真空加热活化法提高内嵌钴粒子的碳纳米管的水裂解产氢催化活性

采用真空加热活化法制备出高催化活性的内嵌金属钴纳米粒子的碳纳米管材料.通过增加碳纳米管材料的本征碳缺陷位点,显著提升了材料的催化活性(7倍).高分辨透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)和拉曼(Raman)光谱表征结果显示,真空加热活化增加了碳纳米管的本征碳缺陷,并减少了碳纳米管碳层的杂原子含量.电化学表征和电催化水裂解实验结果表明,增加碳纳米管的本征碳缺陷位既可以在碳纳米管上产生更多的催化位点,又可以提高碳纳米管界面的电荷迁移能力,进而提高对水裂解的催化性能.     

催化裂解低碳烷烃制备碳纳米管薄膜

碳纳米管性质奇特、用途广泛[1]。目前制备碳纳米管薄膜的方法主要有电弧放电法[2]、催化裂解[3]、及真空过滤碳纳米管悬浮液制备“巴基管纸”(Buckypaper)[4]等。本文采用镀镍基板催化裂解低碳烷烃法制备碳纳米管薄膜,考察了镀膜时间、蚀刻和氨水处理等条件对碳纳米管薄膜产物形貌的影响。1　实验部份1 1　镀膜与后处理采用离子溅射法在硅酸盐基板上镀镍,镀镍电流7 5mA,镀镍时间分别为2min、15min、30min、45min或60min;对镀镍基板再进行蚀刻(蚀刻电流7 5mA,蚀刻时间2min)或用氨水浸泡处理(含NH325%,超声振荡30min),然后烘干备用。1 …     

原位还原类钙钛型复合氧化物上碳纳米管的制备(英文)

在流动床反应器上利用原位还原类钙钛复合氧化物所得纳米金属颗粒（Ｆｅ、Ｃｕ）催化裂解ＣＨ４可大量制备尺寸均一的碳纳米管。制备的碳纳米管形貌通过透射电镜（ＴＥＭ）来观察表征。电镜观察结果表明,利用不同的类钙钛型复合氧化物可以合成具有不同结构的碳纳米管。     

催化剂制备条件对碳纳米管的影响

用柠檬酸络合法制备的Ni-La-Mg型催化剂催化裂解甲烷合成碳纳米管，并通过测定活性镍表面积研究了催化剂制备过程中柠檬酸浓度及活化温度对碳纳米管生成的影响，TEM测定结果表明，经凝胶自燃烧产生的催化剂，可通过改变柠檬酸的浓度来制得不同粒径的催化剂颗粒，从而获得一定管径的碳纳米管，另外，在500－700℃内，活化温度对催化剂活性影响不大，只有在较低或较高温度时对活性才有较大的影响。     

催化裂解CH4制备不同形貌的碳纳米管

通过甲烷于较低温度(500～700℃)下在镍催化剂上催化裂解制备了各种形貌的碳纳米管.透射电镜测试结果表明,碳纳米管的外径和内径明显地受催化剂的大小和形貌的影响.本文考察了催化剂前驱体的种类、反应温度和原料气流速对镍催化剂和碳纳米管形貌的影响.     

甲烷在流态化催化剂床裂解生长多壁碳纳米管

甲烷在流态化催化剂床裂解生长多壁碳纳米管;多壁碳纳米管;Ni-Mg-O催化剂;甲烷;流化床;催化化学蒸汽沉积法     

不同活性炭负载的镍基催化剂上废塑料裂解制碳纳米管性能

以椰壳炭、竹炭和木炭三种活性炭为载体,采用浸渍法制备炭负载金属镍的催化剂,考察其在废塑料裂解制备碳纳米管过程中的催化反应性能;采用X射线衍射、扫描电镜、透射电镜、拉曼光谱仪、同步热分析仪、比表面积分析仪等手段分析了催化剂和产物碳纳米管的形貌和结构。结果表明,椰壳活性炭为载体制备的镍基催化剂上碳纳米管产量最高、石墨化程度最好。以椰壳活性炭为载体制备的镍基催化剂为例,研究了反应温度和镍负载量对其催化性能的影响。     

成都中科时代纳米材料事业部

<正>中科时代纳米材料事业部是中国科学院成都有机化学有限公司的直属机构中科时代纳米自1996年开展天然气催化裂解法制备碳纳米管以来,得到了中国科学院院长基金、中国科学院知识创新工程项目、国家"863"计划纳米材料专项及国家重大科学研究计划课题等多个科研计划的支持,在碳纳米管制备和应用方面取得一系列重要成果,为多壁碳纳朱管产品国家标准起     

催化剂对纳米聚团床法制备的纳米碳材料形貌的影响

 在纳米聚团床中用催化化学气相沉积法批量制备了碳纳米管，研\r\n究了过渡金属催化剂对碳纳米管形貌和产量的影响．实验结果表明，含\r\n铁催化剂的活性较低，产率较低，但产品质量较好；含镍催化剂的活性\r\n较高，产率较高，但产品质量较差；在钴催化剂作用下发现了一种新型\r\n的针状纳米碳材料．用含载体较少的铁催化剂可以得到纯度较高且微观\r\n结构较好的碳纳米管，但产率较低；不含任何载体的纯镍催化剂则不能\r\n得到碳纳米管．适宜的催化剂组成、催化剂活性点的均匀分布和裂解速\r\n度的控制等构成了纳米聚团床大批量制备碳纳米管技术的关键．     

成都中科时代纳米材料事业部

<正>中科时代纳米材料事业部是中国科学院成都有机化学有限公司的直属机构。中科时代纳米自1996年开展天然气催化裂解法制备碳纳米管以来,得到了中国科学院院长基金、中国科学院知识创新工程项目、国家"863"计划纳米材料专项及国家重大科学研究计划课题等多个科研计划的支持,在碳纳米管制备和应用方面取得一系列重要成果,为多壁碳纳米管产品国家标准起草单位之一。截止2013年底,中科时代纳米申请中国发明专利39项,获授权专利12项,发表SCI文章80余篇。     

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.     

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.     

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.     

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.