镧钼热阴极表面活性层中的镧超微粒子

为了研究镧钼阴极表面发射机制, 利用新型阴极研究装置研究阴极发射性能与表面元素La, O比例的关系, 发现表面层中La/O比例越高, 阴极的发射性能越好. 在实验基础上提出了金属La超微粒子埋藏于La2O3晶体中的热阴极表面发射模型, 模型认为活性层中的超额镧以镧超微粒子形式存在, La超微粒子中的电子在热激发下越过肖特基势垒进入La2O3晶体的导带进而克服表面电子亲和势逸出到真空, 提供了电子发射的丰富源泉. 由于肖特基势垒远小于La2O3的禁带宽度, 并且超微粒子可以使耗尽层厚度变薄, 极大降低了电子发射到真空的阈值.     

Mo-La2O3模拟阴极的高温XPS/AES研究Ⅱ.激活过程中La的变化及对发射的影响

选用片状样品考察ＭｏＬａ２Ｏ３ 阴极激活过程， 侧重分析Ｌａ 的存在状态和变化对热发射的影响。对高温ＸＰＳ实验结果的分析证实， 激活过程Ｌａ 的化学价态发生了改变， 伴随大量晶格氧的分离，Ｌａ２Ｏ３变成了缺氧化合物ＬａＯｘ（ｘ＜３／２） ， 即形成了超额的金属Ｌａ； 修正的Ａｕｇｅｒ 参数等变化趋势与上述相符。ＬａＯｘ 具有较低的逸出功是由于氧缺位的存在， 氧缺位对电子发射起到积极影响。激活过程促使Ｌａ，Ｏ离子的价电子态密度增加， 配位不饱和的Ｌａ 离子外层６ ｓ 高能价电子易形成电子发射， 即这一变化过程对热电子发射具有积极作用。     

Mo—La2O3模拟阴极的高温XPS／AES研究：Ⅱ.激活过程中La的变化？…

选用片状样品考察Ｍｏ－Ｌａ２Ｏ３阴极激活过程，侧重分析Ｌａ的存在状态和变化对热发射的影响。对高温ＸＰＳ实验结果的分析证实，激活过程Ｌａ的化学价态发生了改变，伴随大量晶格氧的分离，Ｌａ２Ｏ３变成了缺氧化合物ＬａＯｘ，即形成了超额的Ｌａ；修正的Ａｇｅｒ参数等变化趋势与上述相符。ＬａＯｘ具有较低的逸出功是由于氧缺位的存在，氧缺位对电子发射起到积极影响。激活过程促使Ｌａ，Ｏ离子的价电子态密度增加，配位不饱     

钐锶钴阴极/镧锶镓镁电解质界面的元素扩散

采用X射线衍射、扫描电镜及电化学方法考察了固体氧化物燃料电池钐锶钴(Sm0.5Sr0.5CoO3-δ,SSC)阴极烧结温度和时间对镧锶镓镁(La0.9Sr0.1Ga0.8Mg0.2O3-δLSGM)电解质的导电行为和电解质/阴极界面电化学性质的影响.结果表明,当SSC阴极的烧结温度由1173 K升高到1323 K时,LSGM/SSC界面形成了LaSrGaO4和LaSrGa3O7杂相:当烧结温度升高到1373 K时,还形成了高电子电导率的La-Sr-Co-O复合化合物.Co元素的扩散导致LSGM电解质电子电导率升高,氧离子迁移数和电池开路电压降低.延长SSC阴极烧结时间,LSGM电解质的欧姆电阻增大,电解质氧离子迁移数和电池的开路电压降低,这足由于延长SSC烧结时间加剧了LSGM/SSC界面上高阻抗相LaSrGaO4和LaSrGa3O7的生成.阴极中人量Co元素的扩散改变了LSGM电解质内部组成与结构.     

微生物燃料电池非生物阴极催化剂的研究进展

在微生物燃料电池（MFC）中,以氧为电子受体具有很多优点,但氧阴极还原的反应动力学慢,会造成阴极电势的损失。 因此,提高阴极对氧还原的电催化活性和降低催化剂的价格是MFC非生物阴极催化剂的研究重点之一。 本文综述了近年来MFC中非生物阴极氧还原催化剂的研究进展。 重点讨论了贵金属Pt、过渡金属大环化合物以及金属氧化物催化剂对氧还原的电催化活性。 其中,非贵金属氧化物及过渡金属大环化合物催化剂具有良好的性能,而且价格低廉,有望成为MFC非生物阴极Pt基催化剂的替代催化剂。     

尿素熔体中镧钴电解共沉积的研究

采用循环伏安曲线，电子探针，Ｘ射线衍射法，研究了尿素－ＮａＣｌ－ＮａＡｃ－ＣｏＣｌ２－ＬａＣｌ３熔体中镧钴电解共沉积，阴极电位，电流密度，熔体中Ｌａ＾３＋／Ｃｏ＾２＋摩尔比以及电极基体均影响沉积物中的含镧量。沉积物由Ｃｏ和Ｌａ组成，两者并末形成金属间化合物。     

某些结构受阻氧鎓盐的吸收和荧光

氧锅盐是一类带正电行的杂环化合物，作为一种合成中间体，氧锅盐在有机合成方面已得到广泛的应用［’］近年来人们对其发光和光谱性质的研究也给予足够的注意．这是由于很多氧锅盐化合物有着很强的荧光发射【’J，并且其中有些已被用作激光染料出或Q一开关材料卜1由于氧钠盐强烈的亲电特性，因而它在聚乙烯咋哇电照相体系中也受到特殊的注意，即通过它来捕获电子和诱导分子内正空穴向负电极方向迁移问染料分子的刚性化对激发分子的弛豫过程往往会带来巨大的影响，如非刚性化分子会通过分子内自由旋转使分子在激发态的弛豫过程中形成不同的…     

Mo-Y2O3阴极的热电子发射性能

利用装管发射、电子显微分析等手段系统地研究了含３％～５％（ｗｔ）Ｙ２Ｏ３的ＭｏＹ２Ｏ３热阴极丝的电子发射性能和材料显微结构。结果表明，ＭｏＹ２Ｏ３丝具有良好的热电子发射能力，与ＷＴｈＯ２阴极相比发射效率高、工作温度低。经过与ＭｏＬａ２Ｏ３丝同样的碳化处理后，用Φ０２６ｍｍ的ＭｏＹ２Ｏ３丝作阴极的实验电子管与ＭｏＬａ２Ｏ３阴极电子管相比发射性能更稳定。ＭｏＹ２Ｏ３阴极丝材的显微结构为具有亚结构的纤维状组织，碳化层为粒状晶粒结构，该结构有利于Ｙ２Ｏ３迁移和输送到阴极表面。     

二茂基镧系8—羟基喹啉化合物的合成及其热稳定性研究

通过三茂基镧系化合物Cp_3Ln(Cp=C_5H_5;Ln=Sm,Dy,Ho)与8-羟基喹啉反应(HL),合成了3种新的镧系金属有机化合物,通式为Cp_2LnL(Ln=Sm,Dy,Ho)。经元素分析、红外光谱、X光电子能谱、质谱及分子量测定,推断化合物具有二聚体结构,分子内存在通过喹啉氮原子和氧原子与金属配位而形成的五元螯合环。对化合物的热稳定性进行了研究和比较,发现化合物Cp_2SmL对热不稳定,在180℃以上分解为Cp_3Sm和SmL_3。     

镧在镍铬钴钨合金中的偏聚作用

用扫描俄歇电子能谱和扫描电子显微镜技术，研究微量镧在Ｎｉ２０Ｃｒ２０Ｃｏ１８Ｗ高温合金中的偏聚作用。发现时效状态下镧偏聚在晶界和碳化物相界，降低了界面上碳的含量；镧与杂质元素（硫、氧和氮）结合，形成没有固定成分比的原子尺寸薄膜，其作用是减慢碳化物长大速度，增加杂质的分散度，从而显著地改善合金的持久性能。     

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%.     

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.     

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.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

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.