Synthesis of mesoporous MFI zeolite by dry gel conversion with ZnO particles and the catalytic activity on TMB cracking

A facile synthesis method for mesoporous MFI zeolite (MMZ) has been developed. MFI zeolite was synthesized by a dry gel conversion in the presence of ZnO nanoparticles with a size of 20 nm. The as-synthesized MFI zeolite included crystalline layered zinc silicate and already possessed 5–15 nm mesopores. After calcination, MMZ/zinc silicate composite was treated with hydrochloric acid to remove unreacted ZnO particles. The micropore (1–2 nm) volume was increased after the HCl treatment, suggesting that ZnO nanoparticles (1–2 nm) remained during crystallization as well as zinc silicate. The catalytic activity of MMZ on 1,3,5-trimethylbenzene (TMB) cracking was compared with that of conventional MFI nanocrystals with a size of 80–100 nm. The conversion of TMB on MMZ was much higher than that on the MFI nanocrystals even though crystal size of MMZ is larger than the conventional MFI zeolite. These results suggest that acid sites on the internal surface of mesopores of MMZ contribute to the high conversion of TMB.     

Synthesis and characterization of magnesium hydroxide by batch reaction crystallization

Magnesium hydroxide with high purity and uniform particle size distribution was synthesized by the direct precipitation method using MgCl₂ and NaOH as reactive materials and NaCl as additive to improve the crystallization behavior of the product. The particle size distribution, crystal phase, morphology, and surface area of magnesium hydroxide were characterized by Malvern laser particle size analyzer, X-ray diffraction (XRD), scanning electron microscope (SEM) and Branauer-Emmett-Teller (BET) method, respectively. The purity of products was analyzed by the chemical method. The effects of synthesis conditions on the particle size distribution and water content (filtration cake) of magnesium hydroxide were investigated. The results indicated that feeding mode and rate, and reaction temperature had important effects on water content and the particle size distribution of the product, and sodium chloride improved the crystallization behavior of magnesium hydroxide. The ball-like magnesium hydroxides with the particle size distribution of 6.0–30.0 μm and purity higher than 99.0% were obtained. This simple and mild synthesis method was promising to be scaled up for the industrial production of magnesium hydroxide.     

硅藻土为原料原位晶化合成ZSM-5分子筛

以硅藻土为原料,采用原位晶化方法合成ZSM-5分子筛,考察了晶化时间、水硅比、模板剂用量等因素对合成分子筛的影响。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、热重(TG)手段对所合成的样品进行了表征。得出了最适宜的合成条件:晶化温度170℃,晶化时间为72 h,水硅比为n(H_2O):n(SiO_2)=45~96,模板剂用量为n(模板剂):n(Al_2O_3)=12~20。该法合成的ZSM-5分子筛具有较高的相对结晶度,具有较小的粒径且分布均一,粒径为400~500 nm。     

超增溶自组装原位合成ZSM-5纳米分子筛

采用超增溶胶团法制备纳米ZSM-5分子筛。考察体系水含量、乳化剂用量、晶化温度和焙烧温度等因素对合成分子筛产品的粒径、晶体形貌、孔径、孔容和比表面积等的影响，并采用BET、XRD和TEM等手段对其进行表征。结果表明，制备纳米ZSM-5分子筛的最佳条件：n（H₂O）∶n（SiO₂）=90,乳化剂（RHP）质量分数为10%,晶化温度180 ℃,焙烧温度500 ℃。制得的粒子平均粒径（50～70） nm,大多数粒子为球形，粒径分布较窄，呈单分散且微粒不易团聚。     

The preparation and characterization of NaWO3 particles for heat shielding by Taguchi optimization method

The synthesis of sodium tungsten oxides (NaWO₃) particles was accomplished to apply on the heat shielding film. In this preparation, Taguchi method with L₉ orthogonal array was used to optimize experimental conditions for the formation of NaWO₃ particles. Primary mean particle size and the standard deviation of NaWO₃ particles were considered as the characteristics. Concentration of sodium tungstate (Na₂WO₄), concentration of sodium borohydride (NaBH₄), and pH value were selected as main parameters. As the result of Taguchi analysis in this work, the concentration of sodium tungstate was the most influencing parameter on the particle size and the standard deviation. The pH value had also principal effect on particle size and size distribution. The optimal conditions were determined by using Taguchi optimization design method and NaWO₃ particles with primary mean size (∼100 nm) were prepared. By the analyses of X-ray diffraction and UV–vis spectrum, it was found that the annealed NaWO₃ particles were more effective on heat shielding than non-annealed particles.     

Facile Chemical Synthesis and Characterization of Copper Tungstate Nanoparticles

Copper tungstate nanoparticles were synthesized by a chemical precipitation reaction in aqueous ambient involving direct addition of copper ion solution to the solution of tungstate reagent. Optimization of the synthesis procedure was carried out using Taguchi robust design as a statistical method. In order to controllable, simple and fast synthesis of copper tungstate nanoparticles, effects of some synthesis conditions such as reagents concentrations (i.e., copper and tungstate ions), flow rate of copper feeding and temperature of the reactor on the particle size of synthesized copper tungstate were investigated by the aid of an orthogonal array. The results of optimization process showed that copper tungstate nanoparticles could be prepared by controlling the effective parameters and at optimum conditions of synthesis procedure, the size of prepared copper tungstate particles was about 56 nm. Chemical composition and microstructure of the prepared copper tungstate nanoparticles were characterized by means of X-ray diffraction, scanning electron microscopy, UV–Vis spectrophotometry, FT-IR spectroscopy and Photoluminescence.     

Rapid Crystallization of Silicalite Nanocrystals in a Capillary Microreactor

Silicalite nanocrystals were synthesized in a pressurized capillary microreactor at 150 °C within 11 min with synthesis solutions aged at 80 or 100 °C for 1–6 h. The effects of aging of the synthesis solution and the reaction pressure were examined. The resulting products were characterized by XRD, DLS, TEM, FT‐IR and TG‐DSC. Aging of the synthesis solution played an important role in shortening the crystallization time of the silicalites. The synthesis pressure should be higher than the saturation vapor pressure of water at 150 °C (～0.5 MPa) and silicalite nanocrystals with crystallinities of 70 % and 100 % could be produced from the synthesis solution aged at 100 °C for 2 h with residence times of 11 min at 0.7 MPa and 1 MPa, respectively. The mean particle sizes of these two samples were 102.2 nm and 166.4 nm, respectively. Thus, the crystallization time of the silicalite nanocrystals is shown to be significantly reduced in the capillary microreactor compared to a traditional batch system.     

Rational design of the gram-scale synthesis of nearly monodisperse semiconductor nanocrystals

We address two aspects of general interest for the chemical synthesis of colloidal semiconductor nanocrystals: (1) the rational design of the synthesis protocol aiming at the optimization of the reaction parameters in a minimum number of experiments; (2) the transfer of the procedure to the gram scale, while maintaining a low size distribution and maximizing the reaction yield. Concerning the first point, the design-of-experiment (DOE) method has been applied to the synthesis of colloidal CdSe nanocrystals. We demonstrate that 16 experiments, analyzed by means of a Taguchi L₁₆ table, are sufficient to optimize the reaction parameters for controlling the mean size of the nanocrystals in a large range while keeping the size distribution narrow (5-10%). The DOE method strongly reduces the number of experiments necessary for the optimization as compared to trial-and-error approaches. Furthermore, the Taguchi table analysis reveals the degree of influence of each reaction parameter investigated (e.g., the nature and concentration of reagents, the solvent, the reaction temperature) and indicates the interactions between them. On the basis of these results, the synthesis has been scaled up by a factor of 20. Using a 2-L batch reactor combined with a high-throughput peristaltic pump, different-sized samples of CdSe nanocrystals with yields of 2-3 g per synthesis have been produced without sacrificing the narrow size distribution. In a similar setup, the gram-scale synthesis of CdSe/CdS/ZnS core/shell/shell nanocrystals exhibiting a fluorescence quantum yield of 81% and excellent resistance of the photoluminescence in presence of a fluorescent quencher (aromatic thiol) has been achieved.PACS: 81.20.Ka, 81.07.Bc, 78.67.Bf     

溶胶-凝胶法制备的BaMgAl10O17:Eu前驱体的晶化过程

采用柠檬酸作为螯合物的溶胶-凝胶法制备了BaMgAl10O17：Eu(barium magnesium aluminate,BAM)蓝色荧光粉,并研究了,其晶化过程。通过X射线衍射、扫描电镜和荧光光谱等表征手段,研究了前驱体晶化过程的焙烧条件、结晶动力学、颗粒大小和发光性能等。BAM晶相在1100℃开始产生。温度达1200℃时,前驱体由无定型态完全转变成BAM晶相。在1120～1300℃时晶化反应的表观活化能为233kJ／mol。在室温下测得荧光粉的最大吸收峰和发射峰分别处在334nm和454nm。合成荧光粉的粒径为5μm左右,其形态和粒径取决于前驱体。     

Developing a theoretical relationship between electrical resistivity, temperature, and film thickness for conductors

We address two aspects of general interest for the chemical synthesis of colloidal semiconductor nanocrystals: (1) the rational design of the synthesis protocol aiming at the optimization of the reaction parameters in a minimum number of experiments; (2) the transfer of the procedure to the gram scale, while maintaining a low size distribution and maximizing the reaction yield. Concerning the first point, the design-of-experiment (DOE) method has been applied to the synthesis of colloidal CdSe nanocrystals. We demonstrate that 16 experiments, analyzed by means of a Taguchi L₁₆ table, are sufficient to optimize the reaction parameters for controlling the mean size of the nanocrystals in a large range while keeping the size distribution narrow (5-10%). The DOE method strongly reduces the number of experiments necessary for the optimization as compared to trial-and-error approaches. Furthermore, the Taguchi table analysis reveals the degree of influence of each reaction parameter investigated (e.g., the nature and concentration of reagents, the solvent, the reaction temperature) and indicates the interactions between them. On the basis of these results, the synthesis has been scaled up by a factor of 20. Using a 2-L batch reactor combined with a high-throughput peristaltic pump, different-sized samples of CdSe nanocrystals with yields of 2-3 g per synthesis have been produced without sacrificing the narrow size distribution. In a similar setup, the gram-scale synthesis of CdSe/CdS/ZnS core/shell/shell nanocrystals exhibiting a fluorescence quantum yield of 81% and excellent resistance of the photoluminescence in presence of a fluorescent quencher (aromatic thiol) has been achieved. PACS: 81.20.Ka, 81.07.Bc, 78.67.Bf     

结晶法由硫辛酸厂含铝废水制备铵明矾

以硫辛酸厂含铝废水中的Al3+为原料,采用结晶法制备铵明矾,研究了时间、NH4+/Al3+摩尔比、SO42-/Al3+摩尔比、温度、搅拌速度对废水中铝去除率和铵明矾产量的影响,对所制铵明矾与商品铵明矾进行比较. 结果表明,两者具有几乎相同的晶体结构、形貌和化学组成,所得产品符合同类工业产品标准. 结晶法用硫辛酸厂含铝废水制备铵明矾的适宜条件为：反应时间8 h,NH4+/Al3+ 1.40,SO42-/Al3+ 2.90,温度5~15℃,搅拌速度35~55 r/min. 宏观反应动力学表明,在晶体生长期,Al3+在边界层扩散传质为反应控制步骤,液相主体Al3+浓度C随时间t的变化关系符合方程C=(C0-Ci)e-kt+Ci. 当搅拌速度较低时,铵明矾晶体平均粒径大,分布宽;搅拌速度增加,晶体平均粒径减小,粒径分布变窄.     

Mesoporous silica with short-range MFI structure

A new type of mesoporous silica has been prepared which showed 780 m²/g of BET surface area and 0.6 ml/g of primary mesopores narrowly distributed around 4.2 nm. More importantly however, is that it showed short-range zeolite crystallinity as demonstrated by FTIR and XRD analysis, and hydrophobicity as demonstrated by water and n-hexane adsorption.

This material was synthesized via a dual-template, three-step hydrothermal–flocculation–steaming synthesis procedure developed by us recently. Briefly, MFI nanoprecursors (NPs) were first prepared by a low-temperature hydrothermal step using TPAOH as template for zeolite structure, and then flocculated using a surfactant that served as the template for the mesopores. The collected NPs are mesoporous silica exhibiting short-range MFI domains when directly calcined. However, the steaming step promoted the crystallization of the NPs and created uniform mesopores. It was found that almost every detail in these procedures affected the properties of the final product. The most important variables, however, were identified as the duration the flocculants were kept in contact with the liquid phase, and the humidity under which the steaming was conducted. By properly adjusting the procedures, the said mesoporous silica, as well as nanocrystals having high external surface area, could be produced at will.     

Effect of Polynuclear Complex Content on the Synthesis of Aluminum Nitride from Aluminum Polynuclear Complex

Aluminum nitride powders were synthesized from an aluminum polynuclear complex and glucose. Basic aluminum chloride (BAC) was used as the aluminum polynuclear complex. The effect of the polynuclear complex content on the nitridation reaction and particle size of the AIN powder synthesized was investigated. BAC solutions with various polynuclear complex contents were synthesized using an aqueous solution prepared from AlCl₃ and Al metal with various compositions. In this system, AlN was synthesized through γ-Al₂O₃ as an intermediate regardless of the polynuclear complex content. Polynuclear complex content affects the reactivity of nitridation and the particle size of the synthesized AIN powder. The reactivity of nitridation and specific surface area of the products increased with the polynuclear complex content. When the precursor with a polynuclear complex content of 94% was calcined at 1400°C, the AlN content reached 95%. Crystallite size by X-ray diffraction measurement and particle size calculated from the specific surface area for the products were in good agreement, indicating that AlN particles formed in the synthesis process are in the form of single crystals. AlN powder synthesized from the precursor with a polynuclear complex content above 80% had a fine particle size and narrow size distribution.     

超重力碳分法制备六角片状纳米级氢氧化铝

以偏铝酸钠溶液、CO₂为原料,在超重力旋转床反应器中进行碳分反应,成功制备出纳米级氢氧化铝,采用XRD、TEM、TG-DSC、粒度分布等测试技术对产品进行表征,表明产品的晶型为拜耳石、六角片状、平均粒径<100 nm,且形状规则、粒度分布窄、分散性好.同时对其合成条件进行了优化分析.结果表明,利用超重力旋转床反应器制备六角片状氢氧化铝工艺简单、重复性好、技术上是可行的.     

Synthesis of Silica Nanoparticles by Ultrasound‐Assisted Sol‐Gel Method: Optimized by Taguchi Robust Design

Silica nanoparticles were prepared by ultrasound‐assisted and conventional sol‐gel method. The synthesis procedures were designed and optimized by the Taguchi experimental design method. Molar concentrations of TEOS, H₂O, NH₄OH, and reaction temperature were chosen as main factors. The results showed that the molar concentration of ammonia is the main factor which affects the particle size of the silica nanoparticles. The chemical structure, size, and morphology of the product were investigated by X‐ray diffraction, Fourier transform infrared spectroscopy, laser light scattering, and scanning electron microscopy. By the optimum conditions of the ultrasound‐assisted sol‐gel method, silica nanoparticles with an average particle size of 13 nm were prepared.     

Optimization of parameters for the synthesis of bimodal Ag nanoparticles by Taguchi method

Bimodal Ag nanoparticles were synthesized by modified precipitation process. Taguchi analysis was used in this study and the reaction time and temperature were the most influencing parameter on the particle size and the size distribution, respectively. The optimal conditions were determined by using Taguchi method and nano-sized Ag particles with bimodal shape were obtained.     

Fe3O4纳米晶表面裹负SiO2的制备研究

纳米材料又称超微颗粒材料,是由纳米粒子组成,具有纳米尺寸效应。纳米材料用于化学反应会呈现出不同寻常的反应性能。磁性纳米材料作为一种新型的纳米材料,具有不同于常规材料的独特效应,如量子尺寸效应、表面效应、小尺寸效应、宏观量子隧道效应及顺磁效应等,这些效应使磁性纳米粒子具有不同于常规材料的光、电、声、热、磁敏感特性。近年来有关磁性纳米材料的研究备受瞩目。特别是Fe3O4纳米晶,由于其优异的磁性和表面活性及其在磁流体、微波吸收材料、水处理、催化、生物医药、生物分离等方面的应用前景,正在成为众多领域研究的热点。基于Fe3O4纳米晶的磁性纳米催化剂兼有了磁性纳米材料的所有独特性能,将其应用于催化领域,会呈现出常规催化材料所不具备的催化性能。目前液相制备Fe3O4纳米晶的液相方法主要有沉淀法、水热法、溶胶-凝胶法、微乳液法、微波超声法等。这几种方法制得的Fe3O4纳米晶有较大的差异,往往因其在不同领域的应用而采用不同的方法制备Fe3O4纳米晶。结合前人研究成果,笔者采用共沉淀法在无氮气保护的条件下制备出了粒径分布在15 nm±4 nm之间的Fe3O4纳米晶。考察了n(Fe^2+)/n(Fe^3+)、晶化时间、晶化温度、pH值对Fe3O4纳米颗粒粒径分布的影响,并在Fe3O4纳米晶表面裹负SiO2,提高了其抗氧化性能并增强其表面修饰性能,为进一步表面裹负金属活性组分制备磁性纳米催化剂打下基础。     

KCl掺杂高纯度方钠石的合成

在硅铝酸盐胶体中掺杂KCl,采用水热法合成了高纯度的方钠石。考察了KCl掺杂量对合成方钠石的影响,研究表明:在不同含水量的硅铝酸盐胶体中掺杂KCl可以合成高纯度的方钠石,合成的方钠石均为球形颗粒,胶体中含水量越高,球形颗粒的粒径越大。为工业合成方钠石提供了一种新方法。     

以酸解正硅酸乙酯为硅源合成ZSM-5分子筛的过程调控

正硅酸乙酯（TEOS）作为合成ZSM-5分子筛的常用硅源,其在不同酸碱介质中水解的前驱体聚合状态对ZSM-5分子筛的粒径和孔径分布具有调控作用。以酸性介质TEOS水解缩合的前驱体为硅源,在水热条件下合成ZSM-5分子筛,并利用XRD、SEM、BET、FI-IR等方法对反应不同阶段的样品进行表征分析。主要考察了水解程度、水解时间、合成过程的pH、晶化温度、晶化时间及模板剂用量对ZSM-5分子筛合成过程的调控,结果表明：以乙醇为共溶剂,以TEOS在硫酸介质pH=2.0时水解20 h的前驱体为硅源,水热合成过程中加入模板剂四丙基氢氧化铵（TPAOH）,铝源为氢氧化铝,180 ℃晶化30 h合成了粒径约为200 nm的ZSM-5分子筛,其比表面积提高了35.6%,平均孔径降低了48.6%。     

Synthesis of aluminophosphate molecular sieve AlPO4-11 nanocrystals

AlPO₄-11 nanocrystals, 0.05×0.08 μm in size, were synthesized by optimizing the following chemical parameters: the crystallization temperature and time, the H₂O content, the molar ratio of phosphorus to organic template (P₂O₅/R), and the HF content. The products were characterized by powder X-ray diffraction and scanning electron microscope. AlPO₄-11 nanocrystals could not be obtained by optimizing only the crystallization temperature, time and the water content, but obtained by optimizing the molar ratio of P₂O₅/R, the organic template, and the HF content.