放电等离子体烧结稀土钼材料次级性能的研究

采用溶胶凝胶(Sol Gel)和两步氢还原法,成功制备了掺杂复合RE2O3(RE2O3=La2O3 Y2O3)的稀土钼粉末,粒度分析结果表明粉体的平均粒径为80nm。采用放电等离子快速烧结方法(SPS)制备了致密样品,能谱结果表明稀土元素分布非常均匀。次级发射测试结果表明,经高温激活后,材料的次级发射系数达到2.94。     

Ga2O3-La2O3-Yb2O3-Er2O3(HO2O3)体系光谱性质的研究

根据稀土离子能级的特点,对Ga2O3-La2O3-Yb2O3-Er2O3(HO2O3)体系的光谱性质进行了探讨,发现它们有二类发光性质:Stokes发光和反Stokes发光,研究了发光强度和发射波长与掺杂离子的依赖关系,观察到由能量的共振转移引起的荧光浓度猝灭现象,并取得了最大发光强度时的掺杂离子浓度和一些规律性结果.     

影响稀土氧化物-钼阴极次级发射性能的因素

通过不同的工艺制备了稀土氧化物-钼(RE2O3-Mo)阴极材料的次级发射体，测定了材料的次级发射性能，采用SEM和能谱分析等手段研究了材料的微观结构。实验结果表明，影响材料次级发射性能的因素有：材料的化学成分、掺杂方式、烧结方法、热激活温度等。所有利于提高材料表面稀土氧化物含量的因素均可以提高材料的次级发射性能，这是因为稀土氧化物中的自由电子比较少，由一次电子激发出的二次电子在离开材料时，与材料体内自由电子碰撞的机会就小，而提高材料的次级发射性能。     

Y2O3包覆LiCo1/3Ni1/3Mn1/3O2的电化学性能

通过在硝酸钇水溶液浸渍并焙烧的简单工艺, 在LiCo1/3Ni1/3Mn1/3O2材料表面包覆了一层Y2O3. 采用X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM), 循环伏安(CV)和恒流充放电对包覆和未包覆的LiCo1/3Ni1/3Mn1/3O2进行了测试分析. 结果表明, Y2O3包覆并没有改变LiCo1/3Ni1/3Mn1/3O2的晶体结构, 只存在于LiCo1/3Ni1/3Mn1/3O2的表面; 与未包覆的材料相比, Y2O3包覆后的材料在高电位下具有更好的容量保持率和放电容量. CV测试表明, 包覆层的存在有效抑制了材料层状结构的转变及电极与电解液的负反应.     

Y2O3包覆LiCo1/3Ni1/3Mn1/3O2的电化学性能

通过在硝酸钇水溶液浸渍并焙烧的简单工艺,在LiCo1/3Ni1/3Mn1/3O2材料表面包覆了一层Y2O3.采用X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),循环伏安(CV)和恒流充放电对包覆和未包覆的LiCo1/3Ni1/3Mn1/3O2进行了测试分析.结果表明,Y2O3包覆并没有改变LiCO1/3Ni1/3Mn1/3O2的晶体结构,只存在于LiCo1/3Ni1/3Mn1/3O2的表面;与未包覆的材料相比,Y2O3包覆后的材料在高电位下具有更好的容量保持率和放电容量.CV测试表明,包覆层的存在有效抑制了材料层状结构的转变及电极与电解液的负反应.     

核壳型Gd2O3:Eu3+@Y2O3纳米发光材料的制备与发光性能

采用均相沉淀法制备了均匀球形的Gd2O3:Eu3+@Y2O3核壳结构纳米发光材料.XRD结果表明经过800℃焙烧后样品为立方晶系的Gd2O3,并且晶体发育良好,包覆Y2O3之后Gd2O3的衍射峰位置无明显变化,但随着包覆厚度的增加,出现了立方晶系Y2O3的衍射峰.FTIR谱图观测到了Gd-O,Y-O伸缩振动吸收峰,随着包覆厚度的减少吸收峰增强,认为当包覆层的厚度适当时,颗粒表面的悬空键(断键)变少,Gd(Eu,Y)-O键增多所致.SEM表明包覆前后样品为均匀分散的球形结构.XPS分析进一步证明了表面包覆上了Y2O3.荧光光谱表明:纳米Gd2O3:Eu3+表面包覆不同厚度的基质Y2O3后,均观测到Eu3+离子的特征红光发射,当包覆厚度R=4:1时的发光强度比未包覆的Gd2O3:Eu3+增强,认为核-壳型样品降低了纳米Gd2O3:Eu3+的表面效应给发光强度带来的负面影响.     

硝酸镁在γ-Al2O3上的热分解及MgO/γ-Al2O3的碱性

研究了不同载量时Mg(NO3)2 在γ Al2O3 上存在状态和热分解行为差异.考察了Mg含量不同时MgO/γ Al2O3 的碱性变化情况 ,并与水滑石焙烧产物Mg(Al)O的碱性进行了对比.结果表明,Mg(NO3)2 可单层分散于γ Al2O3 表面 ,Mg(NO3)2 的分散决定了MgO的分散阈值 ;单层态的Mg(NO3)2 比晶态的分解温度低 ;MgO/γ Al2O3 在阈值附近具有单位表面最高碱量 ,碱位分布与Mg(Al)O相似 ,单位表面碱量高于Mg(Al)O.由于γ Al2O3 的织构可以方便地调节 ,且MgO/γ Al2O3很容易制备 ,MgO/γ Al2O3 是一个很有应用前景的固体碱.     

H2O2-Na2S2O3反应对pH和反应物起始浓度比的依赖性

在H2O2-Na2S2O3反应体系中，pH值和[H2O2]0/[Na2S2O3]0对反应产物的浓度大小起着关键作用.本文通过考察这两种因素对反应产物的影响，以及对反应机理的模拟，得出了pH值和氧化剂与还原剂浓度比影响反应产物浓度的一般规律.结果表明：pH< 3时，反应主要生成单质硫， 3< pH< 6时， 较为稳定，提高pH和[H2O2]0/[Na2S2O3]0有利于SO42-生成，在中性或弱碱性溶液中S(Ⅳ)(HSO42-或SO32-)物质浓度出现峰值.     

CuO—ZnO—La2O3—AI2O3催化剂上的甲醇水蒸汽重整

研究了La助剂对甲醇不蒸汽重整制氢CuO-ZnO-AI2O3催化剂性能的影响。结果表明,加入La助剂后,催化剂的低温活性和稳定性都得到明显提高;稳定性实验表明,在合适的反应条件下,CuO-ZnO-La2O3-AI2O3催化剂经600h实验,其甲醇转化率稳定在87．5％以上,CO含量低于0．35％,显示出良好的工业应用前景。XPS研究表明,加入La助剂后,铜组分在催化剂表面得到了更好的分散,且反应过程中在该催化剂表面Zn的富集量远高于在CuO-ZnO-AI2O3催化剂表面上。     

α-Fe2O3掺杂对In2O3电导和气敏性能的影响

用化学共沉淀法制备了α Fe2O3掺杂的In2O3纳米晶微粉,研究了α Fe2O3掺杂对In2O3电导和气敏性能的影响. 结果表明, α Fe2O3和In2O3间可形成有限固溶体In2－xFexO3(0≤x≤0.40); Fe3＋对In2O3晶格中In3＋格位的部分取代,大大增强了阴阳离子间的结合力,导致材料中氧空位VO×数骤降、 自由电子的浓度变稀和电导下降. n(Fe3＋):n(In3＋)=5 :5的共沉淀粉于800 ℃下灼烧4 h所得的α Fe2O3掺杂In2O3传感器元件,对45 μmol•L－1 C2H5OH的灵敏度达54.0,为相同浓度干扰气体汽油的8倍多.     

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.     

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.     

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.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

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.     

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.