The Research Progress of Polymer/Graphene Nanocomposites

石墨烯以其优异的力学、光学、电学和热学性能,得到日益广泛的关注和研究。本文介绍了石墨烯的结构、性能和特点,并对石墨烯的改性方法进行了概括。本文着重综述了高分子／石墨烯纳米复合材料的研究现状和进展,并介绍了高分子／石墨烯纳米复合材料的三种制备方法,即原位插层聚合法、溶液插层法和熔融插层法。此外,还对高分子／石墨烯纳米复合材料的应用前景进行了展望,并对石墨烯复合材料研究存在的问题和未来的研究方向进行了讨论。     

生物高分子-氧化石墨烯三维多功能复合凝胶的制备及其血液净化性能

以生物高分子(壳聚糖、白蛋白、脱氧核糖核酸)为交联剂与氧化石墨烯片层进行三维自组装,冻干后得到生物高分子-氧化石墨烯复合凝胶。通过扫描电镜、原子力显微镜、纳米粒度分析仪等分析其物化性能。结果表明:生物高分子成功组装到氧化石墨烯片层上,并形成三维多孔结构,制备的凝胶显示出极好的血液相容性,有效抑制了红细胞的溶血现象,对阳离子毒性分子及重金属离子有较高的吸附量。     

静电纺丝技术制备聚苯乙烯/石墨烯复合纳米纤维

通过静电纺丝技术制备了聚苯乙烯/石墨烯复合纳米纤维膜,利用扫描电子显微镜、傅里叶变换红外光谱、粉末X-射线衍射和激光拉曼光谱等技术对所制备的纤维膜结构和组成进行表征,并通过电化学法考察该复合纳米纤维膜的电活性。结果表明,石墨烯已掺杂到聚苯乙烯纤维中。与聚苯乙烯纤维膜相比,聚苯乙烯/石墨烯复合纳米纤维膜导电性能增强,表明本实验成功实现了对聚苯乙烯纤维的改性。     

TiO2/石墨烯复合材料的光生电荷分离调控与光催化产氢性能研究

半导体光生电荷分离是光催化过程中的关键步骤之一,其效率极大地影响了最终光催化性能.将TiO₂纳米片与石墨烯复合,能够促进TiO₂中光生电子和空穴的分离,从而提高其光催化活性.为了研究光生电荷的分离对TiO₂/石墨烯复合材料光催化性能的影响,通过调控TiO₂纳米片的尺寸来调节TiO₂/石墨烯复合材料中光生电荷分离的能力,然后研究其对TiO₂/石墨烯复合材料光催化性能的影响.合成了一系列不同厚度的TiO₂纳米片,将其与石墨烯复合,并通过光沉积负载Pt纳米颗粒作为助催化剂,用于光催化产氢.实验结果显示,随着TiO₂纳米片厚度减小,其与石墨烯形成的复合结构的光催化性能显著提高.这主要是由于TiO₂纳米片厚度减小时,光生电子沿厚度方向穿过TiO₂纳米片迁移到石墨烯的距离缩短,从而减少了光生电子在迁移过程中与空穴的复合;同时TiO₂纳米片厚度减小使其比表面积增大,使得TiO₂/石墨烯界面面积增大,从而使石墨烯更好地分离出TiO₂中的光生电子,有更多的光生电子到达石墨烯参与催化反应,提高TiO₂/石墨烯复合材料的光催化性能.此研究表明通过控制TiO₂纳米片的尺寸来调控TiO₂/石墨烯复合材料中光生电子和空穴的分离,是显著提高其光催化性能的有效途径.     

氧化石墨烯/金银纳米粒子复合材料的制备及其SERS效应研究

近年来,氧化石墨烯/金银纳米粒子复合材料由于其优异的表面增强拉曼散射（SERS）性能引起了人们极大的关注,在污染物检测、化学传感和癌症诊断等领域具有重要的应用价值。本文综述了氧化石墨烯片层上修饰金银纳米粒子、氧化石墨烯包覆金银纳米粒子、氧化石墨烯附着在金银纳米粒子层三种氧化石墨烯/金银纳米粒子复合材料的制备方法,对其SERS效应进行了详细介绍。SERS研究表明,结合了金银纳米粒子与氧化石墨烯两种材料各自在SERS研究与应用中的优势,氧化石墨烯/金银纳米粒子复合材料的SERS性能比单纯金银纳米粒子更加优异。氧化石墨烯在其中起到了化学增强、分子富集、钝化保护、荧光猝灭的重要作用。氧化石墨烯/金银纳米粒子复合材料在表面增强拉曼光谱中具有广阔的应用前景。     

层状仿生高分子纳米复合材料

自然界中,鲍鱼壳具有有机-无机多级次层状结构以及大量的复合界面作用,力学性能优异。这一独特的层状结构主要由霰石碳酸钙片层构成,并通过体积分数约为5%的生物高分子在层间进行粘合。受鲍鱼壳这一微观结构的启发,我们利用不同的基元材料如纳米蒙脱土、碳纳米管以及氧化石墨烯等构筑仿鲍鱼壳层状结构,并结合多种界面设计,实现不同界面、不同基元材料之间的协同作用,得到了力学性能优异的高分子纳米复合材料。仿生高分子纳米复合材料的成功制备,为今后的研究提供了崭新的思路,拓宽了高分子纳米复合材料的应用前景。     

锗酸锌纳米棒@石墨烯复合负极材料的制备及储锂性质

以二氧化锗和二水合醋酸锌为原料,采用水热法制备了锗酸锌纳米棒,并将其与氧化石墨烯复合,制备了石墨烯包覆的锗酸锌纳米棒三维复合材料. SEM等测试表明,锗酸锌纳米棒均匀地穿插在石墨烯片中,阻止了石墨烯片之间相互堆垛,而石墨烯片层之间相互连接,形成三维的空间导电网络,提高了材料的电子导电性.电化学测试表明,石墨烯片作为稳定的框架,能够有效缓冲活性物质在脱嵌锂过程中产生的体积变化,在500 mA·g^-1电流密度下循环190次后, Zn₂GeO₄@RGO复合材料的嵌锂容量仍有1189.5 mAh·g^-1;在3.2 A·g^-1的大电流密度下,嵌锂容量达到449.5mAh·g^-1,表明该复合材料具有优异的长循环稳定性和良好的倍率性能.     

微波辅助仿生矿化增强石墨烯与聚乳酸的界面相互作用

石墨烯纳米片在提高聚乳酸(PLA)复合材料力学性能和气体阻隔性能等方面具有良好的应用前景,但通常在不同程度上受限于较差的界面相互作用.本文通过高效且环境友好的微波辅助水相仿生矿化方法,在石墨烯纳米片表面直接生成高结晶度、高结构规整度的羟基磷灰石纳米晶须,获得了具有良好分散性和界面结合力的仿生矿化石墨烯(BMGr)纳米杂化体.将BMGr纳米杂化体均匀分布于聚乳酸纤维表面,通过受限成型(60℃,3 MPa)获得了具有强界面结合的复合薄膜,大幅提高了力学性能.值得强调的是,BMGr增强聚乳酸复合薄膜的拉伸强度、杨氏模量和拉伸韧性分别达到22.6 MPa,199 MPa和6.6 MJ/m³,是纯PLA纤维膜的6.46,3.75和8.25倍.本文不仅发展了有效修饰石墨烯纳米片的技术路线,更为制备高强度高韧性的聚乳酸复合材料并阐述其结构-性能关系提供了研究思路.     

石墨烯/高分子复合薄膜的制备及应用

石墨烯是一种单原子厚度的二维碳纳米材料,具有优异的光、电、热和力学性能,以及巨大的比表面积.石墨烯与高分子之间能够通过共价或非共价作用(氢键、π-π作用、静电作用等)进行复合.这些相互作用既增加了石墨烯在高分子中的溶解性或分散性,也可以提高复合材料的性能或拓展其功能.目前常用的制备石墨烯高分子复合材料的方法有溶液混合、熔融共混和原位聚合等.该类复合材料可以通过蒸发溶剂、溶液涂覆、真空抽滤、层层自组装等途径加工成相应的复合膜.石墨烯高分子复合薄膜在制备高强度结构材料、超级电容器、光伏器件、锂离子电池负极材料以及传感器等方面具有重要的应用价值.本文综述了近年来石墨烯高分子复合薄膜的制备和应用方面的研究进展,并对该领域进行了展望.     

仿鲍鱼壳石墨烯多功能纳米复合材料

石墨烯具有力学性能高、电导率优异等特点,然而单层石墨烯纳米片在组装成为宏观纳米复合材料的过程中,往往会出现片层团聚、界面作用弱、无规取向等问题,导致宏观石墨烯纳米复合材料性能远低于单片石墨烯。因此,如何将微观石墨烯纳米片层的高性能在宏观纳米复合材料中体现出来,是目前研究的热点和难点。本专论结合目前石墨烯纳米复合材料的研究现状,简要讨论了受天然鲍鱼壳的“砖-泥”结构的启发,仿生构筑高性能石墨烯纳米复合材料的最新研究进展。并对本课题组在仿鲍鱼壳石墨烯多功能纳米复合材料领域近年来的工作进行介绍,包括石墨烯纤维、薄膜和块材等多种宏观石墨烯纳米复合材料,系统总结构筑仿鲍鱼壳结构和反鲍鱼壳结构两种策略,在一定程度上解决了石墨烯在组装过程中的科学问题。同时,详细阐述了仿鲍鱼壳石墨烯多功能纳米复合材料的增强增韧机制和功能化策略,分析了今后研究工作中可能遇到的问题,并展望了未来的发展趋势。     

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.