甲基丙烯醛氧化酯化制甲基丙烯酸甲酯催化剂的制备与应用

甲基丙烯醛氧化酯化制甲基丙烯酸甲酯催化剂的制备与应用;催化剂; 甲基丙烯酸甲酯; 甲基丙烯醛; 氧化-酯化反应     

微波技术在催化剂制备中的应用

微波作为一种独特的加热手段在化学领域已得到广泛应用。本文综述了微波技术在催化剂的合成、活性组分的负载等方面的研究应用,重点探讨了在分子筛催化剂的合成中微波技术所表现出的优越性,对微波合成催化剂的作用机理及影响因素作了评述,并展望了微波技术在催化领域的发展前景。     

非晶态合金催化剂研究

本文对非晶态合金催化剂的制备及在催化领域中的应用进行了评述.通过骤冷法、化学还原法、浸渍还原法可以得到满足不同催化反应需要的非晶态合金催化剂,并可以通过制备条件的变化调变催化剂的性能.制备过程中焙烧温度、负载量以及不同催化剂载体的选用都会影响所得催化剂的性能.非晶态合金催化剂的非晶态结构、表面形态、活性中心分布等可以通过XRD、EXAFS、DSC、SEM、TEM、XPS等方法进行表征、定性.对于非晶态合金催化剂在含有不饱和基团化合物加氢反应中的研究、应用进行了阐述.     

Polymerized Micelle-Protected Platinum Clusters. Preparation and Application to Catalyst for Visible Light-Induced Hydrogen Generation

Platinum clusters protected by polymerized micelles were prepared by radical polymerization of unsaturated surfactants which were involved in micelle-protected platinum clusters. The micelle-protected platinum clusters were successfully prepared by photoreduction of hexachloroplatinic acid in water in the presence of unsaturated surfactants. The platinum clusters thus obtained were characterized by electron microscopy and IR and ¹H-NMR spectroscopies. The average diameter of the platinum particles was about 1 nm by electron microscopy, and the polymerization was confirmed by IR and ¹H-NMR spectra. The platinum clusters thus obtained proved to be highly active catalysts for visible light-induced hydrogen generation in the system of EDTA/Ru(bpy)₃ ²⁺/MV²⁺. The polymerized micelle-protected platinum clusters showed higher catalytic activity than the linear polymer-protected one. The catalytic activity was affected by the electric charge of the surfactants in the polymerized micelle-protected platinum clusters. Nonionic polymers were superior to those having anionic and cationic hydrophilic groups from the viewpoint of catalytic activity. The nonionic polymerized micelle forms rigid hydrophobic cores which help charge separation and the formation of a sequential potential field.     

双功能Pd/ZrHP催化剂的制备及其在苯酚选择性加氢反应中的应用

苯酚加氢制备环己酮是合成纤维（尼龙）生产过程中的重要环节。采用微波法快速合成了具有层状结构的固体酸（磷酸氢锆,ZrHP）和ZrHP负载的Pd催化剂,利用X射线衍射（XRD）、扫描电子显微镜（SEM）、高倍透射电子显微镜（HRTEM）、氮气吸附-脱附、X射线光电子能谱（XPS）和程序升温脱附（TPD）技术对催化剂的结构、形貌和表面特性进行了详细的表征,并将其应用于苯酚选择性加氢制环己酮的反应中。研究发现：在温和条件（100℃,1.0 MPa H₂）下,Pd/ZrHP比传统的氧化物（Al₂O₃、SiO₂、MgO）、分子筛（H-Beta）、活性炭（XC-72）负载的Pd催化剂具有更高的活性和稳定性,催化剂表面Pd原子的比活性最高可达612.2 h^-1,并且经过5次循环使用后催化剂无明显失活。结合表征结果推断,金属中心Pd与ZrHP表面的酸性位点之间的协同作用可能是影响苯酚加氢产物停留在环己酮阶段的关键因素。     

Merrifield树脂负载的膦钯催化剂制备及其在Suzuki反应中的应用

合成了一种Merrifield树脂负载的芳基膦钯催化剂, 并将其应用于催化Suzuki反应. 结果表明, 该催化剂对碘代芳烃和溴代芳烃与苯硼酸的Suzuki反应显示出较好的催化效果, 得到相应的联苯. 催化剂循环使用五次, 活性无显著下降.     

碳化硅为载体的氨合成催化剂的制备及性能研究

A sol-gel process catalyzed by oxalic acid was used for the preparation of SiC precursor from raw materials of tetraethyl orthosilicate (TEOS) and sucrose. The precursor thus obtained was homogeneous. Sintered with a certain heating program in an argon flow, the precursor was converted into the high surface area SiC. The high specific surface area silicon carbide was used as catalyst support for ammonia synthesis. The effect of the surface of the support, promoter and the amount of Ru on the catalytic activity for ammonia synthesis was studied. The results show that when the high specific surface area SiC of 113 m²·g^-1 is used as support, the prepared SiC-supported ruthenium catalyst has a relatively high activity(11.85%) under Ru 4wt%, Ba 4wt%, K 8wt%, 475 ℃, 10.0 MPa and 10 000 h^-1.     

Cu-Co合成醇催化剂制备方法的研究

在一般金属催化剂上，由CO和H2选择合成高级醇是合成气化学的重要研究方向［1－4］．IFP在1982年提出的＊u－C。催化剂至今还是非常重要的体系＊’］．它的特点是液体产物中除水外，都是直链伯醇，CI醇占较大的分数·但是，这类催化剂存在热稳定性差，活性低的缺点·为了改善催     

硝基苯加氢合成对氨基酚用负载铂催化剂的制备

 用甲醛还原沉积法制备了活性炭负载的铂催化剂（Pt／AC）和不\r\n同载体负载的铂催化剂，并考察了催化剂对硝基苯加氢制备对氨基酚反\r\n应的催化性能．结果表明，还原Pt（Ⅳ）的甲醛用量是影响催化剂性能\r\n的关键因素，甲醛必须过量而且存在一个最佳值．增加催化剂的铂负载\r\n量，不能有效提高加氢反应速度，反而易降低对氨基酚选择性；低铂负\r\n载量催化剂具有较高的活性、选择性及稳定性．XPS和TEM表征结果表明\r\n，金属铂集中分布于活性炭颗粒外部，其颗粒大小介于2～12nm间．炭\r\n载体催化剂的活性和选择性明显高于金属氧化物载体催化剂．掺入适量\r\n的Mg可显著提高Pt／AC催化剂的活性和选择性．     

A New Generation of Titanosilicate Catalyst: Preparation and Application to Liquid-Phase Epoxidation of Alkenes

A novel titanosilicate with the MWW topology, Ti-MWW, has been prepared by direct hydrothermal synthesis using boric acid as a structure-supporting agent, and also by post-incorporation of tetrahedral Ti species into MWW silicalite through controlled structural conversions between three-dimensional crystalline silicalite and the lamellar precursor. Ti-MWW is further converted by delamination into a thin sheet material applicable to the reaction of bulky reactants. Both direct hydrothermal synthesis and postsynthesis methods make it possible to introduce a controllable amount of Ti species into the MWW structure. An acid treatment of uncalcined samples is essentially important for the removal of the extraframework octahedral Ti species located on the exterior layer surface. The catalytic properties of Ti-MWW have been compared with those of conventional titanosilicates (TS-1, TS-2, Ti-Beta, Ti-MOR, Ti-MCM-41, etc.) in the epoxidation of various alkenes with hydrogen peroxide. Hydrothermally synthesized Ti-MWW proves to be more effective in the epoxidation of linear alkenes including functionalized ones, and also exhibits considerable activity for cycloalkenes. Moreover, it shows a unique shape selectivity not shared with other titanosilicates in the epoxidation of cis/trans geometric alkene isomers. Postsynthesized Ti-MWW, nearly free of boron, catalyses the alkene epoxidation more effectively as a result of the tetrahedral Ti species different from those resulting from the direct synthesis, which turns out to be the most active epoxidation titanosilicate catalyst so far. Delaminated Ti-MWW, possessing an extremely open and accessible surface area but maintaining the basic structure of zeolite, catalyses the epoxidation of various cycloalkenes more actively than large pore titanosilicates including mesoporous Ti-MCM-41.     

Pt/TiO2催化剂的制备及其在氨催化氧化中的应用

二氧化钛具有优良的光催化性能,以其为载体通过光催化还原沉积可在其表面实现单质金属活性组分负载。本研究选择二氧化钛颗粒为载体,通过紫外光照射在二氧化钛颗粒表面还原沉积铂单质,形成Pt/ TiO2核壳结构,并将该新型催化剂用于氨催化氧化反应。所制备的Pt/TiO2催化剂铂负载量减为0.2 gPt/ gTiO2,比表面积增达10 m2/ g。以该催化剂催化氨氧化反应,氨转化率在600-700 篊即可达100 %,低于目前硝酸工业中氨氧化反应温度800-900 篊,也低于PtO2升华温度850 篊。该催化剂经400 h连续反应,其铂载量、及催化活性均无降低,具有工业应用前景。     

In/SBA-15催化剂的一步法制备及其在水介质中Barbier反应中的应用

采用金属In的石蜡溶液浸渍载体, 一步法制备具有介孔结构的In/SBA-15催化剂. 在水介质中苯甲醛与烯丙基溴的Barbier反应中, 发现负载量为w(In)＝13%的In/SBA-15的催化活性显著高于金属In颗粒催化剂, 而选择性相似, 目标产物1-苯基-3-丁烯基-1-醇的得率可达89.2%. In/SBA-15的高活性主要归因于In活性位在SBA-15上的高分散, 以及规整的介孔结构有利于反应物分子的扩散. 同时, 金属In与SBA-15间较强的相互作用也可稳定In活性位, 显示出良好的应用潜力.     

用无机硅剂水热法合成纳米NiO/SiO2及其催化乙炔分解制备纳米碳管

以硅溶胶为硅源．水热法制备NiO／SiO2催化剂，用于化学气相沉积法(Chemical Vapor Deposition，CVD法)制备碳纳米管通过SEM表征，研究了催化剂原料及其配比，水热制备工艺条件对催化效果的影响．结果表明：用硅溶胶可替代正硅酸乙酯作为硅源；制备的最佳条件为：MSiO2：MNi（NO3）2=1：12～1：14，水热温度为180～200℃，压力为1．2～1．5MPa．保温时间为0．5～2h．     

Physicochemical Grounds for Application of Schungite for Neutralization of 1,1-Dimethylhydrazine in Wastewater

Chromatography–mass spectrometry and MALDI mass spectrometry have been used to study the interaction of 1,1-dimethylhydrazine and products of its oxidation with the surface of mineral schungite in aqueous solutions. A comparative analysis has been performed for organic compounds contained in initial and equilibrium 1,1-dimethylhydrazine solutions brought in contact with schungite, as well as compounds desorbed from the modified surfaces of the mineral and its inorganic components. The analysis has revealed the efficiency of schungite as a low-cost and environmentally friendly sorbent capable of catalyzing the profound oxidation of 1,1-dimethylhydrazine and products of its transformation to nontoxic low-molecularmass substances. Environmentally safe methods have been proposed for the regeneration of used schungite.     

Montmorillonite,an Efficient Catalyst for the Preparation of Dialkoxymethanes

The reaction of various alcohols with paraformaldehyde in presence of montmorillonite to give dialkoxymethanes (2a-g) in very good yield is described.     

稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能

以工业生产中碱法溶硅剩余的稻壳残渣为碳源,采用硫酸磺化法制备稻壳碳基固体酸催化剂,考察了其催化木糖脱水制备糠醛的性能.采用红外光谱、元素分析及表面酸浓度测定等手段对催化剂进行了表征.对固体酸催化剂的制备条件进行了优化,所得催化剂的表面酸浓度可达1.03 mmol/g.以木糖脱水制备糠醛为模型反应,考察了溶剂类别、反应温度和反应时间对固体酸催化剂催化性能的影响.实验结果表明,以二甲基亚砜(DMSO)为反应溶剂效果优于水,并且随着反应温度的升高和反应时间的延长,反应产率逐渐增加,最高可达75.8%.此外,还对催化剂的循环性能进行了研究,探讨了其失活原因和再生方法.     

Mechanochemistry of the 5f-element compounds

The effect of the mechanoactivation on UO₃ and U₃O₈ in agate or stainless steel vessels in air or in toluene is studied. UO₂(OH)₂ is the main product of UO₃·H₂O activation in steel vessel in air. The presence of toluene leads to strong amorphization and dispersity increase and, probably, to the formation of U₂O₅. The activation of U₃O₈ leads to its reduction to U₃O₇ which relative content in the reaction mixture depends on the mechanoactivation conditions.     

用于制备齐格勒-纳塔催化剂的氯化镁载体

氯化镁载体型齐格勒-纳塔催化剂具有高活性、聚合物形态可控等优点,是目前聚烯烃工业中最普遍使用的催化剂。氯化镁载体是此类催化剂的主要组份之一,对载体型齐格勒-纳塔催化剂的研发具有重要意义。氯化镁载体制备技术是氯化镁载体型齐格勒-纳塔催化剂研发的关键技术之一。本文简要介绍了载体型齐格勒-纳塔催化剂的发展历程,从氯化镁的结构出发分析了氯化镁作为载体的优势,重点介绍了氯化镁载体制备的关键技术:氯化镁活化方法和载体形态控制方法,尤其是球形氯化镁载体的成形技术。     

微波促进卤素交换氟化反应合成对硝基氟苯：新型高分子相转移催化剂的作用

聚二烯丙基二甲基氯化铵;微波促进卤素交换氟化反应合成对硝基氟苯：新型高分子相转移催化剂的作用     

Preparation of Organic Nanoacid Catalyst for Urethane Formation

Metal-free catalysts are preferred during these days in organic synthesis or in polymerizations.Sulfonic acid is reported to be efficient in catalyzing reactions between isocyanates and alcohols.In this work,synthesis of sulfonic acid immobilized organic nanoparticles (nanoacid) and its application in catalyzing urethane formation,are elaborated.The nanoacid can be simply prepared by miniemulsion polymerization with a reactive surfactant,namely sodium 4-((perfluoronon-8-en-1-yl) oxy) benzenesulfonate,followed by an acidification.From the images of scanning electron microscope,the nanoacid obtained is found to be narrowly dispersed and the average diameter is around 90 nm.The measured sulfur content is 0.5%,from which the content of sulfonic acid in the nanoparticles is calculated to be 0.16 mmol/g.When catalyzing urethane formation based on hexamethylene diisocyanate and n-butanol,the nanoacid catalyst exhibits considerable efficiency.