聚苯胺纳米纤维的共溶剂界面聚合及储能性能研究

本文采用以盐酸溶液为水相、四氯化碳为有机相的界面聚合法,通过向水相中分别引入具有非对称结构的甲醇和乙醇,以及具有对称结构的异丙醇和丙三醇作为共溶剂,成功制备出聚苯胺纳米纤维.采用场发射扫描电镜、紫外可见光谱和傅里叶红外光谱对其形貌和结构进行了表征分析,并通过循环伏安测试、恒流充放电测试和交流阻抗测试着重研究了不同共溶剂...     

静电纺丝法制备纤维素纳米纤维的研究进展

纤维素纳米纤维很好的结合了纤维素的重要属性和纳米材料的各项特性,但纤维素大分子之间存在大量氢键,使得纤维素较难溶于普通溶剂,导致通过静电纺丝法直接制备纤维素纳米纤维具有一定的难度.而先采用静电纺丝法制备纤维素衍生物纳米纤维,再对纤维素衍生物纳米纤维进行水解也是制备纤维素纳米纤维的一种有效方法.本文对近年来这两种纤维素纳米纤维制备方法的研究进行了综述,并对静电纺制备纤维素纳米纤维的发展前景做出了展望.     

纳米纤维制备工艺进展及其对壳聚糖的适用性分析

壳聚糖是一种性质独特、可生物降解及生物相容的海洋多糖,以其为原料制备的纳米纤维目前已经得到了广泛应用.传统的壳聚糖纳米纤维/纳米复合纤维制备方法主要采用湿法纺丝与静电纺丝,但是这些方法通常需要复杂的过程和挥发性有机溶剂的参与,安全性较低.为了探寻更简单、更安全的壳聚糖纳米纤维制备方法,本文综述了6种最新颖的纳米纤维制备过程,这些过程被分为"由小到大捆绑"与"从大到小粉碎"两大类."由小到大捆绑"包含各种纺丝(例如离心甩丝法、手纺法、溶液吹喷法)和两种冷冻铸造(直接冷冻干燥法和射流急速冷冻法),而"从大到小粉碎"则以星爆系统法为例.我们从纤维直径、纤维取向与对壳聚糖的适用性的角度对比讨论了它们各自的优缺点并融合了每种方法给予的灵感,提出了一种全新的"超声喷雾结合冷冻铸造"的壳聚糖纳米纤维制备理念.超声喷雾与冷冻铸造相结合的方法彻底摆脱了挥发溶剂的使用.以这种安全性较高的新方法制备出的壳聚糖纳米纤维在生物医学工程与食品科学工程领域具有广阔的应用潜能.     

聚乳酸-聚己内酯复合纳米纤维支架的制备和表征

在二氧六环/乙醇溶剂体系中,采用凝胶抽提相分离法制备了聚乳酸-聚己内酯(PLLA-PCL)复合纳米纤维支架,研究了凝胶温度、聚合物比例、聚合物浓度、致孔剂及二氧六环/乙醇(溶剂/非溶剂)比例对复合纳米纤维支架结构与性能的影响.结果表明,当凝胶温度处于-20~-10℃,PCL含量为30%~50%,非溶剂含量不超过15%,致孔剂与溶质质量比不超过20∶1时,均能得到具有类似于天然细胞外基质的纳米纤维(50~500 nm)结构的PLLA-PCL复合纤维支架.随着PCL含量的增加,复合纤维支架的弹性模量减小;PCL含量为30%时,复合支架的相容性和结晶性最好.该复合纤维支架具有良好的生物活性和一定的降解性能.     

β-环糊精功能化聚丙烯腈纳米纤维的制备及对亚甲基蓝的吸附性能

以N,N-二甲基甲酰胺(DMF)为溶剂,利用静电纺丝法制备了聚丙烯腈(PAN)/β-环糊精(β-CD)纳米纤维.通过场发射扫描电镜、红外光谱和粉末XRD对纳米纤维进行了表征,并检测了纺丝溶液的电导率和黏度.结果表明,β-CD的添加量可以改善纳米纤维的形貌,固定在纤维上的β-CD保留了空腔结构,为其在纳米纤维中发挥超分子...     

仿生分级结构NiO纳米线/纳米纤维的可控制备及光催化性能

采用静电纺丝技术和"自下而上"的溶液相自组装技术, 制备了具有仿生主次分级结构的三维NiO纳米线/纳米纤维. 采用扫描电子显微镜(SEM)、 X射线衍射仪(XRD)和比表面积分析仪分别对其形貌、 晶型和孔结构进行了表征. 以水体中的有色染料亚甲基蓝为模型污染物, 研究了分级结构NiO纳米线/纳米纤维的光催化性能. 结果表明, 在180 min内, 以分级结构NiO为催化剂时, 亚甲基蓝的降解率达到了97%, 分别是以纳米纤维和纳米粒子为催化剂时的1.24倍和2.16倍.     

Y掺杂的ZnO纳米纤维材料的制备及其气敏传感器作用机理

采用静电纺丝法成功制备了Y掺杂的ZnO纳米纤维.并通过X射线衍射(XRD),扫描电子显微镜(SEM),能量色散X射线(EDX),透射电子显微镜(TEM)以及热重差热分析(TG-DTA)等手段对样品的结构和形貌进行了表征分析.同时用纯的ZnO和Y掺杂的ZnO纳米纤维制备了传感器,对浓度为(1-200)×10^-6 (体积分数)丙酮的气敏特性进行了测试分析.测试结果表明,可以通过简单控制纳米纤维中Y的含量,来微调该传感器的气敏特性.同时也发现通过Y掺杂, ZnO纳米纤维对丙酮的气敏特性有所改善,表现出很高的响应.纯ZnO和Y掺杂ZnO制成的传感器对几种潜在干扰气体表现出良好的选择性,比如氨气、苯、甲醛、甲苯以及甲醇.本文最后也讨论了该传感器的气敏作用机理.     

尼龙6纳米纤维膜固相膜萃取-高效液相色谱法测定塑料瓶装矿泉水中双酚A

采用静电纺丝法制备尼龙6纳米纤维膜,结合固相膜萃取-高效液相色谱法测定了矿泉水中的双酚A。对洗脱溶剂及其体积、进样速度、样品体积、样品pH值、尼龙6纳米纤维膜的用量、及其活化方式和使用次数等影响因素进行了研究。结果表明:10mL样品调至pH8.0后,以3mL/min流速通过1.5mg尼龙6纳米纤维膜,300μL甲醇即可将膜上吸附的双酚A完全洗脱,每张膜至少可重复使用6次。在此最优化条件下,方法的线性范围为0.20～20.0μg/L;检出限为0.15μg/L,膜内和膜间的相对标准偏差均小于4.5%(n=6)。本方法应用于6种不同品牌的矿泉水中双酚A的分析测定,在1.0μg/L加标水平下,测得回收率为95.0%,双酚A测得浓度低于0.30μg/L。与固相萃取方法相比,本方法高效、环保,表明尼龙6纳米纤维膜是极具潜力的萃取介质     

静电纺丝中空纳米纤维在催化领域的应用

更大的比表面积、更丰富的界面组成及更高效的传质路径是构筑多元催化体系,实现催化剂效率提升的关键.中空纳米纤维具有的多元空腔结构赋予其比表面积和界面组成上广阔的调变空间,使其成为制备高效异相催化剂的理想平台.静电纺丝技术的发展为中空纳米纤维的可控制备提供了更简易高效的方法,促进了中空纳米纤维的结构创新和应用扩展.本文从构筑策略、结构特点及结构与性能的对应关系3个角度总结了基于静电纺丝法制备的不同组成和形态的中空纳米纤维材料在催化领域(包括光催化、电催化、热催化)应用中的独特优势.首先展示了创新的静电纺丝方法结合后续工艺制备的中空纳米纤维的不同结构形态,然后梳理了基于中空纳米纤维构筑高效催化剂的研究进展,最后展望了中空纳米纤维在催化领域应用的未来发展趋势,以期为高效异相催化剂的设计提供有益的参考.     

静电纺制备丝素蛋白纳米纤维及其复合纳米纤维的研究进展

将生物材料通过静电纺丝制备成的纳米纤维,具有比表面积大、空隙率高、生物相容性好等优点,因此得到广泛研究。本文主要综述了近年来国内外静电纺丝制备丝素蛋白纳米纤维的研究现状,重点介绍了采用不同溶剂制备的纯丝素蛋白纳米纤维和丝素蛋白与其它材料复合制备的丝素蛋白复合纳米纤维,并展望丝素蛋白纳米纤维潜在的应用前景。     

Self-assembled aggregates of amphiphilic perylene diimide-based semiconductor molecules: effect of morphology on conductivity

Two amphiphilic perylenetetracarboxylic diimide derivatives modified with different side chains at imide nitrogen, N-n-hexyl-N'-(2-hydroxyethyl)-1,7-di(4'-t-butyl)phenoxy-perylene-3,4:9,10-tetracarboxylic diimide (PDI 1) and N,N'-di(2-hydroxyethyl)-1,7-di(4'-t-butyl)phenoxy-perylene-3,4:9,10-tetracarboxylic diimide (PDI 2), were fabricated into organic nanostructures via solution-phase self-assembly. Their self-assembling properties in methanol and n-hexane have been comparatively studied by electronic absorption, fluorescence, and Fourier transform infrared spectroscopy (FT-IR). The morphologies and structures of the self-assemblies were examined by scanning electronic microscopy (SEM), atomic force microscopy (AFM), as well as X-ray diffraction (XRD) techniques. The conducting properties were evaluated by current-voltage (I-V) measurements. Due to the presence of different number of hydroxyethyl groups in the molecule of PDI 1 and PDI 2, the self-assembly of the two molecules in methanol and n-hexane results in nanostructures with distinctly different morphology as follows: nanobelts and nanoleaves for PDI 1 and nanobelt dendrites and nanosheets for PDI 2, respectively. Analysis of the spectral change for the aggregates relative to that of monomeric PDI in solution revealed that in polar and apolar solvents, both nanobelts and nanoleaves precipitated from PDI 1 adopt the H aggregation mode, whereas nanobelt dendrites and nanosheets from PDI 2 adopt H and J aggregation mode, respectively, implying the effect of both side-chain substituent and solvent on tuning the intermolecular stacking. Furthermore, the conductivity of the aggregates of either PDI 1 or PDI 2 from methanol is more than ca. 1 order of magnitude higher than those from n-hexane. In particular, the well-defined, one-dimensional (1D) nanobelts of PDI 1 show excellent semiconducting property with the electrical conductivity as high as 3.3×10(-3) S cm(-1), which might serve as promising candidates for applications in nano-electronics.     

Tubular or subsurface morphology of octabutoxyphthalocyanine upon self-assembly in polymer matrices: effect of the casting solvent

Spontaneous phase-separated, controlled aggregate structures of photo- and electroactive molecules in polymer matrices are of interest for device fabrication. We show that the self-assembly of octabutoxyphthalocyanine (Pc) in polymer matrices leads to tubular morphology of Pc when the film is prepared with tetrachloroethane (TCE) and subsurface droplet morphology with chloroform. The same morphology is seen with both bisphenol A polycarbonate (BPAPC) and poly(methyl methacrylate) (PMMA) as the matrix. The subsurface morphology results from the rapid association of Pc in the polymer matrix, as the film forms. With the tubular morphology in the films prepared with TCE, percolation threshold is reached with a concentration of Pc as low as 3% (wt) in the polymer. Such phase-separated self-assembly occurs, without any annealing of the films. Even in the absence of the polymer, Pc crystallized from TCE also shows tubular morphology, whereas it exhibits a columnar morphology with chloroform. X-ray diffraction of Pc crystallized from either solvent shows the columnar stacking of the Pc molecules. However, the morphology is tubular when TCE is used. We attribute the difference in the morphology to the higher viscosity of TCE and the diffusion-limited growth, which causes the tubular morphology, whereas the instantaneous self-assembly in less-viscous chloroform leads to droplets. The solvent effect observed here could be used to tailor the morphology of such photoconductive molecules in polymer matrices.     

Self-assembly morphology and packing structures depend on the ‘head’ of organic cations anchored on polyoxometalate anions in hybrids

Two organic-polyoxometalates (organic-POMs) hybrids were constructed by fan-shaped 1-methyl-3-[3, 4, 5-tris(octadecyloxy) benzyl]imidazolium salts (labelled as I–Cl) and triethyl-[3, 4, 5-tris (octadecyloxy) benzyl] ammonium salts (labelled as Q–Cl) and Keggin anions [SiW₁₂O₄₀]^4? by electrostatic interaction. Self-assembled behaviours of two aggregates in organic solvent and solid state were investigated in detail by scanning electron microscopy, transmission electron microscopy and X-ray analysis. The mixed solution of chloroform–methanol or chloroform–acetone provided the stable environment for aggregates and aggregates showed a uniform micron size. X-ray analysis results showed that flower-like aggregates morphology of I₄[SiW₁₂O₄₀] based on imidazole ring as ‘head’ in organic cations was formed by the stacking of multilamellar discs and kept the lamellar structure in solid state. Bulk thorn spheres appeared in Q₄[SiW₁₂O₄₀] aggregates, which were formed by closely interspersed of lots flatted blocks with hexagonal structure characteristics in solid state. The comprehension for the self-assembly morphology and solid structure of organic-polyoxometalate hybrids would help us to use easily modified organic moiety and functional inorganic polyoxoanions as blocks to build novel and giant supramolecular architecture.     

Controlling chemical self-assembly by solvent-dependent dynamics

The influence of the ratio between poor and good solvent on the stability and dynamics of supramolecular polymers is studied via a combination of experiments and simulations. Step-wise addition of good solvent to supramolecular polymers assembled via a cooperative (nucleated) growth mechanism results in complete disassembly at a critical good/poor solvent ratio. In contrast, gradual disassembly profiles upon addition of good solvent are observed for isodesmic (non-nucleated) systems. Due to the weak association of good solvent molecules to monomers, the solvent-dependent aggregate stability can be described by a linear free-energy relationship. With respect to dynamics, the depolymerization of π-conjugated oligo(p-phenylene vinylene) (OPV) assemblies in methylcyclohexane (MCH) upon addition of chloroform as a good solvent is shown to proceed with a minimum rate around a critical chloroform/MCH solvent ratio. This minimum disassembly rate bears an intriguing resemblance to phenomena observed in protein unfolding, where minimum rates are observed at the thermodynamic midpoint of a protein denaturation experiment. A kinetic nucleation-elongation model in which the rate constants explicitly depend on the good solvent fraction is developed to rationalize the kinetic traces and further extend the insights by simulation. It is shown that cooperativity, i.e., the nucleation of new aggregates, plays a key role in the minimum polymerization and depolymerization rate at the critical solvent composition. Importantly, this shows that the mixing protocol by which one-dimensional aggregates are prepared via solution-based processing using good/poor solvent mixtures is of major influence on self-assembly dynamics.     

制备溶剂对NiCoB非晶态合金催化剂结构及糠醛加氢性能的影响

采用化学还原法在不同单一和复配溶剂体系中制备了一系列NiCoB非晶态合金催化剂,对其液相糠醛加氢性能进行了考察,并采用N_2吸附-脱附等温线、ICP、FE-SEM、HRTEM、XRD、XPS等手段进行了表征。结果表明,在相同反应条件下,制备溶剂的表面张力、黏度、极性大小和溶解度常数等对NiCoB非晶态合金催化剂的组成、形貌和结构及其糠醛加氢反应性能均产生重要影响。由甲醇/乙二醇复配溶剂(MEG,体积比1∶1)制备的NiCoB-MEG催化剂具有最理想的糠醛液相加氢制糠醇性能,糠醛转化率达到96.4%,糠醇选择性达到83.49%,这可归因于甲醇和乙二醇之间的协同作用促进了金属组分的分散和还原。     

α-含氧取代酞菁的聚集性质研究

以3-硝基邻苯二腈为原料分别与苯酚和甲醇反应合成3-苯氧基邻苯二腈和3-甲氧基邻苯二腈, 这些α-取代的邻苯二腈以二甲氨基乙醇为溶剂, 在有无醋酸锌条件下环合, 分别形成α-四苯氧基锌酞菁、α-四苯氧基无金属酞菁、α-四甲氧基锌酞菁、α-四甲氧基无金属酞菁, 对产物结构进行了表征. 光谱分析结果表明, 此类锌酞菁在氯仿等非配位溶剂中能自发形成J型聚集体, 其Q带出现一个红移吸收带, 经UV-Vis光谱、荧光光谱及MALDI-TOF质谱分析表明, 该聚集体的形成机理为基于酞菁分子间的锌-氧自配位相互作用.     

Tuning the morphology of amphiphilic copolymer aggregates by compound emulsifier via emulsion–solvent evaporation

A series of poly(4-vinylpyridine)-b-poly{6-[4-(4-butyloxyphenylazo)phenoxy]hexyl methacrylate} (P4VP-b-PAzoMA) were employed to fabricate aggregates via the emulsion–solvent evaporation method. The emulsion was stabilized by compound emulsifier composed of SDS and span60. By tuning the ratio of two emulsifiers, P4VP-b-PAzoMA could self-assemble into various morphologies including porous microspheres, tremella-like aggregates, bowl-like aggregates and wrinkled microspheres. The transformation of the morphologies could be ascribed to three major aspects: the stability of emulsified chloroform droplets, the permeation of water into chloroform and the dispersity of the interior water droplets with regard to different HLB values. Besides, the morphology could even be tuned by changing the block ratio and the concentration of P4VP-b-PAzoMA, and the HLB dependent morphology changing was also proved within other block ratio or different concentration. The study uncovers a convenient and effective technique to manipulate the morphology of amphiphilic copolymer aggregates.     

Oleophilic ion-exchange resins. IV. Swelling of quaternary ammonium polymers in mixed solvents

The swelling characteristics of an oleophilic anion-exchange resin in methanol–benzene and ethanol–chloroform mixed solvent systems were compared with those of a conventional anion-exchange resin. The oleophilic resin was prepared by amination of chloromethylated polystyrene 1% DVB with N,N-dimethyldodecylamine. It showed a large shift of the swelling peak from polar to less polar solution compositions in both methanol–benzene and ethanol–chloroform systems as compared with the swelling of conventional resins. Total solvent uptake and solvent distribution between resin and solvent phases were also determined. The less polar solvent (benzene or chloroform) was sorbed preferentially by the oleophilic resin over a wide range of composition, while preference for the more polar solvent (methanol or ethanol) by the conventional resin was shown over the entire composition of the mixed solvent systems. The Newman-Krigbaum treatment of mixed solvents was applied to swelling data on the ethanol–chloroform–oleophilic resin system, where the volume of the gel network plus the solvent imbibed was relatively constant over the entire range of composition. The result suggests a strong similarity of the liquid–liquid interaction terms in this gel phase compared with those in the pure binary liquid phase.     

Self-assembly behavior of carbon nanotubes modified by amphiphilic block copolymer

Block copolymers of poly(tert-butyl methyacrylate) (PtBMA) and polystyrene (PSt) were grafted onto multi-walled carbon nanotubes (MWNTs) by the reaction of azide groups at the copolymer chain end with the surface of MWNTs. After hydrolysis, PtBMA block was transformed to polymethyacrylic acid (PMAA) block, and amphiphilic diblock copolymer-modified MWNTs were finally obtained. The modified MWNTs were characterized by XPS, TGA, FTIR, and Raman, and the results showed that the amphiphilic diblock copolymers were grafted onto MWNTs by the covalent bond. The TEM and SEM observation showed that PMAA-b-PSt copolymer modified MWNTs (S2) formed self-assembly tube bundles with the size up to 20 μm in both ethanol and chloroform. However, PtBMA-b-PSt copolymer modified MWNTs (S1) only formed small-size aggregates or dispersed as single-modified MWNTs. The dispersion stability tests showed that S1 had good dispersion stability in several solvents (water, ethanol, acetone, and chloroform) even after 20 days. Due to the big-size tube bundles formed by self-assemble S2, the dispersion stability of S2 in above all solvents decreased, but it was still much better than that of pristine MWNTs.     

Self-assembled helical nanostructures from an asymmetrical perylene diimide

An asymmetrical perylene diimide 3, N-（4-methoxyphenyl）-N＇-（4-nitrophenyl）-perylene-3,4,9,10-tetracarboxylic diimide, was synthesized, and its self-assembly and dissociation behaviors in chloroform was studied in detail by UV-vis and fluorescence spectroscopies. The resulting unique helical nanostructures from 3 were proposed to be self-assembled via the cooperative actions of π-π stacking, steric hindrance and electrophile-nucleophile type pairing.