层柱人工水热合成皂石的制备与表征(英)

利用具有理想皂石结构的人工水热合成蒙皂石为层原料，通过与羟基聚合铝离子（[Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺）交换反应合成得到了一种层柱粘土。实验对于该铝柱皂石进行了粉末XRD，FT-IR和TG-DTA表征。氮气吸附实验说明其高温活化（773K，2 h）产物具有很高的BET比表面（360 m²·g^-1）。相对于层柱蒙脱土，层柱皂石显示了更高的催化裂解性能和热稳定性。层柱皂石的异丙苯裂解转化率达到了65%；而层柱蒙脱土的转化率只有4%。这说明层材料的四面体取代对于层柱粘土Br?nsted酸位的形成具有重要的决定作用。氨程序升温脱附实验发现铝柱皂石在350～650 ℃区间具有较强的氨脱附量，表明层柱皂石具有层柱蒙脱土所没有的强酸中心。     

载体酸性对铜基交联黏土催化剂上C3H6选择性催化还原NO反应的影响

采用聚合羟基复合阳离子合成交联蒙脱土Al-Ce-PILC, 并分别用NH4NO3和(NH4)2SO4处理后， 将其作为载体, 采用浸渍法制备了应用于C3H6选择性催化还原NO反应的铜基交联黏土催化剂Cu/Al-Ce-PILC. 用Py-IR， IR和DSC等表征技术研究了不同处理方式对Al-Ce-PILC的结构、 酸性和催化剂活性的影响. 结果表明, 未经处理的Al-Ce-PILC中同时存在L酸和B酸, 以L酸为主, Cu/Al-Ce-PILC上NO的最大转化率仅为18。5％; 用NH4NO3处理提高了L酸量, NO转化率降低; 而用(NH4)2SO4处理改变了Al-Ce-PILC的酸性结构, 增大了B酸量, 并形成了超强酸中心, 催化剂上NO转化率显著提高, 在350 ℃时达最大值50.2％. B酸对于Cu/Al-Ce-PILC上NO的还原是必要的, 它有利于C3H6吸附并适度氧化为活性中间物种, 其酸量和酸强度的增加是催化剂活性改善的主要原因.     

Thermogravimetric Analysis for Acidity Determination in Pillared Clays

Thermogravimetric analysis of pyridine adsorption was applied to study the acidity at different temperatures of clays pillared with Al pillars and mixed Al-Ga pillars, in relation to the starting montmorillonite. These results were compared with those obtained by means of a pulse-chromatographic technique. The pillaring process produces a large number of acid centers in the samples. Al-Ga-PILC has a higher acidity than Al-PILC. This revised version was published online in July 2006 with corrections to the Cover Date.     

A Lamellar MWW Zeolite With Silicon and Niobium Oxide Pillars: A Catalyst for the Oxidation of Volatile Organic Compounds

In this work, an MWW-type zeolite with pillars containing silicon and niobium oxide was synthesized to obtain a hierarchical zeolite. The effect of niobium insertion in the pillaring process was determined by combining a controllable acidity and accessibility in the final material. All pillared materials had niobium occupying framework positions in pillars and extra-framework positions. The pillared material, Pil-Nb-4.5 with 4.5 wt % niobium, did not compromise the mesoporosity formed by pillaring, while the increase of niobium in the structure gradually decreased the mesoporosity and ordering of lamellar stacking. The morphology of the pillared zeolites and the niobium content were found to directly affect the catalytic activity. Specifically, we report on the activity of the MWW-type zeolites with niobium catalyzing the gas-phase oxidation of volatile organic compounds (VOCs), which is an important reaction for clean environmental. All produced MWW-type zeolites with niobium were catalytically active, even at low temperatures and low niobium loading, and provided excellent conversion efficiencies.     

Spectroscopic characterization of some iron-containing pillared clays

Bentonites, when pillared with Al₂O₃-oxide clusters, can generate materials with BET surface area in the 290–310 m² g⁻¹ range having high cracking activity for gas oil conversion. The high coke make tendency of these catalysts has been attributed to their strong Lewis type acidity.Mössbauer and X-ray photoelectron spectroscopy have shown that iron in pillared clays can be found on the clay platelets, between the clay silicate layers or in the clay octahedral layer in substitution for Al. On heating, iron migration occurs. When iron is found near the pillars it can easily catalyze secondary cracking reactions and greatly enhances the already high coke make generation observed during gas oil conversion.     

Montmorillonite-based porous clay heterostructures (PCHs) intercalated with silica-titania pillars—synthesis and characterization

Porous clay heterostructures (PCHs) were synthesized using natural montmorillonite as a raw material. Apart from pure silica pillars also silica-titania pillars were intercalated into the interlayer space of the parent clay. The detailed studies of the calcination process of the as-prepared PCH samples as well as thermal stability of the pillared structure of these materials were performed. The pillared structure of PCHs intercalated with both silica and silica-titania clusters was found to be thermally stable up to temperatures exceeding 600 °C. It was found that titanium incorporated into the silica pillars was present mainly in the form of separated tetracoordinated cations. For the samples with the higher Ti loading also small contribution of titanium in the form of the polymeric oxide species was detected. Titanium incorporated into the PCH materials significantly increased their surface acidity forming mainly Brønsted acid sites.     

Arsenic adsorption onto pillared clays and iron oxides

Arsenic adsorption was carried out on simple materials such as goethite and amorphous iron hydroxide, and more complex matrices such as clay pillared with titanium(IV), iron(III), and aluminum(III). These matrices were synthesized from a bentonite whose montmorillonitic fraction was pillared according to optimized parameters. These sorbents were characterized by various methods: XRD, FTIR, BET, DTA/TGA, surface acidity, and zetametry. Elimination of arsenite and arsenate as a function of pH was studied. Arsenate elimination was favored at acidic pH, whereas optimal arsenite elimination was obtained at 4相似文献   

交联镓皂石表面酸性及催化性能的研究

用水热法合成出两种不同镓含量的镓皂石，并用羟基铝低聚物对其进行了交联。对其表面酸性的考察发现，样品的酸量随嫁含量的增加而增大；样品均含有Ｂ酸和Ｌ酸中心，交联样品的Ｂ酸中心比交联前少。对样品催化性能的研究发现，催化活性与镓含量及酸量呈顺变关系。     

Pillared clays as efficient catalysts for cyclohexanol oxidation

Summary Iron, aluminium and mixed iron aluminium pillared clays were prepared by partial hydrolysis method and doped with 10% V and Mo. The samples were characterised by XRD, FTIR and surface area and pore volume measurements. Oxidation of cyclohexanol with hydrogen peroxide was done as probe reaction to test catalytic activity. Iron pillared systems exhibited maximum activity. The effects of various reaction variables on the reaction were studied.     

A novel catalyst for alkylation of benzene

In this research, acid-activated and pillared montmorillonite were prepared as catalysts for alkylation of benzene with 1-decene for production of linear alkyl bebzene (LAB). The catalysts were characterized by X-ray diffraction (XRD), FT-IR spectroscopy, scanning electron microscopy (SEM), N₂ adsorption-desorption isotherms, temperature programmed desorption (TPD) of NH₃ and elemental and thermal analysis techniques. The reaction conditions were optimized by varying catalyst concentration, reactants ratio and temperature in a batch-slurry reactor. It was found that acid-activation increased the porosity and surface acidity of the catalysts. Pillaring of the sample improved the surface area, micro-mesoporosity and acidity. Under optimized conditions more than 98% conversion of 1-decene was observed. All products were LABs and no major side reaction was observed.     

Montmorillonite intercalated with SiO2, SiO2-Al2O3 or SiO2-TiO2 pillars by surfactant-directed method as catalytic supports for DeNOx process

The intercalation of natural montmorillonite with SiO₂, SiO₂-Al₂O₃ or SiO₂-TiO₂ pillars by the surfactant-directed method resulted in the formation of high surface area porous materials; these were tested as catalytic supports for the process of selective catalytic reduction of NO (DeNOx). The incorporation of titanium or aluminium into the structure of the silica pillars significantly increased the surface acidity of the clay samples. Iron and copper were deposited onto the surface of the pillared clays mainly in the form of monomeric isolated cations and oligomeric metal oxide species. The contribution of the latter species was higher in the clay intercalated with SiO₂-TiO₂ pillars than in the samples modified with SiO₂ and SiO₂-Al₂O₃ pillars. The pillared clay-based catalysts were active in the DeNOx process but, in this group, the best results were obtained for the clay intercalated with SiO₂-TiO₂ pillars and doped with iron and copper. The catalytic performance of the samples is discussed in respect of their surface acidity and active forms of transition metal species deposited.     

Atomic scale imaging of pillared rectorite catalysts with the atomic force microscope

An atomic force microscope (AFM) has been used to investigate the surface features of two samples of natural rectorite (from Arkansas) pillared with alumina clusters. AFM images of the surface of natural rectorite consists of a collection of bright spots in a well ordered hexagonal pattern with distances between nearest and lateral neighbors that, in contrast to montmorillonites, do not change after exchange with Al₁₃ clusters and drying. When MgCl₂ solutions are used to flocculate and separate the clay from its impurities, AFM images of the Mg-rectorite show on its surface spheroids spaced at about 9.0 and 13.0 Å, believed to be Mg²⁺ ions. After pillaring, atomic scale resolution images of the clay surface consist instead of hexagonal arrays of bright spots with nearest and lateral neighbors at 5.4 and 9.7 Å, in agreement with the geometry of the basal plane of 2:1 clay minerals. These dimensions are retained even after steaming at 760°C per 5 h. The clay rigidity has been attributed to the presence of mica-like layers in the pillared rectorite structure. The presence of alumina debris or clusters on the silicate layers was not observed in any image examined, suggesting that (as previously observed in pillared montmorillonites) the expended clay coking tendency during gas oil cracking can be attributed mainly to the strong Lewis-type acidity of the alumina pillars between its montmorillonite-like layers.     

Étude de l’activité catalytique des argiles pontées aluminium,zirconium et cérium dans la synthèse du 2,2-diméthyl-1,3-dioxolane

The purified Tunisian clay G and the commercialized American clay W were pillared with zirconium, aluminum and mixed pillars zirconium–aluminum, cerium–zirconium, cerium–aluminum, and cerium–zirconium–aluminum. These different clays were used in the synthesis of 2,2-dimethyl-1,3-dioxolane 3 by acetalyzation of acetone 2 with ethylene glycol 1 under autogenously pressure and without solvent. Results indicate that the yield of product 3 depends of the nature and the acidity of the clay used and the time of reaction.     

高稳定性层柱粘土分子筛的催化性能

本文用酸碱滴定和红外光谱等方法对新型多孔材料——高稳定性层柱粘土分子筛(简称AlR)的表面酸性,催化活性和选择性进行了测定和研究,发现AlR的催化特性与HY和U8Y沸石有明显差别。根据实验研究,可以推测,AlR这种新型催化剂材料适用于有效酸强度较弱的大分子酸催化反应。     

Alkylation of benzene with 1-octene over titania pillared montmorillonite

Linear alkylbenzene sulfonic acid, the largest-volume synthetic surfactant, in addition to its excellent performance, is important due to its biodegradable environmental friendliness, as it has a straight chain and is prepared by the sulphonation of linear alkylbenzenes (LAB). To ensure environmental protection, the commercial benzene alkylation catalysts HF or AlCl₃ are replaced and we have developed a clean LAB production process using a pillared clay catalyst capable of not only replacing the conventional homogeneous catalysts, but also having high selectivity for the best biodegradable 2-phenyl LAB isomer. Pillared clay catalysts having high Br?nsted acidity show efficient conversion in gas phase alkylation of benzene with 1-octene with a good 2-phenyl octane selectivity.     

Role of temperature and time in the formation of infinite -M-O-M- linkages and isolated clusters in MOFs: a few illustrative examples

The role of temperature and time of reaction in the formation of metal-organic frameworks (MOFs) has been studied in two systems of compounds, manganese oxybis(benzoate) and manganese trimellitates, and the results compared and contrasted with other similar studies in the literature. The investigation reveals the formation of six different phases in oxybis(benzoate) and three phases in trimellitate systems. The low-temperature phases in both systems of compounds possess Mn 4 cluster units linked by the carboxylate ligands, while the high-temperature phase, irrespective of the duration of the reaction, has a three-dimensional structure with -Mn-O-Mn- linkages with brucite-related layers pillared by oxybis(benzoate) and Kagome-related layers pillared by trimellitate ligands. In all of the preparation, the reactions appear to have thermodynamic control as a function of the temperature. The isolation of low-dimensional structures in manganese oxybis(benzoate) at moderate time and temperature indicates possible kinetic control. The formation of reactive low-dimensional phases has been rationalized by considering the local charge distribution around the Mn site and also invoking a possible dissolution-recrystalization mechanism.     

聚乳酸/氧化锌柱撑皂石纳米复合材料制备与性能及结构表征

通过微波水解法制备了ZnO柱撑皂石,并以其为加工助剂制备了聚乳酸(PLA)/ZnO柱撑皂石纳米复合材料.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、对ZnO柱撑皂石及PLA/ZnO柱撑皂石纳米复合材料的结构进行了表征,并对其力学性能和热稳定性能进行了测试.微观结构分析表明,ZnO柱撑皂石呈现剥离状,并均匀分散在PLA基质中.力学性能研究表明0.3%ZnO柱撑皂石的加入有助于改善PLA复合材料的断裂伸长率.SEM分析表明PLA复合材料的断面发生明显改变,表现良好韧性;DSC结果显示纳米ZnO柱撑皂石可以降低复合材料的玻璃化转变温度、结晶温度,有助于提高PLA复合材料的结晶度,与XRD分析相吻合;热重分析表明ZnO柱撑皂石可以提高PLA复合材料的热稳定性.测试结果表明,ZnO柱撑皂石在PLA基质中起到了异相成核的作用,促进了PLA基质的结晶.     

Density functional theory of adsorption in pillared slit-like pores

We propose a density functional theory to describe adsorption of Lennard-Jones fluid in pillared slit like pores. Specifically, the pillars are built of chains that are bonded by their ends to the opposite pore walls. The approach we propose combines theory of quenched-annealed systems and theory of nonuniform fluids involving chain molecules. We compare the results of theoretical predictions with grand canonical ensemble Monte Carlo simulations and compute theoretical capillary condensation phase diagrams for several model systems.     

氧化铬层柱苯膦酸锆的合成与选择氧化性能

采用乙胺预胶体化方法合成了一系列氧化铬层柱苯膦酸锆和氧化铬层柱磷酸锆催化剂,其铬含量达到22.5%-36.5%,比表面为316-462m^2/g,中孔孔容占总孔容的70%以上,孔径集中在2nm左右。氧化铬层柱苯膦酸锆的热稳定性较高。以30%H~2O~2为氧化剂时,这类催化剂对苯、甲苯、乙苯、环己烷、环己烯、正庚烷和正丁醇等有机化合物具有比CrAPO-11和CrMCM-41更高的选择氧化活性。     

对苯乙烯磺酸在水滑石层间的柱撑及聚合

对苯乙烯磺酸在水滑石层间的柱撑及聚合;水滑石;对苯乙烯磺酸;柱撑;聚合