高T_c LaBa_2Cu_3O_(7-δ)超导相的制备和结构研究

我国蕴藏着丰富的稀土元素,利用镧代替钇,研究高T_c超导体具有一定的经济意义。但镧和钡的原子半径相近而比钇大得多,这给制备工作带来了困难。国内曾有几个单位制备出了T_c80K的超导相,但都难以重复。日本A.Maeda等人合成了T_c80K的正交LaBa_2Cu_3O_(7-δ)超导相,测定了晶体结构和相转变温度。最近我们也开展了对这个体系的研究,本文将给出隐定的高T_cLaBa_2Cu_3O_(7-δ)超导相的制备方法、相变温度、晶体结构以及超导性能与正交性的关系。     

复氧化物超导相的结构化学

1.氧化物超导体的发展1911年,荷兰昂纳斯发现Hg在4K转变为超导态。随后,在金属合金体系(包括金属间化合物)中进行了大量新超导体的探索工作,但其超导转变温度T。提高得很慢,直至1973年才获得Nb_3Ge的T_c约为23K的超导相。每年大约仅提高0.3K。从1967年发现SrTiO_3和NaWO_3在0.3K转变为超导态,1973年发现LiTi_2O_4的T。为13.7K,1975年发现BaPb_(1-x)Bi_xO_3,x=0.3的T_c为13K,氧化物超导体的T_c提高甚快。1986年Bednorz和Muller注意到钙钛矿型结构的BaPb_(1-x)Bi_xO_3具有超导性,而其载流子浓     

Bi(Pb)-Sr-Ca-Cu-O体系中110K超导相的制备和结构研究

自K.A.Müller等人发现氧化物超导体以来,在二年的时间内,寻找更高T_c超导材料的工作在世界范围内发展很快,目前已在Bi-Sr-Ca-Cu-O和Tl-Ba-Ca-Cu-O二个体系中分别获得零电阻转变温度为110K和120K的超导体。相对而言,获得120K的Tl_2Ba_2Ca_2Cu_3O_(10)[简记为TI-2223]超导体要容易一些,我们研究室已经测定了这个超导相的结构。但是Tl_2O_3的高温易挥发性和剧毒性,给Tl系超导体的制备带来了困难,从而限制了达个体     

K对Mn—Co—O的结构及氧化活性的影响

利用XRD,TPD,TFD-MS及催化氧化反应等实验技术,研究了K对Mn-Co-O的结构及氧化活性的影响。XRD结果表明,Mn-Co-O系已形成反尖晶石型的MnCo_2O_4结构;K-Mn-Co-O系中除MnCo_2O_4型结构外,还有新相KMnO_2存在。根据O_2的TPD-MS及吡啶的TPD结果,Mn-Co-O中添加适量的K能提高供氧活性和增加供氧数目,但酸中心数目减少,强度降低。K对Mn-Co—O催化剂氧化活性的影响随反应物分子结构的不同而异,对乙酸乙脂、苯甲酰氯等极性有机物的完全氧化反应,K能提高氧化活性,但对苯、正己烷等非极性有机物的完全氧化反应,K使其活性降低。     

掺加Nd和K改性对Co_3O_4催化分解N_2O活性的影响（英文）

用水热法和共沉淀法分别制备了Nd-Co_3O_4催化剂,催化分解N_2O。其中,水热法制备的Nd-Co_3O_4催化活性较高。在不同组成的Nd-Co_3O_4中,优化出了较高活性的0.01Nd-Co_3O_4催化剂,在其表面浸渍K_2CO_3溶液制备K改性催化剂(K/Nd-Co_3O_4)。用X射线衍射(XRD)、N_2物理吸附、扫描电镜(SEM)、X射线光电子谱(XPS)、程序升温还原(H_2-TPR)、O_2程序升温脱附(O_2-TPD)等技术表征催化剂结构。结果表明,Nd-Co_3O_4和K改性催化剂均为尖晶石结构;K改性弱化了催化剂表面Co-O键,有利于表面氧的脱除,提高了催化剂活性。有氧有水气氛350℃连续反应40 h,K/Nd-Co_3O_4催化剂上的N_2O分解率超过90%,稳定性较好。     

O2对燃煤烟气中As2 O3均相反应生成途径影响研究

应用量子化学密度泛函理论研究了燃煤烟气中As和AsO与O_2均相生成As_2O_3的反应机理。首先计算确定了各反应物、中间体、过渡态和产物的结构和能量,然后运用热力学和动力学方法对As_2O_3均相生成过程进行分析。结果表明,由As和AsO与O_2均相生成As_2O_3的最大反应能垒分别为32.9和157.2kJ/mol,在烟气中由As转化为As_2O_3更为容易进行。在500-1900 K下,各反应的正逆反应速率常数均随温度的提高而增大,但不同反应过程受温度影响的程度不同。As与O_2反应生成AsO和AsO_2的两个反应过程的平衡常数在所研究的温度范围内均大于10~5,能完全反应,可以认为是单向反应。AsO与O_2反应生成AsO_2的过程平衡常数在所研究的温度范围内小于10~5,反应不完全,转化率低。AsO与AsO_2生成As_2O_3(D3H)构型的平衡常数极低,反应难以进行,而生成As_2O_3(GAUCHE)构型反应能垒低,可自发进行。     

Yb_2O_3在LiF-CaF_2熔盐中的溶解度研究

氟盐体系是熔盐电解稀土氧化物制备稀土金属及其合金的较好体系。为了明晰Yb_2O_3在氟盐体系(LiF-CaF_2)熔盐中的溶解规律。采用等温饱和法测定Yb_2O_3在LiF-CaF_2熔盐中的溶解度的变化规律,通过X射线衍射(XRD)物相初步分析Yb_2O_3在LiF-CaF_2熔盐中的溶解机制。结果表明:在1353 K时, Yb_2O_3在LiF-CaF_2熔盐中溶解达到平衡所需的时间约为2.5 h,在1293～1413 K实验温度范围内, Yb_2O_3的溶解度随温度升高呈线性增长;通过对LiF-CaF_2-Yb_2O_3体系溶解平衡后的水淬、空冷产物进行物相分析,结果表明:Yb_2O_3在LiF-CaF_2熔体中的溶解过程存在物理性的溶解,但氟化过程的溶解仍然是主要溶解形式。     

一步水热合成Y-Co_3O_4复合氧化物催化剂及催化分解N_2O（英文）

用一步水热、分步水热、浸渍等方法分别制备Y-Co_3O_4复合氧化物,用于催化分解N_2O的反应,其中,一步水热法制备的催化剂活性较高。再用一步水热法制备了不同Y/Co物质的量比的Y-Co_3O_4复合氧化物,在优化出的催化剂(0. 03YCo_3O_4)表面浸渍K_2CO_3溶液,制备K改性催化剂(0. 02K/0. 03Y-Co_3O_4)。用X射线衍射(XRD)、N_2物理吸附、H_2程序升温还原(H_2-TPR)、O_2程序升温脱附(O_2-TPD)、扫描电镜(SEM)、X射线光电子谱(XPS)等技术表征催化剂结构。研究发现,Co_3O_4和Y-Co_3O_4同为尖晶石结构,但Y-Co_3O_4的催化活性显著高于Co_3O_4。K改性增加了催化剂表面的活性位(Co~(2+)),还有利于吸附氧的脱除,从而提高了催化剂活性。在无氧无水、有氧无水、有氧有水气氛中,K改性催化剂上的N_2O全分解温度分别为325、350、375℃,催化剂活性较高。有氧有水气氛350℃连续反应50 h,K改性催化剂上N_2O分解率保持90%以上,稳定性较高。研究发现,Y-Co_3O_4及K改性催化剂上N_2O分解反应的Ea和lnA之间存在动力学补偿效应。     

1988年无机化学的重要事件

高温超导体化学的新进展去年我们介绍了高温超导体的发现以及由之而引起的世界性的超导热.当时达到的最高转变温度(T_c)为95K,得自“1-2-3”化合物YBa_2Cu_3O_7-x(X~0.1).一年来,世界各地的科学家以强烈的竞争姿态进行了深入的研究将转变温度提高到125K.这一进展和新型超导体的发现都足以令人乐观,但距离实现室温超导的目标仍然还很远. 在过去一年中,新型超导材料的合成与表征取得了很大的进步.但科学发展中往往出现     

Nd2O3—PbO系中间相的研究

前人研究表明:La_2O_3、Sm_2O_3和Gd_2O_3均与PbO形成通式为RE_2O_3·4PbO的中间化合物。我们曾发现Eu_2O_3-PbO系有一个化学配比约为Eu_2O_(3·)(PbO)_(3.7)的四方结构中间相,Sleight曾报道过Nd_2O_3和PbO能形成不稳定的Nd_2O_3·2PbO化合物,但未对Nd_2O_3-PbO系平衡固相作全面考查,本文报道我们对Nd_2O_(3·)2PbO系中间相的研究结果。 取纯度99.99％的Nd_2O_3和化学纯的PbO,按多种比例研磨混合后压成园柱形样品,     

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.