MCM—41中孔分子筛的合成及其性质

以十六烷基三甲基省化铵（ＣＴＡＢ）作模板剂，研究了水热体系中孔ＭＣＭ－４１分子筛的合成条件。在Ｈ２Ｏ／Ｓｉ介于１２－１００，Ｓｉ／Ａｌ介于１０－∞，ＣＴＡＢ／Ｓｉ介于０．０８－０．２时，可以合成出ＭＣＭ－４１分子筛，在国入煤油等混合烃的合成体系中，可以合成出孔径大于４ｎｍdisplay structure     

纳米多级孔分子筛：简短的综述

分子筛是一种三维微孔结构的硅铝酸盐晶体,具有灵活多变的骨架和组成、较高的物理和水热稳定性、无毒、高比表面积、离子可交换性以及很低的成本等特点,因而在油品精制、石油化学、农业、水和污水处理等众多领域中用作离子交换剂、催化剂和吸附剂。尽管分子筛的应用是基于其本身的微孔结构,但微孔也导致体积较大的反应物和产物分子的传质阻力高。通过制备纳米尺度和多级孔结构的分子筛等多种手段可克服常规分子筛所具有的传质限制。人们已经开发了多种方法制备了新型的分子筛材料,并考察了它们在各种催化反应和吸附反应中的性能。在反应体系中采用这种多级孔的纳米分子筛,有可能提高催化剂的使用寿命和催化性能,抑制积碳和失活。本综述概述了多级孔分子筛和纳米分子筛的高性能及其合成方法的最新进展,讨论了每个合成方法的优缺点,简述了纳米分子筛和二级孔结构分子筛的催化应用,并与常规分子筛进行了比较。     

引导剂对合成ZSM—5沸石分子筛性能影响的研究

本文采用在无胺的凝胶体系中加入引导剂的方法合成ZSM－5分子筛催化剂其物化性质和催化性能与用纯有机胺合成的ZSM－5分子筛催化剂相一致；考察 了加入不同品种和数量的引导剂对所合成的分子筛 的物化性能和催化性能的影响；在1001合成釜上进 行放大试验，得到了满意的结果；这种催化剂在100ml反应器（CO＋H2两段法合成汽油）上经过4400h的运转，其活性稳定性和选择性 仍然没有下降的趋势；考察了高温水蒸汽和理对催化剂的 活性稳定性和芳构化的影响。     

XRD法研究V2O5与NaY,NaM分子筛的相互作用

负载于多孔性、高比表面载体上的V_2O_5是工业上SO_2、CO及碳氢化合物氧化的催化剂。多年来人们对催化剂中V_2O_5的存在状态进行了广泛的研究,发现非晶相表面层V(Ⅴ)具有较高的催化活性。本文试图根据唐有祺、谢有畅等提出的氧化物在载体表面的自发分散现象,将     

Co/AlPO4-5催化剂中Co的状态及其作用

本文用IR,TEM,FABMS,ESCA,XRD以及还原度的测定等方法,描述了Co/AlPO_4-5上Co_3O_4在氢作用下变成Co°,CoO以及未还原的Co_3O_4三种状态的还原过程和钴的颗粒分布的变化,并表明在还原过程中,可能有钴的簇状物生成,导致B酸形成。     

钛硅分子筛催化剂的研究进展

钛硅分子筛催化剂的研究进展张小明张兆荣索继栓１）李树本（中国科学院兰州化学物理研究所精细石油化工中间体国家工程研究中心兰州７３００００）关键词钛硅分子筛催化氧化中孔分子筛分类号Ｏ６４３．３２含钛催化剂在有机化合物氧化反应中的作用是众所周知的［１，２］...     

超细分子筛的合成,结构特性及在催化中的应用

超细粒子通常是指尺寸小于几百纳米的微小固体颗粒,是一类介于原子簇和宏观物体之间的介观物质,其表面原子数与体相总原子数之比随粒径尺寸的减小而急剧增大,显示出明显的体积效应、表面效应和量子尺寸效应,从而使超细粒子成为具有独特的物理化学性质的新材料．超细分子筛又称纳米分子筛,作为此类新材料中的一员,它独特的催化性能和对气体的分离能力,近年来引起了人们极大的兴趣,成为催化领域中的研究热点之一．我们综述了超细分子筛的合成方法及其结构和性能的表征,着重介绍超细分子筛在催化领域中的应用,并对其发展前景进行了展…     

微孔-微孔复合分子筛的结构特征及应用

微孔-微孔复合分子筛是指两种(或多种)微孔分子筛的复合晶体,不仅具备单一分子筛的特性,而且由于复合过程中产生的结构畸变使其具有独特的孔道结构和酸性质,进而体现出优异的催化反应特性,成为当今分子筛领域的研究热点。微孔-微孔复合分子筛可分为共晶分子筛和共生分子筛两种,前者通过两种分子筛晶体的无限成分单元重排,有利于构成新的完整的晶体结构,后者则是两种分子筛共生长过程中得到的两相交错生长的复合体,产生微结构畸变和界面效应。本文对微孔-微孔复合分子筛进行归纳和分类,并系统介绍了微孔-微孔复合分子筛的研究进展,着重阐述了共晶分子筛和共生分子筛的合成与微结构特点以及在催化反应领域中的应用。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.