酚醛树脂包覆氧化天然石墨作为锂离子电池负极材料

天然石墨经过浓硫酸氧化处理,酚醛树脂包覆并高温碳化后形成具有核壳结构的碳包覆氧化天然石墨复合材料.采用扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线衍射(XRD),激光显微拉曼光谱(Raman)等检测技术对氧化处理以及酚醛树脂热解碳包覆前后天然石墨材料的结构与形貌进行分析与表征.结果表明,氧化处理与适量的酚醛树脂热解碳包覆有效修复了天然石墨表面的一些缺陷结构,使其表面更为光滑.电化学测试结果显示,经过氧化处理与酚醛树脂热解碳包覆后天然石墨材料电化学性能得到明显提高.酚醛树脂包覆量为9%时,复合材料表现出最好的电化学性能,其首次放电比容量为434.0mAh·g-1,40次循环后,放电比容量保持在361.6mAh·g-1,而未经处理的天然石墨放电比容量仅为332.3mAh·g-1.该改性方法有效提高了天然石墨材料的比容量,对其进一步应用具有重要意义.     

锂离子电池酚醛树脂裂解碳负极材料的研究

应用低温 (<10 0 0℃ )裂解商品热固性酚醛树脂制备锂离子电池的碳负极材料 .热重分析和X射线衍射分析表明该碳材料具有非晶态聚并苯结构 .随着热解温度的提高 ,其结构逐渐规整 ,首次充放电容量下降 .热解碳材料的比容量取决于热解温度 ,并与可贮锂的纳米孔有关 .     

多孔酚醛树脂热解碳材料的制备与结构

用苯酚和甲醛在氨水催化下合成了可溶性酚醛树脂, 经掺杂不同质量比发泡剂(氯化锌)后在惰性气氛下进行热裂解(500～900 ℃), 制备了多孔热解碳导电材料(PPAS); 用FTIR, XRD, TG, SEM, BET等方法对所制备材料进行了结构表征, 详细讨论了发泡剂的加入对热解碳导电材料结构和性能的影响. 研究发现: 酚醛树脂经掺杂一定量发泡剂后再进行热裂解, 一方面加快了酚醛树脂分子间的脱水速度, 降低了热裂解温度范围; 另一方面, 裂解产物内部结构的微晶尺寸和层间距发生了明显变化, 未掺杂发泡剂的裂解产物呈现尖锐棱角的无定形结构, 而掺杂发泡剂的裂解产物则为多孔的球形和椭球形结构; 表面吸附实验测试结果表明, 当酚醛树脂与发泡剂的质量比为1∶3, 升温速率为30 ℃/h, 热裂解温度为600 ℃时, 热裂解产物的比表面积可达2150 m2&#8226;g－1, 平均孔径在11 Å左右.     

硅藻土辅助制备有序介孔碳及其电催化性能

以共聚物F127 为软模板, 酚醛树脂为碳源, 引入硅藻土充当暂态支架, 在不同硅藻土与酚醛树脂质量比下, 用蒸发自组装法合成有序介孔碳材料. 利用XRD, TEM, N₂ 吸附-脱附对其结构进行表征, 结果显示, 与单一软模板相比,在硅藻土辅助下获得的介孔碳材料不仅具有高度有序的孔道, 还具有更大的比表面积(717～773 m²·g^-1)和孔径(3.9～11.3 nm). 依据原料比例与介孔碳结构两者间的变化规律, 初步探讨了硅藻土在制备中所起的辅助作用. 采用微波多元醇还原法制备介孔碳载Pt 电催化剂, 在甲醇溶液中进行循环伏安测试, 发现比表面积的增大有利于碳材料的电催化性能提高, 当硅藻土与酚醛树脂的比例为0.5 时, 制备出的有序介孔碳比表面积最大, 载Pt 后呈现的正向氧化峰电流也最大.     

高温下煤焦的碳微晶及孔结构的演变行为

以贵州煤为原料,在热解温度950℃~1400℃制备了各种慢速和快速热解焦,主要对高温热解过程中煤焦的碳微晶和孔结构的演变行为进行了研究,同时也研究了高温气化过程中煤焦的孔结构变化规律。结果表明,慢速热解焦和快速热解焦的C和H含量明显不同;随热解温度的升高,煤焦的碳微晶结构向有序化方向发展,但慢速热解煤焦比快速热解煤焦的"石墨化"程度大;快速热解煤焦的微孔比表面积和微孔容积明显高于慢速热解煤焦,即快速热解煤焦的孔隙结构明显比慢速热解煤焦发达;在气化反应初期,煤焦的微孔比表面积下降,微中孔比表面积增加,反应后期煤焦的总比表面积快速下降。     

锂离子电池负极硅-热解碳-石墨复合材料的制备及性能

以沥青为碳前驱物,通过加热分解法制备了具有不同热解碳含量的硅-热解碳-石墨复合材料,并测试及分析了材料的形貌、结构及电化学性能。结果表明,沥青质量在320～560℃的温度区间内迅速减小,沥青质量的减小是由于氢元素的去除。经过高温分解制得的热解碳与沥青的质量比率为65%。在硅-热解碳-石墨复合材料中,硅颗粒分散在石墨表面,热解碳覆盖在硅颗粒表面,热解碳增强了硅颗粒与石墨间的界面结合力。适当含量的热解碳增大了复合材料的放电比容量且改善了循环稳定性;过量的热解碳不能进一步提升复合材料的放电容量。     

溶胶-凝胶法合成β-SiC超细粉末

引言目前文献报道的溶胶法合成β-SiC超细粉末多以TEOS(Si(OC_2H_5)_4)和/或PTES(C_6H_5Si(OC_2H_5)_3)等有机硅和碳的化合物为原料,经溶胶-凝胶过程制SiC先驱体,然后在惰性气氛中热解合成.由于所用原料价格较贵,制备出的SiC粉末成本高,难以实现工业化生产.本文旨在探讨采用廉价硅源来制备β-SiC超细粉末的可行性,以加速我国SiC高技术材料的研究和应用.     

Co@N-石墨烯/C催化甲苯衍生物氧化胺化研究

核壳结构纳米催化剂的发展一直备受化学家的关注.我们通过热解碳担载乙酸钴和1,10-菲哕啉复合物制备出具有核壳结构的氮掺杂石墨烯包裹钴催化剂,并对其进行了系统的表征和催化性能研究.研究发现,该催化剂在TBHP和H2共存的条件下,在催化硝基苯和甲苯的选择性还原-氧化胺化合成N-烷基化胺反应中展现出较好的催化性能和良好的官能团耐受性.透射电镜表征表明氧化钴纳米颗粒被厚度约1.12～1.87 nm的含氮石墨烯壳包裹.X射线光电子能谱表征发现壳层中的石墨烯氮和作为核的氧化钴纳米颗粒间具有较明显的相互作用.我们对催化体系的普适性以及反应机理也进行了较为系统的研究.     

Co@N-石墨烯/C催化甲苯衍生物氧化胺化研究（英文）

核壳结构纳米催化剂的发展一直备受化学家的关注.我们通过热解碳担载乙酸钴和1,10-菲啰啉复合物制备出具有核壳结构的氮掺杂石墨烯包裹钴催化剂,并对其进行了系统的表征和催化性能研究.研究发现,该催化剂在TBHP和H_2共存的条件下,在催化硝基苯和甲苯的选择性还原-氧化胺化合成N-烷基化胺反应中展现出较好的催化性能和良好的官能团耐受性.透射电镜表征表明氧化钴纳米颗粒被厚度约1.12~1.87 nm的含氮石墨烯壳包裹.X射线光电子能谱表征发现壳层中的石墨烯氮和作为核的氧化钴纳米颗粒间具有较明显的相互作用.我们对催化体系的普适性以及反应机理也进行了较为系统的研究.     

碳热还原制备不同形貌的碳化硅纳米线

以酚醛树脂为碳源，正硅酸乙酯为硅源，硝酸镧和表面活性剂为调控剂，通过溶胶-凝胶和碳热还原反应制备了不同形貌的碳化硅纳米线。采用X射线衍射、扫描电子显微镜、透射电子显微镜和X射线散射能谱对所制备的碳化硅纳米线进行表征。结果表明，通过此方法所制备的碳化硅纳米线均为立方结构的β-SiC，分别具有直线状、竹节状和链珠状、分枝状等不同形貌。金属催化剂和表面活性剂对碳化硅纳米线的结构和形貌变化有重要影响。     

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.