铁氰酸镍膜修饰金电极的研制及应用

通过层层组装的方法,将Ni^2＋和[Fe（CN）6]^3-交替沉积在巯基乙酸功能化的金电极表面．首次成功制备了铁氰酸镍多层膜修饰电极,用循环伏安法研究了该多层膜的电化学行为,实验表明峰电流随膜层数的增加而增加,膜均匀增长．该修饰电极对一价金属离子Na^＋,K^＋,NH4^＋具有选择性响应,尤其对K^＋存在准能斯特响应,响应范围0．01～1．0mol／L;而且该电极对抗坏血酸（AA）和S2O3^2-体系的氧化具有良好的电催化作用,线性范围分别为：1．14×10^-4～1．14×10^-3mol／L和5．0×10^-4～3．1×10^-3mol／L．     

丙烷选择氧化制丙烯醛催化剂中Ce的作用

考察了一系列助剂如:Cu、Zn、Mn、W、Ce、Pr、Nd等对Ag-Mo-P-O催化剂丙烷选择氧化制丙烯醛的影响.其中添加助剂Ce的Ag-Mo-P-O催化性能较好.添加Ce降低了丙烷氧化反应的活化能并有利于中间产物丙烯转化为丙烯醛.采用BET、XRD、H2-TPR、O2-TPD、C3H8-TPD和EPR等方法,研究了含Ce催化剂的结构和性质.结果表明,助剂Ce改善了催化剂的可还原性,并调变了催化剂中Mo5＋/Mo6＋比例,有利于催化剂上丙烷选择氧化生成丙烯醛,这可能归因于催化剂中形成Ce3＋＋Mo6＋Ce4＋＋Mo5＋氧化-还原循环的缘故.     

Cu-Ni/Zn催化剂甲醇裂解机理原位XPS研究

利用原位XPS 和TPD MS 技术研究了Cu Ni/Zn催化剂在甲醇裂解反应中的机理和活性中心.TPD MS脱附产物中仅检测到CH3OH、H2和CO,而未发现CH4和CH3OCH3、HCOOCH3等其它含氧物种,说明在CH3OH裂解过程中仅包括O－H、C－H键的断裂,而不存在C－O键的断裂过程.In situ XPS的研究发现,在反应温度升高到200 ℃以上时,Cu/Zn催化剂中的Zn明显被还原,反映出Cu/Zn催化剂失活过程的Cu Zn合金生成过程,而在Cu Ni/Zn催化剂中未观察到Zn的还原,且表面出现Cu＋/Cu0共存的现象.Cu＋和Cu0很可能共同构成催化剂表面的活性中心,Cu＋应该是在甲醇裂解反应过程中形成的中间态.产物氢从Cu Ni/Zn 催化剂表面脱附为反应的控速步骤.     

Cu/Zn、Cu/Zn/Ni催化剂甲醇部分氧化制氢

研究了甲醇在Cu/Zn及Cu/Zn/Ni催化剂上部分氧化热耦合裂解制氢的反应,系 统地考察了不同O2/CH3OH比及反应温度下催化剂性能.当O2/CH3OH=0.2时,催化剂的性能最 佳.在同样条件下, Cu/Zn催化剂对CO的选择性较Cu/Zn/Ni催化剂低,更具优势. Cu/Zn催化 剂用于甲醇部分氧化反应时,甲醇转化率在150 h寿命实验中基本保持在90％左右. XRD谱图 表明Cu/Zn合金的生成是导致Cu/Zn系催化剂在甲醇裂解反应中快速失活的主要原因,而在部 分氧化反应中, O2的存在可抑制Cu/Zn合金的生成,使Cu/Zn催化剂表现出高度的稳定性.     

H2O2在具有纳米结构的Rh微电极上的电催化氧化（英文）

在含有C12EO8(Octaethyleneglycol Monododecyl Ether)的H1溶致液晶相中Pt微电极上电沉积Rh介孔膜.该电极在中性、低浓度(CH2O2<10 mmol.L-1)条件下,对H2O2有较好的氧化还原响应及稳定性.由于电流磁滞效应,H2O2在Rh介孔膜微电极上的氧化与电位相关,且遵循与Rh(OH)3有关的CEE(Chemical reaction step by two sequential electrochemical steps)反应机制.H2O2浓度较大时,由于孔电极表面其结合点位趋于饱和或孔内溶液酸化的反应限制,电流呈现一平台.Rh介孔膜厚度小于200 nm的电极,H2O2浓度校正曲线符合膜孔反应一维扩散模型.     

氧化银纳米粒子的制备及其动态受激荧光

采用真空蒸发沉积法和辉光放电氧化法,制备了粒径在5～30 nm之间的可控、空间分布均匀、高纯度的氧化银纳米薄膜,使薄膜成岛状生长和避免光照是制备过程中的两个关键问题.用XPS分析了Ag 3d和O 1s轨道的结合能,计算了银和氧的原子比,证明其成分为Ag2O,用XRD确定了氧化银纳米薄膜最强的衍射峰分别对应Ag2O的（111）、（110）、（200）、（211）晶面族.研究了这种薄膜在可见光波段的光吸收,计算得氧化银的禁带宽度为2.8 eV.在蓝光持续照射几分钟激活后,观察到了其中纳米粒子在蓝光激发下发黄光和绿光,在绿光激发下发红光的现象,这种光致发光具有动态“闪烁”的特点.提出了氧化银光分解引入缺陷能级（如Ag3O, Ag2＋O和Ag3＋O）新的理论模型并对此现象进行定性的解释.     

LaFeO_3的光催化性

LaFeO3属钙钛矿(ABO3)型复合氧化物.其结构、磁性和导电性都已有许多报道[1～3],但对其光催化性报道很少.目前普遍采用的光催化剂TiO2具有光、化学稳定性好、无毒、催化活性高、氧化能力强等优点.由于TiO2禁带宽度(Eg)较宽(约为3.2eV),太阳能的利用率低[4].对钙钛矿(ABO3)型复合氧化物的光催化活性的研究发现,禁带宽度与A—O,B—O的电负性差值有关.如,A—O电负性差值较小的PbO(1.6eV)与B—O电负性差值较大的TiO2(2.0eV)合成的PbTiO3的Eg为2.7eV,正好处在1.77～3.09eV之间(可见光波长700～400nm对应光子的能量范围)吸收可见光…     

Au(111)表面上乙醇选择性氧化反应机理的密度泛函理论研究(英文)

采用密度泛函理论研究了吸附有O原子的Au(111)表面上乙醇选择性氧化的反应机理.反应结果表明,除O原子和中间产物二齿醋酸根(CH3CHOO)外,其他中间产物在Au(111)表面扩散能垒均较低,不会对反应速控步骤的确定造成影响.乙醇羟基氧化脱氢为反应的第一步骤,当氧化剂为吸附态的O原子或者为OH基时,反应活化能分别为0.20和0.17eV.氧化产物乙氧基(CH3CH2O)进一步氧化脱氢生成乙醛则需要表面吸附的O原子或另一表面吸附的OH基的参与,所需活化能为0.29或0.27eV.同时,乙醛易与表面吸附的乙氧基反应生成乙氧基半缩醛(CH3CHOOC2H5),其可进一步与O原子作用,脱氢形成乙酸乙酯.此外,在乙醛深度氧化成酸的过程中需要克服较高的反应能垒,因而在表面反应温度较低时无法进行,这与实验结果相符.     

[M(en)3]2Sn2Se6(M=Mn,Zn)的制备及其热稳定性

用有机溶剂热生长技术(SolvothermalTechnique)制备过渡金属锰和锌硒化物[Mn(en)3]2Sn2Se6(Ⅰ),[Zn(en)3]2Sn2Se6(Ⅱ).用单晶X射线衍射技术对其进行晶体结构分析.[Zn(en)3]2Sn2Se6样品的热分析结果表明,该化合物的热分解分三步进行.光学性质测试表明它们是半导体材料,[Mn(en)3]2Sn2Se6的能带隙为1.76eV.[Zn(en)3]2Sn2Se6的能带隙为2.49eV.     

稀土元素对合金高温氧化的影响

研究表明在形成Cr2O3/Al2O3膜的合金内添加微量稀土元素,可促进Cr/Al的选择性氧化,改变Cr2O3/Al2O3膜的生长传质机制,降低氧化膜的生长速率并改善其粘附性,从而显著提高合金的抗高温氧化性能。然而,稀土元素对合金高温氧化行为的影响机制目前尚存争议。在系统归纳近年来前人研究成果的基础上,对已有稀土元素微观作用模型进行了总结,并从稀土元素对Cr2O3和Al2O3膜的生长传质机制和氧化膜及氧化膜与金属基体界面的物理、化学特性的影响等方面探讨了其作用机制。     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.