polymer/zeolite composite is then treated with HF aqueous solution to allow the self-aggregation of the polymer and the inorganic components to form the polymeric layers and inorganic layers. Unique microscale flowerlike polymer superstructures are obtained after further treatment with HF aqueous solution. Different techniques, such as scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry (TG), have been used to characterize the microflowers.