Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响

采用Fe粉置换氯化镍溶液中的Ni²⁺制备了Ni-Fe催化剂, 并应用于催化二硝基甲苯加氢合成甲苯二胺的反应中。运用XRD、低温氮吸附-脱附、H₂-TPD、XPS和TEM等技术手段对不同Ni/Fe物质的量的比(n_Ni/n_Fe)下催化剂进行了表征。结果表明, n_Ni/n_Fe对Ni-Fe催化剂表面性质影响显著。当n_Ni/n_Fe为1:4时, Fe抑制Ni氧化的作用达到最大, Ni-Fe催化剂化学氢吸附量和活性物种Ni的分散度分别达到了0.16 mmol·g^-1和23%, 催化剂性能得到较大的提升。在优化的催化剂制备条件下, DNT(二硝基甲苯)的转化率和TDA(甲苯二胺)的选择性分别达到了~100%和99%。另外, 对Ni-Zn漆原镍(Urushibara Ni)催化剂和Ni-Fe催化剂催化DNT加氢反应进程进行了研究, 发现它们有相同的加氢中间产物, 但反应不同阶段的催化速率存在差异。     

Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响

采用Fe粉置换氯化镍溶液中的Ni²⁺制备了Ni-Fe催化剂,并应用于催化二硝基甲苯加氢合成甲苯二胺的反应中。运用XRD、低温氮吸附-脱附、H₂-TPD、XPS和TEM等技术手段对不同Ni/Fe物质的量的比(n_Ni/n_Fe)下催化剂进行了表征。结果表明,n_Ni/n_Fe对Ni-Fe催化剂表面性质影响显著。当n_Ni/n_Fe为1:4时,Fe抑制Ni氧化的作用达到最大,Ni-Fe催化剂化学氢吸附量和活性物种Ni的分散度分别达到了0.16 mmol·g^-1和23%,催化剂性能得到较大的提升。在优化的催化剂制备条件下,DNT(二硝基甲苯)的转化率和TDA(甲苯二胺)的选择性分别达到了~100%和99%。另外,对Ni-Zn漆原镍(Urushibara Ni)催化剂和Ni-Fe催化剂催化DNT加氢反应进程进行了研究,发现它们有相同的加氢中间产物,但反应不同阶段的催化速率存在差异。     

制备高比表面积碳化硅的几种影响因素

采用溶胶凝胶法，以蔗糖和正硅酸乙酯(TEOS)为原料，草酸为TEOS水解的催化剂，制备均相碳化硅前驱体，在氩气氛和高温条件下(1 350～1 600 ℃)将碳化硅先驱体进行碳热还原，制备出高比表面积的SiC。考察了水/TEOS物质的量的比、碳/硅物质的量的比及镍盐等因素对碳化硅比表面积的影响。结果表明，当n_water/n_TEOS=7.5，n_C/n_Si=4时，适宜的镍催化剂(n_Ni/n_TEOS=0.005)，凝胶形成的时间最短，镍盐的加入可使碳热还原温度降低200 ℃。     

P123软模板对CuO-CeO2结构及其CO催化氧化性能的影响

采用软模板水热法制备了不同Cu/Ce物质的量之比的CuO-CeO₂(n_Cu ∶ n_Ce=1∶9、2∶8、3∶7、4∶6、5∶5、6∶4、7∶3)催化剂。考察了n_Cu:n_Ce和制备方法(软模板水热法和无模板共沉淀法)对CuO-CeO₂催化剂低温催化氧化CO性能的影响, 并采用XRD、N₂-吸附脱附、TEM、H₂-TPR和XPS等表征手段对催化剂的结构、氧化还原特性和表面化学状态等进行了分析。结果表明, 随着n_Cu ∶ n_Ce的增加, CuO-CeO₂催化剂的CO催化氧化活性先升高后降低。当n_Cu ∶ n_Ce=5∶5时, 催化剂在100 ℃时CO转化率即达到90%以上。采用软模板水热法制备的CuO-CeO₂催化剂大的比表面积、狭窄的孔道分布结构、活性CuO物种高的分散状态和CuO与CeO₂之间存在强相互作用是其具有优异的CO催化氧化活性的主要原因。     

Al-Ni2P/SBA-15催化剂的制备、表征及加氢脱硫催化性能

以磷酸氢二铵为磷源,硝酸镍为镍源,硝酸铝为助剂铝源,制备了n_P/n_Ni=0.8,Al含量为1.06wt%~6.35wt%的一系列Al-Ni₂P/SBA-15催化剂。采用XRD、TEM和N₂吸脱附等技术对催化剂的结构进行了表征研究,以二苯并噻吩(DBT)作为模型化合物,在微型固定床反应器上对催化剂的加氢脱硫(HDS)性能进行了评价。结果表明,Al修饰的Al-Ni₂P/SBA-15催化剂仍然保持介孔结构,当Al含量低于5.29wt%时,催化剂的物相主要是Ni₂P,当Al含量在5.29wt%-6.35wt%之间时,催化剂的物相为Ni₂P和Ni₁₂P₅。Al含量为4.24wt%的3-Al-Ni₂P/SBA-15催化剂具有最好的二苯并噻吩加氢脱硫催化活性,在反应温度为360 ℃,反应压力为3.0 MP的条件下,3-Al-Ni₂P/SBA-15催化剂对二苯并噻吩的转化率可达99.0%。     

Co2+含量对CoAl-LDHs焙烧产物结构、组成及其生长碳纳米管的影响

采用成核晶化隔离法将Co²⁺引入层状双金属氢氧化物(LDHs),得到了含不同Co²⁺/Al³⁺物质的量的比为1∶1,2∶1,3∶1的二元钴铝碳酸根型LDHs(CoAl-LDHs)。通过X射线衍射(XRD)、透射电镜(TEM)、扫描电镜-能量散射谱(SEM-EDS)、拉曼光谱(Raman)、程序升温还原(TPR)及X射线光电子能谱(XPS)等方法对CoAl-LDHs焙烧产物的结构、组成及其化学气相沉积(CCVD)催化生长多壁碳纳米管(CNTs)进行了研究。结果表明：CoAl-LDHs前体中钴的含量可以明显改变焙烧产物的组成分布和还原性能,并最终影响CNTs的生长,其中以n_Co²⁺/n_Al³⁺比为2/1的LDHs作为催化剂前体可以得到管径均匀和石墨化程度高的CNTs,这与还原得到的纳米活性Co颗粒均匀分散有关。     

水热法制备锂电池正极材料o-LiMnO2及其碳纳米管改性

MnCl₂、LiOH、EDTA和NaClO混合溶液一步水热反应合成锂离子电池正极材料正交LiMnO₂(o-LiMnO₂),进一步在反应体系中添加碳纳米管(CNTs)制备碳纳米管改性的o-LiMnO₂(o-LiMnO₂/CNTs复合材料)。采用X-射线衍射和扫描/透射电镜表征产物的晶体结构、微观形貌,循环伏安法和恒流充放电测试得活性材料电化学性能。结果表明,体系中n_Li:n_Mn控制为8:1,在180℃反应24h得到目标产物;反应体系中添加CNTs形成复合材料可降低o-LiMnO₂颗粒粒径、提高导电率。o-LiMnO₂首次放电容量为76.0mAh·g^-1,100周后容量保持为124.1mAh·g^-1;o-LiMnO₂/CNTs复合材料首次及100周放电容量(基于o-LiMnO₂/CNTs的质量)分别高达94.1和159.8mAh·g^-1。     

高活性固体碱Na2O/Al2O3-MgO的合成与表征

过量NaOH易引起铝离子流失,造成以Al₂O₃-MgO为载体的催化剂性能不稳定,为此以NH₃为沉淀剂制备了Mg-Al共沉淀物,进而通过Na₂CO₃浸渍、老化、焙烧处置,制备了Na₂O/Al₂O₃-MgO催化剂,借助XRD、SEM、SEM-EDS、TG-DSC、N₂吸附-脱附等手段对其结构及形貌进行表征,以蒜头果油甲酯化率对其活性进行评价,结果表明：采用共沉淀-浸渍的处理方法可以获得类水滑石片层结构的催化剂前驱体,该前驱体主要分解温度在200~500℃之间,经高温煅烧处理后所得催化剂中有Na-Al及Na-Mg-Al氧化物形成。制备高活性Na₂O/Al₂O₃-MgO催化剂的条件为：镁铝离子比n_Mg/n_Al=3∶1~1∶3、老化时间12 h、焙烧温度550℃、焙烧时间5 h。以n_Mg/n_Al=1∶1时制备的催化剂进行验证实验发现,所得催化剂比表面积为30 m²·g^-1、平均孔径为8.8 nm,是一种介孔催化剂,该催化剂在蒜头果油甲酯化实验中表现出高的催化活性,蒜头果油甲酯化率最高达到96.4%。     

HAlMCM-41介孔分子筛催化1,3-苯并二噁茂烷合成的研究

研究了HAlMCM-41分子筛催化邻苯二酚与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、正己醛、正辛醛、苯甲醛、二苯甲酮等十余种醛(酮)的缩合反应. 考察了反应时间、酚与醛(酮)的配比、HAlMCM-41分子筛用量、硅铝比、催化剂重用次数等因素对邻苯二酚与醛(酮)反应的影响. 结果表明, 当邻苯二酚与醛(酮)物质的量比为1∶1.4, 催化剂用量为3.5 g/mol邻苯二酚, 反应4 h, 分子筛n(SiO₂)/n(Al₂O₃)为15时, 选择性一般在99.4%以上, 转化率也一般在85.6%以上, 因此, HAlMCM-41分子筛对邻苯二酚与醛(酮)的反应有较好的催化性能.     

Cu-β沸石的合成、表征及催化性能

采用水热合成法在SiO₂-CuO-(TEA)₂O-H₂O-NH₄F体系中合成了Cu-β沸石,运用X射线衍射、红外光谱、紫外-可见固体漫反射光谱、热重-差热分析、扫描电镜和等离子体发射光谱仪等对样品进行了表征,并探讨了影响Cu-β沸石合成的因素。结果表明,按化学组成(物质的量的比)n_SiO2∶n_CuO∶n_(TEA)2O∶n_H2O∶n_NH4F=60∶(0.5~5.0)∶(16~18)∶(550~650)∶(25~50)配制初始反应混合物,可以制备出结晶良好的Cu-β沸石,且Cu原子进入了沸石骨架。所得Cu-β沸石(n_Si/n_Cu=30)在H₂O₂氧化苯酚的羟基化反应中表现出较好的催化活性,苯酚的转化率为25.1%,邻苯二酚和对苯二酚的选择性分别为63.9%和32.5%。     

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%).     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.