Ce-SBA-15的制备及其苯酚甲醇烷基化性能

采用后合成法制备Ce-SBA-15介孔分子筛.通过XRD、N_2吸附-脱附、SEM、EDS、NH_3-TPD、Py-FTIR和TGDTA手段对样品进行表征.结果表明,Ce-SBA-15催化剂具有介孔结构,活性组分CeO_2能够很好地分散在载体表面.在固定床反应装置上,考察了Ce负载量、焙烧温度和焙烧时间对Ce-SBA-15催化苯酚甲醇烷基化性能的影响.最佳组成和制备条件为:Ce负载量为15%,焙烧温度为550℃,焙烧时间为4.5 h.在苯酚/甲醇摩尔比1/4,反应温度460℃,质量空速3.0 h~(-1),常压的条件下,Ce-SBA-15分子筛催化苯酚甲醇烷基化性能最好,苯酚转化率达到66.89%,邻甲酚选择性达到55.43%.     

植物还原法制备负载型金纳米催化剂催化乙醇选择氧化反应

采用侧柏叶提取液还原氯金酸制备负载型金纳米催化剂,通过乙醇选择氧化反应,筛选出催化性能较好的TiO2载体。以TiO2载体为载体,考察了Au负载量、焙烧温度、催化剂用量、碳酸氢钠添加量及催化剂反应条件(时间、温度、压力)等因素对乙醇选择氧化反应的影响。结果表明,1.5%Au/TiO2催化剂(Au负载量为1.5%,质量分率,下同)催化乙醇选择氧化反应性能最佳,产物为乙醛、乙酸乙酯和缩醛,0.5%碳酸氢钠添加剂可抑制缩醛的生成,并可显著提高乙醇转化率和乙酸乙酯选择性。通过优化催化反应条件(1.5%Au/TiO2催化剂焙烧温度为400℃、用量为0.4 g、反应温度为100℃、氧气压力为3 MPa、反应时间为3 h时),乙醇转化率为47.9%,乙酸乙酯选择性为89.1%。     

催化剂Zn-Sr-SiO2的制备及其 对甲醇脱氢制备无水甲醛的催化性能

采用溶胶凝胶法制备了催化剂Zn-Sr-SiO₂，其结构经SEM、 XRD、 N₂吸附/脱附、NH₃-TPD和CO₂-TPD表征。利用固定床反应器评价了Zn Sr SiO2对甲醇脱氢制备无水甲醛反应的催化性能。研究了焙烧温度，Zn负载量，Zn/Sr摩尔比，载气流量，质量空速等因素对催化性能的影响，以及催化剂的寿命、失活与再生。结果表明：制备催化剂的最佳条件为焙烧温度700 ℃， Zn负载量为15%， Zn/Sr为5/1。反应温度为600 ℃，甲醇的质量空速为4.47 h^-1时，甲醇的转化率为25.35%，甲醛的选择性为91.98%。催化剂寿命为33 h。再生后，催化剂的中强碱性位得到了再生。     

制备条件对MoS2/Al2O3耐硫甲烷化催化剂性能的影响

本文研究了前驱体MoO_3的负载量、浸渍温度和焙烧温度等制备条件对Mo S2/Al_2O_3耐硫甲烷化催化剂性能的影响,并通过XRD和H2-TPR表征了催化剂的物相和还原性能。结果表明,随着负载量增加,MoO_3与Al_2O_3间的相互作用增强,Al2(Mo O4)3相增多,导致催化剂更难被还原硫化,MoO_3还原温度升高。浸渍温度对CO转化率和CH4选择性有一定的影响,浸渍温度为70℃时,MoO_3的生成增多,且还原温度最低,CO转化率较高,而CH4选择性和CO_2选择性变化不大。随着焙烧温度升高,CO转化率先升高后降低,对CH4和CO_2选择性影响不大,其中以450℃焙烧的CO转化率最高,600℃焙烧的CO转化率最低。当焙烧温度在400~450℃时,Al2(Mo O4)3和Mo4O11的特征峰基本上消失,能够完全生成MoO_3,且结晶度较好。因此,合适的焙烧温度为400~450℃。     

KN03／MCM-48催化酯交换法合成碳酸二丙酯

对KNO，／MCM-48用于丙醇和碳酸二甲酯进行酯交换合成碳酸二丙酯的催化性能进行了考察．用X射线衍射（XRD）、红外光谱（IR）和X射线荧光法研究了催化剂的结构特征和表面性质．XRD结果表明，随着K负载量的增加，载体特征峰强度逐渐减弱，但仍保留MCM-48的晶体结构．随着焙烧温度的升高，KNO3逐渐分解成K2O．分别考察了活性组分负载量、焙烧温度、焙烧时间和催化剂的用量以及反应时间对反应的影响．结果表明，KNO3／MCM-48催化剂对碳酸二丙酯的合成具有很高的催化活性．在反应温度363K，反应时间6h，催化剂用量5％，丙醇与碳酸二甲酯摩尔比为4的条件下，碳酸二甲酯的转化率可达99．9％，产物碳酸二丙酯选择性93．4％，产率93．3％．     

Mo-V-Te-Nb-O催化剂上丙烷选择氧化制丙烯酸 I．催化剂的制备条件及稳定性

研究了催化剂的制备条件(焙烧方式、焙烧气氛和焙烧温度)对Mo-V-Te-Nb-O上丙烷选择氧化制丙烯酸反应的影响．结果表明，制备条件对催化剂的催化性能具有很大的影响．与敞开式焙烧制得的催化剂相比，封闭式焙烧制得的催化剂具有较高的丙烯酸选择性，但丙烷转化率较低．在空气中焙烧制得的催化剂对丙烯酸无选择性，但在氮气和氩气中焙烧制得的催化剂具有很高的丙烷转化率和丙烯酸选择性．随着焙烧温度的升高，丙烷转化率降低，丙烯酸选择性升高，适宜的焙烧温度为600℃．催化剂制备条件对催化剂的晶相结构也具有重要的影响．在惰性气氛中采用600℃下封闭式焙烧制得的Mo-V-Te-Nb-O催化剂经210h反应后，丙烷转化率保持为19％，而丙烯酸选择性持续升高，由32％升至50％．     

纳米Cr2O3系列催化剂上CO2氧化乙烷脱氢制乙烯反应

 采用溶胶－凝胶法和共沸蒸馏法耦合技术制备了纳米Cr2O3催化剂，并采用共沉淀法和共沸蒸馏法耦合技术制备了纳米Cr2O3／Al2O3，Cr2O3／ZrO2和Cr2O3／MgO复合催化剂．应用BET，XRD，XPS，TPR和TEM等物理化学方法对催化剂的结构和物化性质进行了表征，并考察了该系列催化剂上CO2氧化乙烷脱氢制乙烯的反应性能．结果表明，纳米Cr2O3催化剂上乙烷和CO2的转化率均明显高于常规Cr2O3催化剂，但乙烯的选择性低于常规Cr2O3催化剂；纳米复合催化剂中的复合成分显著影响催化剂的催化性能．其中，10％Cr2O3／MgO纳米复合催化剂在温度为973K时，乙烷转化率和乙烯选择性分别可达到61．54％和94．79％．纳米催化剂表面Cr的还原性以及Cr6＋／Cr3＋比值是影响乙烷转化率和乙烯选择性的重要因素．     

新型高性能Cu/HMS催化剂的合成及其在草酸二甲酯催化加氢合成 乙二醇反应中的应用

采用原位合成法合成了介孔Cu/HMS催化剂, 并以草酸二甲酯催化加氢合成乙二醇为探针反应考察了不同焙烧温度对反应催化性能的影响, 结果表明焙烧温度为650 ℃时合成的催化剂在该反应中表现出最佳的催化性能. 在反应温度为200 ℃、压力为3 MPa、氢酯比为50、液时空速为0.74 h－1的条件下, 草酸二甲酯的转化率达到100%, 并且乙二醇的选择性达到97%. 采用X射线粉末衍射、N2低温吸附、H2-TPR、N2O滴定、X射线光电子能谱及傅利叶变换红外光谱对系列催化剂进行了系统表征, 阐述了焙烧温度对催化性能影响的本质原因. 研究表明焙烧温度能够影响活性铜物种的分散度和铜物种与载体间的相互作用, 从而影响草酸二甲酯催化加氢的催化性能.     

ReOxZrO2催化甲醇一步合成二甲氧基甲烷的研究

利用负载型ReOxZrO2催化剂，将甲醇选择性氧化并一步合成二甲氧基甲烷。考察了反应时间、反应温度以及铼负载量对反应的影响。并利用N2吸附/脱附、X射线光电子能谱、氨程序升温脱附(NH3-TPD)和氢程序升温还原(H2-TPR)等手段对催化剂进行了表征。结果表明，较高的反应温度有利于提高甲醇的转化率，但对二甲氧基甲烷的选择性不利；催化剂上所负载铼的质量分数对甲醇转化率影响较大，在铼的质量分数为1.64%时转化率达到最大值25.1%；负载于ZrO2上的ReOx 具有双功能催化性质：它既可作为氧化中心氧化甲醇，在还原后又可作为酸中心催化醇醛缩合。     

KF/MgO 催化碳酸二甲酯与月桂醇酯交换合成碳酸二月桂酯

 研究了 KF/MgO 催化剂对碳酸二甲酯 (DMC) 与月桂醇酯交换反应制备碳酸二月桂酯 (DDC) 的催化性能. 考察了催化剂 KF 负载量及焙烧温度对反应的影响, 并采用 X 射线衍射、傅里叶变换红外光谱、扫描电镜和 N2 吸附-脱附等对催化剂进行了表征. 结果表明, 催化剂 KF/MgO 在空气中较高温度焙烧后生成新相 K2MgF4 和 K2CO3, 它们为催化剂的主要活性组分. 催化性能测试结果表明, 该催化剂具有良好的催化活性, KF 的最佳负载量为 30%, 催化剂的最佳焙烧温度为 873 K. 还考察了反应条件对 KF/MgO 催化剂性能的影响. 当在反应物月桂醇:DMC 摩尔比 = 4, 催化剂用量为反应物总质量的 0.75%, 反应时间为 4 h 的条件下, 反应性能最佳, DMC 转化率和 DDC 收率分别为 86.7% 和 86.2%.     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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%).     

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.     

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.