铁酸盐的制备、表征及其催化性能的研究

采用空气氧化湿法制备了含Zn、 Ni、 Co的尖晶石型铁酸盐。运用XRD、IR、UV-DRS和TPR等方法对所制备的样品进行了表征。研究了铁酸盐的化学组成、结构和氧化还原性质。考察了铁酸盐对二氧化碳选择性氧化乙苯制苯乙烯的催化性能,并讨论了催化剂的结构、组成对反应活性的影响以及二氧化碳的作用。     

CoFe2O4纳米微粒的制备及其催化性能

采用溶胶-凝胶法制备了铁酸钴纳米微粒催化剂，运用XRD、IR、TPR以及BET比表面测试等手段对所制备的样品进行了表征。研究了铁酸钴的结构和氧化还原性质，考察了铁酸钴对二氧化碳选择性氧化乙苯制苯乙烯的催化性能。结果表明：制备的铁酸钴微粒的比表面积为36.3m^2/g，晶粒大小约为30nm。在由二氧化碳选择性氧化乙苯制苯乙烯的反应中表现出较好的催化活性。     

铁酸镁系列超微粒子催化剂的氧化脱氢反应行为乙苯和环己烷的氧化脱氢反应

采用四种不同的方法制备了系列铁酸铁超微粒子催化剂，考察了其对乙苯和环己烷的氧化脱氢反应性能．结果表明，（Ｄ）样品具有最佳的乙苯氧化脱氢反应活性：４００℃，Ｏ２／Ｃ６Ｈ５Ｃ２Ｈ５（ｍｏｌ）＝３．０时，乙苯转化率为５０％，苯乙烯选择性为８０％，苯乙烯单收达４０％．催化剂对乙苯氧化脱氢反应的活性随样品的粒径变小而提高，对环己烷氧化脱氢反应则恰好相反，即活性随粒径变小而降低．这种差别归因于反应物分子结构与催化剂表面原子配位结构的匹配作用．ＥＳＲ结果对比表明，粒径小的粒子的原子配位结构对称性较低．     

铁酸镁系列超微粒子催化剂的氧化脱氢反应行为:乙苯和环己烷的氧化脱氢反应

采用四种不同的方法制备了系列铁酸镁超微粒子催化剂，考察了其对乙苯和环已烷的氧化脱氢反应性能，结果表明，（Ｄ）样品具有最佳的乙苯氧化脱氢反应活性：４００℃，Ｏ２／Ｃ６Ｈ５Ｃ２Ｈ５（ｍｏｌ）＝３．０时，乙苯转化率为５０％，苯乙烯选择性为８０％，苯乙烯单收达４０％，催化剂对乙苯氧化脱氢反应的活性随样品的粒径变小而提高；对环已烷氧化脱氢反应则恰好相反，即活性随粒径变小而降低，这种差别归因于反应物分子结构与     

FeZSM－5中不同化学环境的铁上乙苯氧化脱氢制苯乙烯的催化活性

ＦｅＺＳＭ－５中不同化学环境的铁上乙苯氧化脱氢制苯乙烯的催化活性张春雷，吴志芸，阚秋斌（吉林大学化学系，长春１３００２３）关键词ＦｅＺＳＭ－５沸石，铁，化学环境，乙苯，氧化脱氢，苯乙烯，多功能催化剂杂原子引入分子筛，除能调变分子筛的酸性和微孔孔径外，...     

乙苯氧化脱氢反应Fex/TiO2的催化性能研究

新型氧化钛负载铁催化剂Fex/TiO2在低温乙苯空气氧化脱氢制苯乙烯反应中具有良好的催化活性。350 ℃,使用Fe7/TiO2催化剂,当Fe的质量分数为7%时,可获得14.6%乙苯单程转化率和99.0%的苯乙烯选择性。通过X衍射、表面吸附、热分析及扫描电镜仪器分析表征,考察氧化钛负载铁催化剂在乙苯低温氧化脱氢反应中的催化作用。350 ℃乙苯可被活化,催化剂活性的高低取决于活性物种Fe(III)的分布状态和质量分数。     

溶胶-凝胶法制备Fe2(MoO4)3超微粒子催化剂

以硝酸铁和钼酸铵为原料，采用溶胶－凝胶法和微波加热技术制备了F 2(MoO4)3超微子催化剂，使用DTA－TG，IR，XRD以及BET比表面测试等手段，考察了制备条件对复合氧化物超微粒子形成、晶相和比表面积的影响。同时测试了该样品对甲苯选择性氧化制苯甲醛的催化性能。结果表明：制备Fe2(MoO4)2超微粒子的适宜条件为：初始溶液pH=1.0,mol柠檬酸：mol(铁＋钼）＝0．4。在此条件下制得的干凝胶，经微波加热处理后粒子的比表面积为36.4m^2/g，粒径约为35nm。在由甲苯气相选择氧化制苯甲醛的反应中表现出较高的催化活性。     

尖晶石型铁酸盐的制备和表征研究

本文采用空气氧化湿法制备尖晶石铁酸盐，得到最佳生成条件为：Ｒ－２ＯＨ＾－／（Ｍ＾２＋＋Ｆ２＋）≥１．０；Ｍ＾２＋／Ｆｅ＾２＋＝０．５摩尔比；氧化温度３４３－３５８Ｋ；氧化时间１０－２５小时。通过ＸＲＤ、ＴＰＲ和ＴＰＤ等方法对其进行表征，讨论了尖晶石型铁酸盐的氧化－还原活及其化学组成和结构的变化。     

不同沉淀剂制备的Ag／TS－1催化丙烯直接气相氧化合成环氧丙烷

 在423K、常压固定床石英反应器中，以丙烯直接气相氧化为探针反应，考察了催化剂制备方法、沉淀剂的种类和浓度对制备的Ag／TS－1催化剂催化性能的影响，采用TEM，XRD和UV－Vis等表征手段对Ag／TS－1催化剂进行了分析．结果表明，沉积－沉淀法是最佳的催化剂制备方法，但浸渍法也可制得具有环氧丙烷选择性的催化剂．K2CO3是一种良好的沉淀剂．以K2CO3为沉淀剂，硅钛比为64的TS－1为载体制备的Ag／TS－1催化剂上的丙烯转化率为1．72％，环氧丙烷选择性为98．2％．少量单质银的存在有利于环氧丙烷的生成，除银粒子的分散状态外，银粒子与载体TS－1间的相互作用对提高催化剂的选择性具有决定性作用．     

尖晶石型铁酸盐的制备及表征研究

本文采用空气氧化的湿法制备了尖晶石型铁酸盐，得到最佳生成条件为：在空气流速为２００ｍｌ／ｍｉｎ和配料比Ｒ＝２ＯＨ－／（Ｍ２＋＋Ｆｅ２＋）≥１．０，Ｍ２＋／Ｆｅ２＋＝０．５（摩尔比）下氧化温度和时间分别为３４３－３５８Ｋ和１０－２５ｈ。使用ＸＲＤ、ＴＰＲ和ＴＰＤ等方法对所制备的铁酸盐进行了表征，研究了其结构特征及氧化－还原活性，并讨论了该活性与化学组成及结构的关系。     

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

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.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.     

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.