La1-x-yBaxREyMnO3(RE:Dy,Y)超细粒子的制备和其对CH4燃烧的催化性能

使用Na2CO3·10H2O和NaOH为沉淀剂,采用共沉淀法制备了钙钛矿型结构的La1-x-yBaxREyMnO3 (RE=Dy,Y)超细粒子,具有较大的比表面积(经700,1000 ℃ 2 h 分别焙烧后,其比表面积能达到47和16.9 m2*g-1;颗粒尺寸为17和68 nm).该超细粒子随LaMnO3中A位的La3 被Ba2 及稀土元素(Dy3 ,Y3 )部分取代后,显示出良好的热稳定性及对CH4完全燃烧的高活性.     

纳米TiO2-SiO2复合氧化物的制备与性质

采用溶胶-凝胶结合CO2超临界干燥方法制备了比表面积大、热稳定性好的纳米TiO2-SiO2复合氧化物.考察了原料组成和焙烧温度对复合氧化物比表面积、热稳定性和酸性的影响,通过加氢脱硫反应考察了该复合氧化物作为加氢精制催化剂载体的可行性.结果表明,采用该方法制备的复合氧化物为纳米颗粒,在n(Ti)/n(Si)=1时,其比表面积和孔容最大;与纯TiO2相比,引入SiO2明显提高了复合氧化物的热稳定性和晶型稳定性;以此复合氧化物为载体的加氢精制催化剂具有很好的低温脱硫活性,TiO2-SiO2复合氧化物载体的酸性特征影响了催化剂的加氢脱硫活性.     

R_3GeVO_9(R=Y,La)∶Eu~(3+)(或Dy~(3+))的合成及其发光性质

采用高温固相法合成了稀土复合钒锗酸盐R3GeVO9(R =Y ,La)体系 ,并以此为基质研究了Eu3+和Dy3+在其中的发光性质 ,以Eu3+为结构探针探讨了Eu3+在R3GeVO9(R =Y ,La)中的格位情况。同时 ,还研究了被取代离子R3+的Z/r对Eu3+的红橙比和Dy3+的黄蓝比的影响以及浓度、温度和Bi3+对它们发光强度的影响。     

掺杂元素对铈锆固溶体性能的影响

用共沉淀法制备了CeZr,CeYZr,LBCeZr,LaCePrZr,LaCePrYZr和LaCePr固溶体,并对样品进行了XRD,BET,OSC以及催化性能测试和分析,表明所制备的固溶体全部为立方相结构,少量掺杂Y可以提高固溶体的比表面积和热稳定性;少量掺杂La也可以提高固溶体的热稳定性,但掺杂量过大时固溶体的比表面积和热稳定性均下降;用包头稀土矿提Nd后的LaCePr富集物制备的LaCePrZr和LaCePrYZr固溶体也具有较大比表面积和较好热稳定性.同时也采用浸渍法用Al2O3和SiO2对CeZr固溶体进行了包覆,CeZr固溶体包覆Al2O3和SiO2后比表面积和老化后的比表面积都有很大的提高.     

稀土对Al2O3陶瓷烧结温度、显微组织和力学性能的影响

研究了Y2O3, La2O3 等稀土氧化物对Al2O3陶瓷烧结温度、力学性能和显微组织的影响. 结果表明, 添加稀土氧化物可以降低Al2O3陶瓷的烧结温度, 改善显微组织, 提高力学性能. 添加复合稀土氧化物(Y2O3+La2O3)后, Al2O3陶瓷的抗弯强度和断裂韧性分别提高1.8倍和2.08倍. 其性能提高的主要原因是稀土氧化物对细晶强化、净化界面、固溶强化、自增韧补强等作用的贡献.     

离子掺杂效应对二氧化锆热稳定性的影响

利用X-射线衍射技术及比表面测试,研究了La3+, Ce4+, Ti4+掺杂离子对亚稳态t-ZrO2晶相转变及对t-ZrO2比表面积的影响.最后发现掺杂离子能有效的提高亚稳态t-ZrO2的热稳定性能.其中La3+和Ce4+能有效的推迟亚稳态t-ZrO2的晶相转变温度.并发现离子掺杂效应对二氧化锆热稳定性作用大小排列顺序为 La3+＞Ce4+＞Ti4+.     

稀土对Si3N4陶瓷力学性能和显微组织的影响

研究了Y2 O3,La2 O3,Nd2 O3等稀土氧化物对Si3N4 陶瓷力学性能和显微组织的影响。添加稀土氧化物的Si3N4 陶瓷可以获得较好的力学性能。添加复合稀土氧化物 (Y2 O3 La2 O3)后 ,断裂韧性达 7 8MPa·m1 2 ,抗弯强度达 962MPa,其性能提高的主要原因是稀土氧化物改善了材料的显微组织 ,提高了 β Si3N4 晶粒的长径比。     

Ce基复合氧化物同时催化去除碳烟-NO_x的性能研究

我们采用柠檬酸配合法制备了Ce基复合氧化物催化剂,分别在热重分析仪(TG)和管式反应器中测试了其氧化碳烟及同时脱除NOx的催化活性;并利用XRD、BET、H2-TPR、XPS表征手段考察其结构.其中,Co0.1/C e La0.05复合氧化物同时催化去除碳烟和NOx的性能最佳,碳烟脱除率为50%的反应温度为301℃,N2产率为41.4%.实验结果表明,Co主要以氧化物形式均匀分散在Ce-La固溶体表面,Co3+与Co2+价态共存,离子间的变价有利于提高催化剂的氧化还原性能,有效降低了碳烟的起燃温度.La的引入增大了催化剂的比表面积,抑制了Ce O2晶粒长大,进而提高了N2产率.部分La和Co形成了微量的La Co O3,形成了更多氧空位,有利于提高催化氧化碳烟的活性.     

新型固体电解质Ce5.2RE0.8MoO15-δ 的合成及电性质

采用溶胶-凝胶方法合成了系列新型氧化物Ce5.2RE0.8MoO15-δ(RE=Ce, Y, La, Sm, Gd, Dy, Ho, Er). 通过XRD, Raman和XPS等手段对氧化物的结构进行了表征, 采用交流阻抗谱测试其导电性能. 研究结果表明, RE3+的掺杂可增加氧离子的空位浓度, 改善母体电导率, 晶胞参数随RE3+半径的增大而增大. 掺杂离子Dy3+的半径(0.0908 nm) 与母体基质离子Ce4+的半径(0.0920 nm) 相近, 形成的掺杂氧化物晶格弹性应变最小, RE3+与氧空位间的缔合焓(ΔHA)最小, 因而氧化物Ce5.2Dy0.8MoO15-δ具有相对较高的电导率(7.02×10-3 S/cm)和较低的激活能(1.056 eV).     

纳米La0.8A’0.2Mn1-xCuxO3（A’=Ce and/or Sr）的制备、表征及其高效催化NO+CO的性能研究

采用柠檬酸-溶胶凝胶法制得钙钛矿型复合氧化物La0.8Ce0.2Mn1-xCuxO3(x=0.2,0.3,0.4),La0.8Sr0.2Mn0.6Cu0.4O3,La0.8Ce0.1Sr0.1Mn0.6 Cu0.4 O3,并采用X射线衍射(XRD)、扫描电镜(SEM)、比表面积(BET)、X射线光电子能谱(XPS)对其进行表征,测试了复合氧化物对CO+NO的催化活性。结果表明:La0.8Ce0.1Sr0.1Mn0.6Cu0.4O3催化活性最好,150℃时CO转化率91.8%,300℃时NO转化率100%;对于La0.8Ce0.2Mn1-xCuxO3(x=0.2,0.3,0.4),比表面积和颗粒的大小及分散度是影响催化活性的主要因素;对于La0.8Ce0.2Mn0.6Cu0.4O3,La0.8 Sr0.2 Mn0.6 Cu0.4 O3,La0.8 Ce0.1 Sr0.1 Mn0.6 Cu0.4 O3,催化剂的组成是影响催化活性的关键因素。     

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.     

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.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.