不对称配位磷酸钴铵增强电催化水氧化反应性能（英文）

钴基材料被认为是有望替代贵金属材料的电催化水氧化反应催化剂之一.研究发现,高活性的钴基催化剂常发生表面重构行为,深入研究表面重构行为对于阐明真实的催化活性位点和指导合成高性能的电催化剂至关重要.但是受到复杂的催化剂结构以及多种性能影响因素限制,钴基材料的配位结构对表面重构和电催化水氧化性能影响仍不清晰.基于此,本文设计了具有配位对称结构和不对称结构的两种磷酸钴基材料用于电催化水氧化反应,探索配位对称性对表面重构和水氧化性能的影响.本文通过调控共沉淀反应中磷酸铵的用量,合成了具有对称配位结构的磷酸钴材料和不对称配位结构的磷酸钴铵材料.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和物理吸附等技术表征了两种材料的物理性质.通过线性扫描法,循环伏安法和恒电位电解法等电化学方法测定两种材料的电催化水氧化活性和稳定性.采用原位电化学阻抗图谱、拉曼光谱(Raman)和XPS图分析水氧化反应中的表面重构过程.晶体结构图表明,磷酸钴材料和磷酸钴铵材料均由六配位的Co O6八面体组成.其中,磷酸钴结构中钴中心由四个水分子和两个磷酸基团或两个水分子...     

大孔膦酸树脂吸附钴的性能及其机理

大孔膦酸树脂吸附钴的性能及其机理熊春华，莫建军（丽水师专化学系，丽水３２３０００）林峰（杭州大学化学系，杭州３１００２８）关键词胰酸树脂，钴，吸附大孔磷酸树脂的合成、结构、某些性能和应用已有报道［１，２］，但是在ＨＡｃ－ＮａＡｃ体系中吸附金属钻（Ⅱ）...     

醇体系中新型晶体磷酸锆的合成和表征

醇体系中新型晶体磷酸锆的合成和表征赵玉娥，宋天佑，徐家宁，徐如人（吉林大学化学系，长春，１３００２３）关键词磷酸锆，合成，表征自１９６４年首次合成磷酸锆晶体［１］以来，人们又合成出多种磷酸锆晶体［２～４］。但在非水体系中合成磷酸锆的工作尚未见报道。本...     

一种新颖的具有螺旋孔道的磷酸钴Co2(HPO4)2·H2O的水热合成与晶体结构

过渡金属磷酸盐是空旷骨架磷酸盐体系中重要的组成部分[1～3]. 几种由碱金属或碱土金属作为平衡阳离子的磷酸钴的研究已被报道[4～5]. 采用有机胺结构导向剂合成的具有空旷磷酸钴骨架结构的化合物亦见报道[6～9]. 本文采用中温水热合成技术合成出新颖的具有螺旋孔道的磷酸钴Co2(HPO4)2*H2O, 这种化合物在沸石拓扑集合中尚未发现结构对应成员.     

在二乙烯三胺体系中含钴磷酸铝分子筛新相的合成

在二乙烯三胺体系中, 以磷酸、氢氧化铝、正硅酸乙脂、乙酸钴为原料, 在水热条件下合成出含钴磷酸铝分子筛新相, 我们把它们分别命名为CoAPSO-101和CoAPO-101型分子筛。X射线粉未衍射分析表明, 这两种分子筛具有六方对称结构, 酸洗脱及分析实验数据表明, 在该分子筛中金属钴有两种形式存在, 一种是骨架钴, 一种有非骨架钴, 同时吸附数据表明, 这两种分子筛均属于小孔结构。     

非水体系中磷酸锌的合成与表征

非水体系中磷酸锌的合成与表征宋天佑，徐家宁，徐如人，岳勇（吉林大学化学系，长春，１３００２３）（中国科学院武汉物理研究所）关键词无机合成，非水体系，磷酸锌，Ｘ射线衍射非水体系中合成磷酸铝的工作开展得较为广泛［１，２］，在水溶液中合成磷酸锌的工作亦有报...     

乙二胺导向合成的微孔晶体磷酸钴的转化现象

以乙二胺为模板剂(SDA)合成微孔晶体磷酸钴, 可以得到多种不同的结构. 本文在合成四种不同结构类型的微孔磷酸钴(命名为CoPO-en-1, CoPO-en-2, CoPO-en-3, CoPO-en-4, en 为乙二胺的英文缩写)过程中发现, 它们之间不仅可以在水热合成条件下相互转化, 在焙烧处理条件下也能实现转化. 研究发现, 在水热合成过程中, CoPO-en-2、CoPO-en-4 分别是CoPO-en-1、CoPO-en-3 的晶化中间物, 在较低晶化温度下或者较高温度的晶化初期, 可以发现它们的身影. 一旦晶化温度升高或者晶化时间延长, 它们就分别转化为CoPO-en-1和CoPO-en-3. 在合成产物的热处理过程中发现: CoPO-en-2、CoPO-en-3、CoPO-en-4 都能够通过焙烧转化为CoPO-en-1. 这种现象表明, 几种微孔磷酸钴结构间的稳定性存在递变关系.     

在改性非水合成的丝光沸石上邻二甲苯异构化

1985年Bibby首次在非水体系中合成了纯硅方钠石,由此开创了一条合成分子筛的新途径。徐文旸等首次在Na_2O-SiO_2-Al_2O_3一有机胺非水体系中合成了丝光沸石(简称非水丝光沸石,用NAM表示)。晶化过程中液相无硅铝酸根离子,固相硅铝比始终保持不变,是典型的固相转化过程。利用非水体系这一特点,可以定向地合成出催化反应所需硅铝比的沸石。与水热体系相比,非水体系合成的丝光沸石在邻二甲苯异构化催化性能上要优于前者。     

在极浓非水体系中ZSM－35沸石的合成及表征

在极浓非水体系中ＺＳＭ－３５沸石的合成及表征李建权，刘光焕，董晋湘，孙继红（太原工业大学精细化工研究所，太原０３００２４）关键词极浓体系，非水体系，ＺＳＭ－３５沸石，合成，表征水热法已广泛用于沸石合成工业过程，尤其是用有机胺作模板剂制备出性能优越的Ｚ...     

Push-Pull型不对称钴(III)咔咯的合成与性质

酸催化下在水-甲醇体系中,合成并分离了3种具有Push-Pull取代基的新型低对称A2B型钴(III)咔咯,其结构经¹H NMR, ¹⁹FNMR和HR-MS(ESI-TOF)表征,并利用光谱学和电化学方法对三种钴咔咯的电子结构进行了深入研究。研究表明：引入Push-Pull型不对称对钴(III)咔咯分子的电子结构有明显的调控作用,且随着引入基团的改变而产生显著的规律性差异,为进一步理性的分子设计、合成及其应用奠定基础。      

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.