Fabrication and electrochemical instrumentation of redox‐active nanofiber mat for polyaniline incorporated with poly(imide sulfonate)

In this study, we demonstrate the fabrication of an electrochemically active nanofiber mat that is a composite of high‐performance poly(imide sulfonate) (PIS) and polyaniline (PANI). First, a nonconductive nanofiber mat comprising nanofibers having diameters of ca. 300 nm was fabricated by the electrospinning of ionomeric PIS in N,N‐dimethylformamide (DMF). Then, the nanofibers were modified using PANI, which was synthesized by the oxidative polymerization of aniline, yielding an electrochemically active nanofiber mat having a diameter of ca. 350 nm. It was confirmed that PANI was successfully incorporated onto the PIS nanofiber mats by X‐ray photoelectron spectroscopy. Subsequently, we conducted electrochemical measurements of the PANI‐modified nanofiber mats using a tailor‐made attachment in which the working electrode gently comes in contact with the nanofiber mat surface. This attachment was observed to be widely useful in the cyclic voltammetry measurements related to redox‐active nanofibers. These observations are expected to contribute to the advancements in application development of the electrochemically active nanofiber mats.     

丙烯腈-衣康酸基纳米纤维纱线的热稳定及碳化研究

碳纳米纤维主要以聚丙烯腈(PAN)作为前驱体,通过纺丝、热稳定、碳化等后处理工艺制备而得.但是,PAN基纳米纤维取向度低、致密性差,热稳定后环化度低,碳化后导电性差等缺点阻碍其在高性能碳纳米纤维领域的发展.因此,在PAN分子链中引入衣康酸(IA),通过溶液聚合法合成了P(AN-co-IA)共聚物并通过静电纺丝法制备了P...     

Carbon Nanofiber–Polystyrene Composite Electrodes for Electroanalytical Processes

Carbon nanofibers provide an active and well‐defined high surface area material for electroanalytical processes. In this study a novel procedure is suggested for compacting carbon nanofiber (CNF) materials (diameter typically 100–200 nm) with a polystyrene (PS) binder and additives into highly conducting and re‐polishable CNF‐PS composite electrodes. Three types of carbon nanofibers (Pyrograf III, 70–200 nm diameter) and a range of compositions are surveyed. A 33 wt% carbon nanofibers in polystyrene electrode provides optimum electrical conductivity and reactivity.     

Characterization of poly(methyl methacrylate) nanofiber mats by electrospinning process

In this study, the aim is to describe the influence of electrospinning parameters on the morphology, the water wetting property and dye adsorption property of poly(methyl methacrylate) nanofiber mats. Specifically, the effects of solution concentration, solvent type, applied voltage, distance between the electrodes and particulate reinforcement on the diameter and shape of the nanofibers were investigated. All poly(methyl methacrylate) nanofiber mats contained beaded nanofiber structures. With increasing the polymer solution concentration, the average fiber diameter also increased. Poly(methyl methacrylate) nanofiber mat electrospun from dimethylformamide solution resulted in thicker fibers when compared with the mat electrospun from acetone solution. Increasing the electric potential difference between the collector and the syringe tip did not increase the average fiber diameter. Besides increasing the distance between the electrodes resulted in a decrease in the average fiber diameter. When compared with PMMA nanofiber mat, thicker fibers were obtained with silica nanoparticles reinforced nanofiber mat. According to the water contact angle measurements, all poly(methyl methacrylate) nanofiber mats revealed hydrophobic surface property. PMMA nanofiber mat with the highest water contact angle gave rise to the highest dye adsorption capacity.     

聚丙烯腈纳米纤维的再细化

通过电纺丝法研究了溶剂种类、溶液浓度、纺丝倾斜角、聚合物分子量对纳米纤维形态和直径的影响,寻找到最佳工艺条件,并得到了平均直径为20nm的超细纤维.     

Fabrication of Electrically Conducting Polypyrrole‐Poly(ethylene oxide) Composite Nanofibers

Summary: Electrically conducting polypyrrole‐poly(ethylene oxide) (PPy‐PEO) composite nanofibers are fabricated via a two‐step process. First, FeCl₃‐containing PEO nanofibers are produced by electrospinning. Second, the PEO‐FeCl₃ electrospun fibers are exposed to pyrrole vapor for the synthesis of polypyrrole. The vapor phase polymerization occurs through the diffusion of pyrrole monomer into the nanofibers. The collected non‐woven fiber mat is composed of 96 ± 30 nm diameter PPy‐PEO nanofibers. FT‐IR, XPS, and conductivity measurements confirm polypyrrole synthesis in the nanofiber.

An SEM image of the PPy‐PEO composite nanofibers. The scale bar in the image is 500 nm.     

A composite polyaniline/graphene–coated polyamide6 nanofiber mat for electrochemical applications

In this study, polyamide6 (PA6) nanofiber mats were fabricated through the electrospinning process. The nanofibers were coated by polyaniline (PANI) using the in situ polymerization of aniline in the presence of graphene oxide. The composite of the PANI/graphene oxide–coated nanofiber mat was treated with hydrazine monohydrate to reduce graphene oxide to graphene, and this was followed by the reoxidation of PANI. Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), wide angle X‐ray diffraction (WAXD), thermal gravimetric analysis (TGA), tensile strength tests, electrical conductivity measurements, cyclic voltammetry (CV), and charge/discharge measurements were conducted on the composite PA6/graphene nanofiber mats. It was found that the surface of the PA6 nanofibers was coated uniformly with the granular PANI and graphene oxide. Besides, the composite nanofibers showed good tensile and thermal properties. Their electrical conductivity and specific capacitance, when used as a separator in the cell, were 1.02 × 10^?4 S/cm and 423.28 F/g, respectively. Therefore, the composite PANI/reduced graphene oxide–coated PA6 nanofiber mats could be regarded as suitable candidates for application in energy storage devices.     

Enhanced conductivity composites for aircraft applications: carbon nanotube inclusion both in epoxy matrix and in carbonized electrospun nanofibers

The potential of carbonized electrospun nanofiber mats to render epoxy resin composites for aircraft applications electrically and thermally more conductive was investigated. The effect of carbon nanotube inclusion both inside the carbon nanofiber and in the epoxy resin matrix material was studied, in order to reveal any synergistic effects of multilevel presence of nanosized reinforcements on the conductivity and mechanical properties. The carbon nanotube inclusion into the carbonized nanofibers increased the electrical conductivity of the samples by 20–50% and the thermal conductivity by approximately three times leading to a higher value than that of the conventional composites. The preparation of layered composites with a conductive upper layer containing nonwoven carbon nanofabric and a load bearing lower layer with conventional unidirectional carbon fiber reinforcement can offer a cost‐effective and weight‐saving solution for the replacement of metal meshes in structural aircraft composites. Copyright © 2014 John Wiley & Sons, Ltd.     

Solution‐blown nylon 6–chitosan core–shell nanofiber for highly efficient affinity adsorption

A facile spinning‐based strategy was developed to fabricate chitosan (CS) surface nanofiber‐based affinity membranes for protein adsorption. The core–shell nanofiber mat of nylon 6–CS was prepared via coaxial solution blowing process. The nanofibers have a diameter range of 60–300 nm. The core–shell structure was confirmed by transmission electron microscopy, and CS was observed as a thin layer that uniformly adhered to the core. The dye ligand of cibacron blue F3GA (CB F3GA) was further covalently immobilized on the nanofibers with a content of 425 µmol/g. The pristine and CB F3GA‐attached mats were studied in protein adsorption. High bovine serum albumin adsorption capacities of 91.9 and 219.6 mg/g were obtained for pristine and CB F3GA‐attached mats, respectively. Given its properties of high flux rate and low pressure drop, CB F3GA‐attached nylon 6–CS nanofiber mat meets the requirements of highly effective affinity membrane chromatography. Copyright © 2016 John Wiley & Sons, Ltd.     

掺杂羧基化碳纳米管的纳米碳纤维前驱体的制备及表征

为获得结构完整、 性能优良的纳米碳纤维前驱体, 采用静电纺丝法制备了掺杂羧基化多壁碳纳米管(MWCNTs)的聚丙烯腈(PAN)纳米纤维. 用扫描电子显微镜、 偏振红外光谱、 透射电子显微镜、 拉曼光谱及拉伸性能测试等对杂化纳米纤维的微观结构和力学性能进行了研究, 分析了MWCNTs含量的影响. 实验结果表明, 5%(质量分数)的MWCNTs掺杂量为杂化纳米纤维直径的突变点, 且MWCNTs的加入有利于PAN分子链的取向, MWCNTs在PAN纤维中大体上沿纤维轴向取向分布. 3%MWCNTs/PAN杂化纳米纤维的拉伸强度和拉伸模量分别达到88.6 MPa和3.21 GPa.     

Fabrication of carbon nanofiber by pyrolysis of freeze-dried cellulose nanofiber

The possibility of fabricating carbon nanofibers from cellulose nanofibers was investigated. Cellulose nanofiber of ~50 nm in diameter was produced using ball milling in an eco-friendly manner. The effect of the drying techniques of cellulose nanofibers on the morphology of carbon residue was studied. After pyrolysis of freeze-dried cellulose nanofibers below 600 °C, amorphous carbon fibers of ~20 nm in diameter were obtained. The pyrolysis of oven-dried precursors resulted in the loss of original fibrous structures. The different results arising from the two drying techniques are attributed to the difference in the spatial distance between cellulose nanofiber precursors.     

Carbon nanofiber supported palladium catalyst for liquid-phase reactions: An active and selective catalyst for hydrogenation of cinnamaldehyde into hydrocinnamaldehyde

Carbon nanofibers (CNFs) prepared by decomposition of ethane over a Ni/alumina catalyst, are used as support for palladium clusters. The carbon support displays a mean diameter of 40–50 nm, lengths up to several tens of micrometers, as highlighted by transmission electron microscopy (TEM) observations and a specific surface area of about 50 m²/g. The spheroidal palladium particles have a relatively homogeneous and sharp size distribution, centered at around 4 nm. This novel Pd/carbon nanofiber catalyst displays unusual catalytic properties and is successfully used in the selective hydrogenation of the C=C bond in cinnamaldehyde at a reaction temperature of around 80°C, under continuous hydrogen flowing at atmospheric pressure. The high performances of this novel catalyst in terms of efficiency and selectivity are, respectively, related to the inhibition of the mass-transfer processes over this non-porous material and to peculiar palladium–carbon interactions. It is concluded that the absence of microporosity in the carbon nanofibers favours both the high activity and selectivity which is confirmed by comparison with the commercially available high surface area charcoal supported palladium catalyst.     

New carbon nanofiber/graphite felt composite for use as a catalyst support for hydrazine catalytic decomposition

Graphite felt supporting 40 nm diameter carbon nanofibers was synthesized and successfully used as a support for a high loaded iridium catalyst (30 wt%) in the decomposition of hydrazine; a strong mechanical resistance and a high thermal conductivity led to a very efficient and stable catalyst as compared to that used industrially, iridium supported on a high surface area alumina.     

Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets

Highly oriented, large area continuous composite nanofiber sheets made from surface-oxidized multiwalled carbon nanotubes (MWNTs) and polyacrylonitrile (PAN) were successfully developed using electrospinning. The preferred orientation of surface-oxidized MWNTs along the fiber axis was determined with transmission electron microscopy and electron diffraction. The surface morphology and height profile of the composite nanofibers were also investigated using an atomic force microscope in tapping mode. For the first time, it was observed that the orientation of the carbon nanotubes within the nanofibers was much higher than that of the PAN polymer crystal matrix as detected by two-dimensional wide-angle X-ray diffraction experiments. This suggests that not only surface tension and jet elongation but also the slow relaxation of the carbon nanotubes in the nanofibers are determining factors in the orientation of carbon nanotubes. The extensive fine absorption structure detected via UV/vis spectroscopy indicated that charge-transfer complexes formed between the surface-oxidized nanotubes and negatively charged (-CN[triple bond]N:) functional groups in PAN during electrospinning, leading to a strong interfacial bonding between the nanotubes and surrounding polymer chains. As a result of the highly anisotropic orientation and the formation of complexes, the composite nanofiber sheets possessed enhanced electrical conductivity, mechanical properties, thermal deformation temperature, thermal stability, and dimensional stability. The electrical conductivity of the PAN/MWNT composite nanofibers containing 20 wt % nanotubes was enhanced to approximately 1 S/cm. The tensile modulus values of the compressed composite nanofiber sheets were improved significantly to 10.9 and 14.5 GPa along the fiber winding direction at the MWNT loading of 10 and 20 wt %, respectively. The thermal deformation temperature increased with increased MWNT loading. The thermal expansion coefficient of the composite nanofiber sheets was also reduced by more than an order of magnitude to 13 x 10(-6)/ degrees C along the axis of aligned nanofibers containing 20 wt % MWNTs.     

Surface morphology and electrical properties of polyurethane nanofiber webs spray‐coated with carbon nanotubes

Multiwalled carbon nanotubes (MWNTs) were spray‐coated on electrospun polyurethane nanofiber webs for electrical conductive application. For the effective coating of MWNTs, hyperbranched polyurethane (HBPU) was used by blending with linear polyurethane, which was synthesized in the A₂ + B₃ approach using poly(ε‐caprolactone)diol, 4,4′‐methylene bis(phenylisocynate), and castor oil. SEM measurements showed that the MWNTs could be coated well along the surface of nanofibers when the HBPU was blended in the linear polyurethane nanofibers. Blending of HBPU in the nanofibers also affected the electrical conductivity of MWNT‐coated nanofiber webs. The low electrical resistance from 20 to 400 Ω/sq was obtained for MWNT‐coated nanofiber webs and their electrical resistance decreased with an increase of spraying frequency. As a potential application of MWNT‐coated nanofiber webs, the electrical heating effect because of applied voltage was demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.     

Well‐dispersed N‐heterocyclic carbene–palladium complex anchored onto poly(acrylic acid)/poly(vinyl alcohol) nanofibers: Novel,superior and ecofriendly nanocatalyst for the Suzuki–Miyaura cross‐coupling reaction

Polymeric nanocomposite@Pd is one of the crown jewels for the catalysis of cross‐coupling reactions. This Pd nanocomposite on various polymeric supports has been well established to catalyze cross‐coupling reactions, but its preparation supported on the surface of nanofibers has been largely overlooked. Herein, we report the preparation of a poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) nanofiber‐supported N‐heterocyclic carbene–Pd complex. The first step involves the preparation of PAA/PVA nanofibers using the electrospinning process. The second step comprises the reaction of water‐soluble poly(ethylene glycol)‐imidazole with modified PAA/PVA nanofibers followed by introduction of PdCl₂ to achieve successfully the desired nanocomposite. The catalytic activity of this nanocomposite was examined in the expeditious synthesis of biaryl compounds using the Suzuki–Miyaura cross‐coupling reaction under mild reaction conditions. The composite offers multiple features such as good hydrophilic properties, high surface area, admirable potential in repeatability tests and being recyclable for several runs without significant loss in its activity under the optimum reaction conditions. Our results showed the superior applicability of this novel nanocatalyst in terms of conversion reaction, yields and turnover frequencies. The structure of the catalyst was characterized using a variety of techniques.     

UV-protection and photocatalytic properties of electrospun polyacrylonitrile nanofibrous mats coated with TiO<Subscript>2</Subscript> nanofilm via sol–gel

UV radiation causes serious damage to skin, and a protective system capable of absorbing or reflecting UV radiation is required to protect skin. This paper describes the UV protection and photocatalytic properties of TiO₂ nanofilm coated electrospun polyacrylonitrile (PAN) nanofibrous mats with various nanofiber diameter and area density. The mats were coated by sol–gel process. The results of this research showed that sol–gel is capable of coating porous nanofibrous mats with a weight increase as low as 0.8%. The TiO₂ nanofilm coated on the nanofibrous mats has a considerable effect on its UV protection. The UV protection factor (UPF) of the mats increases with decreasing nanofiber diameter. In fact decreasing the diameter of nanofibers of the TiO₂ nanofilm coated PAN nanofibrous mats increases their photocatalytic activity. Moreover, this research showed that TiO₂ nanofilm produced through sol–gel process on the PAN nanofibers has a crystalline structure. The UPF of the nanofibrous mat coated with a TiO₂ nanofilm via sol–gel process can be classified as excellent.     

Enhancing the effect of the nanofiber network structure on thermoresponsive wettability switching

This letter reports the enhancing effects of a nanofiber network structure on stimuli-responsive wettability switching. Thermoresponsive coatings composed of nanofibers were prepared by electrospinning from thermoresponsive polymer poly(N-isopropylacrylamide) (PNIPAAm). The nanofiber coatings showed a large amplitude of thermoresponsive change in the wettability from hydrophilic to hydrophobic states compared to a smooth cast film. In particular, the combination of the surface chemistry and unique topology of the electrospun nanofiber coatings enables a transition from the Wenzel state to the metastable Cassie-Baxter state with an increase in temperature and consequently an enhanced amplitude of change in the water contact angles: the apparent contact angle differences between 25 and 50 °C are Δθ*(25-50?°C?)= 108 and 10° for the nanofiber coatings with a diameter of 830 nm and a smooth cast film, respectively. The fabrication of the 3D nanofiber network structure by electrospinning from stimuli-responsive materials is a promising option for highly responsive surfaces in wettability.     

疏水性聚丙烯酸/聚乙烯醇/葡萄糖淀粉酶复合纳米纤维膜的制备及酶学性质

利用混合静电纺丝将葡萄糖淀粉酶(GA)固定于聚丙烯酸(PAA)/聚乙烯醇(PVA)纳米纤维膜上,并通过鉴定固定化GA的酶学特征检验PAA/PVA可否成为一种优良的酶固定化载体。 对其理化性质和酶学特征进行鉴定,经红外光谱(FT-IR)和扫描电子显微镜(SEM)表征发现,GA可成功包埋于PAA/PVA纳米纤维膜内部;对包裹固定的GA进行酶学性质鉴定,发现固定化GA的最适反应温度为68 ℃,比游离GA提高了9 ℃;固定化GA的适用pH值范围明显变宽;热稳定性和存贮稳定性显著增强且可以重复使用。PAA/PVA纳米纤维膜是一种优良的酶固定化载体,可以通过混合静电纺丝包埋法简便地将蛋白质分子固定于其内部,具有一定的应用前景。     

Electrospun glassy carbon ultra-thin layer chromatography devices

The development and application of electrospun glassy carbon nanofibers for ultra-thin layer chromatography (UTLC) are described. The carbon nanofiber stationary phase is created through the electrospinning and pyrolysis of SU-8 2100 photoresist. This results in glassy carbon nanofibers with diameters of ∼200–350 nm that form a mat structure with a thickness of ∼15 μm. The chromatographic properties of UTLC devices produced from pyrolyzed SU-8 heated to temperatures of 600, 800, and 1000 °C are described. Raman spectroscopy and scanning electron microscopy (SEM) are used to characterize the physical and molecular structure of the nanofibers at each temperature. A set of six laser dyes was examined to demonstrate the applicability of the devices. Analyses of the retention properties of the individual dyes as well as the separation of mixtures of three dyes were performed. A mixture of three FITC-labeled essential amino acids: lysine, threonine and phenylalanine, was examined and fully resolved on the carbon UTLC devices as well. The electrospun glassy carbon UTLC plates show tunable retention, have plate number, N, values above 10,000, and show physical and chemical robustness for a range of mobile phases.