一步法制备蒙脱土-石墨烯协同增强聚乙烯醇复合材料

以蒙脱土(MMT)和石墨烯(rGO)为填料,一步法制备了MMT-rGO/PVA纳米复合材料,并研究了不同MMT/rGO比例对PVA复合膜力学性能的影响.结果表明,剥离的MMT片层能够有效阻止石墨烯在被还原过程中的团聚.MMT-rGO二元填料与PVA间形成氢键,极大地改善了填料与聚合物间的界面结合,能够协同提高PVA复合膜的力学性能.1 wt%MMT-GE(2∶1)/PVA复合材料的拉伸强度和杨氏模量最高,分别为85.1 MPa和1627.8 MPa,比纯PVA分别提高了46%和62%.此方法为制备高性能聚合物复合材料提供了有效的途径.     

氧化石墨烯/PMMA和表面官能化的石墨烯/PMMA复合材料的制备及其力学性能的研究

使用简单的溶液共混的方法制备了氧化石墨烯/聚甲基丙烯酸甲酯(GO/PMMA)和表面官能化的石墨烯/聚甲基丙烯酸甲酯复合材料.通过透射电镜(TEM),扫描电镜(SEM)和原子力显微镜(AFM)观察了石墨烯及复合材料的表观形貌.通过拉伸实验表征了其力学性能,研究发现随着石墨烯的加入,其拉伸强度和断裂伸长率都有所改善,而且表面官能化的石墨烯的复合材料的改善效果要优于氧化石墨烯.     

硅烷功能化石墨烯/硅树脂纳米复合材料的制备与表征

先用乙烯基三甲氧基硅烷(A-171)和二甲肼改性并还原氧化石墨烯(GO),制备A-171功能化的石墨烯(FG).研究结果表明A-171与GO上的羟基发生了反应,以共价键连接到了石墨烯的表面;FG能在四氢呋喃中均匀分散并且剥离成厚度约为0.9 nm的单一片层,其干燥后表面呈褶皱状.然后将FG与双组分硅树脂用溶液共混法制备了FG/硅树脂纳米复合材料.运用X射线衍射、扫描电子显微镜、动态热机械分析、拉伸试验等手段分析了复合材料的形态与性能,结果表明,与未处理过的石墨烯相比,FG在复合材料中有更好的分散和更强的界面作用.含0.5 wt%FG的复合材料的拉伸强度较硅树脂提高了87.7%,玻璃化温度提高了23.9℃,失重5%时的温度也提高了20.1℃.     

氧化石墨烯接枝碳纤维新型增强体的制备与表征

利用“Grafting-to”化学修饰法制备氧化石墨烯接枝国产碳纤维新型增强体。利用红外光谱、X射线光电子能谱和原子力显微镜对样品的官能团和表面形貌进行表征;利用接触角测量、单丝拉伸方法研究了接枝前后纤维单丝的润湿性能及拉伸强度,并通过微脱粘法分析了其复合材料的界面剪切强度。结果表明：氧化石墨烯的接枝修饰使国产碳纤维表面粗糙度提高了166%,表面能提高了46.3%,拉伸强度提高了7.8%,复合材料的界面剪切强度提高了111.7%。     

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.     

微波调控石墨烯-碳纳米管协同增强聚氨酯损伤自修复研究

首先采用溶液共混法制备出石墨烯-碳纳米管(G-CNT)/聚氨酯(TPU)复合材料,然后通过拉伸实验及扫描电子显微镜(SEM)表征来考察该材料的拉伸强度和微波自修复特性,并从力学及材料与微波之间的相互作用等角度对其拉伸强度增强和微波修复机理进行研究.结果表明:在拉伸强度方面,与单一的石墨烯或CNT增强TPU相比,G-CNT之间形成的协同效应使TPU拉伸强度得到进一步提高,当石墨烯和CNT的质量比为3∶1时,G-CNT/TPU抗拉强度较纯TPU提高了67%,较G/TPU提高了18%,较CNT/TPU提高了25%;在材料裂纹的微波修复方面,石墨烯和CNT之间的协同效应使TPU材料自修复效果得到有效提高,当石墨烯和CNT的质量比为3∶1时,G-CNT/TPU修复效果达到最高值117%.     

聚甲基乙撑碳酸酯/氧化石墨烯纳米复合材料的制备及性能研究

本文采用改进Hummers法制备氧化石墨烯(GO),通过原子力显微镜对GO片层形貌进行表征;以聚甲基乙撑碳酸酯(PPC)、聚乙烯醇(PVA)和氧化石墨烯(GO)为原料,采用溶液和熔融共混法相结合,制备PPC/PVA/GO纳米复合材料,研究其力学性能、热学性能和动态流变行为。结果表明,当GO含量为0.5 wt%时,拉伸强度达到了22.03 MPa,与纯PPC相比提高了25.8%;当GO含量增大到1.0 wt%时,拉伸强度开始降低;断裂伸长率随GO的加入呈现降低的趋势。GO含量为1.0%时复合材料的热学性能最好,与纯PPC相比,复合材料的完全热分解温度从350℃提高到了400℃以上,并且热分解速率下降了12%/min;复合材料的复数黏度、储能模量和损耗模量随PVA及GO的引入也有一定程度的提高。     

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。     

氧化石墨烯纳米带-碳纳米管/TPU复合材料薄膜的制备及表征

将不同维度纳米填料同时复合,采用纵向氧化切割MWCNTs法制得不同含量比的氧化石墨烯纳米带-碳纳米管(GONRs-CNTs)2种维度纳米材料复合体,随后将上述填料加入到TPU基体中制得GONRsCNTs/TPU复合材料薄膜.采用FTIR、XRD、TG、XPS、TEM和FE-SEM研究了不同反应条件下所得GONRsCNTs复合体的结构及性能,并结合复合材料薄膜的氧气透过率和拉伸测试以及表面形貌观察,研究了GONRs与CNTs的协同作用、二者的含量比对TPU复合材料薄膜阻隔和力学性能的影响.研究表明,GONRs与CNTs的协同效应明显优于MWCNTs,同时当所加GONRs-CNTs复合体中GONRs与CNTs的含量比约为67∶33时,GONRs-CNTs/TPU复合材料薄膜的氧气透过率和拉伸强度相比纯TPU薄膜分别降低51.3%和提高29.3%,阻隔性能和力学性能均得到明显改善.     

石墨烯/铂复合材料的制备及电化学性能研究

采用Hummers法制备氧化石墨,再超声分散于去离子水中形成稳定的氧化石墨分散液。分散液与氯铂酸溶液混合后,氧化石墨烯还原氯铂酸产生大量铂纳米粒子,铂粒子被牢固地锚在氧化石墨烯片上,最后将所得到的氧化石墨烯/铂复合物置于管式炉中在Ar/H2气氛中于800℃下热裂解制备出石墨烯/铂复合材料。形貌与纳米结构分析表明,氧化石墨已被彻底还原成石墨烯,铂纳米粒子均匀分散在褶皱的石墨烯纳米片间。电化学阻抗研究进一步揭示复合材料的电子转移阻抗明显小于石墨烯,呈示铂纳米粒子掺入石墨烯片层大大改善了导电性。石墨烯/铂复合材料应用于对苯二酚的电化学检测,检出限达1.6×10-7mol.L-1,这说明该材料具有优异的电催化性能。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.