静电纺丝制备聚丙烯腈纳米碳纤维

利用静电纺丝制备连续的聚丙烯腈纳米碳纤维;介绍了静电纺丝的原理、影响静电纺丝的主要因素以及制备纳米碳纤维、纳米活性炭纤维、纳米碳纤维复合材料的方法和原理;分析了静电纺丝产率低,难以得到单向平铺的纤维等问题,影响静电纺丝的参数主要有溶液特性、纺丝工艺参数、纺丝环境参数。由静电纺丝得到纳米聚丙烯腈纤维,然后再经预氧化和碳化制备纳米碳纤维,或把纳米纤维预氧化,经活化、碳化制备纳米活性炭纤维。并指出纳米碳纤维具有巨大的潜在应用空间。     

电纺聚丙烯腈基碳纳米纤维在超级电容器中的应用

静电纺丝法制备聚丙烯腈（PAN）基纳米纤维具有较大的比表面积、较高的机械强度、优异的纳米结构及良好的化学稳定性。以PAN纳米纤维为基础,进行多方位设计与合成的电极材料在超级电容器中表现出优异的电化学性能,具有广阔的应用前景。本文根据电极材料分类,主要综述了近年来PAN基多孔结构电极材料、杂原子掺杂电极材料以及与碳系材料、导电聚合物、金属氧化物复合等电极材料的研究进展;讨论了电极材料的结构特征、制备方法及其提高电化学性能的原理;最后指出了上述研究中存在的问题,并对未来PAN基电极材料在超级电容器的发展前景进行了展望。     

Properties of carbon nanofibers prepared from electrospun polyimide

A solution of a polyimide (PI, Matrimid® 5218) in dimethylacetamide was electrospun, and carbonization of the electrospun nonwoven fabrics produced carbon nanofiber fabrics. The effects of iron(III) acetylacetonate (AAI) on carbonization and the resulting morphology were also investigated. The carbonization behavior of the nonwoven fabrics was examined by X‐ray diffraction and Raman spectroscopy. AAI promoted carbonization of the nonwoven fabrics and increased the carbon yield. Addition of 3 wt % AAI increased the crystal dimension of electrospun PI nanofibers from 1.06 to 4.18 nm and decreased the integrated intensity ratio from 3.37 to 1.83 when heat treated at 1200°C. Scanning electron microscopy images of the carbonized nonwoven fabrics showed that AAI remained as particles within the fibers after carbonization. In addition, transmission electron microscopy observations revealed that turbostratic‐oriented graphite layers were observed around the particles even at 1200°C, which have been reported only on carbonization of rigid‐chain solvent insoluble PI materials under tension. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97:165–170, 2005     

电纺法制备聚丙烯腈基纳米碳纤维

用电纺法制备了聚丙烯腈（PAN）纳米纤维,用场发射扫描电镜（FESEM）对其形态进行了研究,讨论了不同工艺参数对纤维直径和分散形态的影响。结果发现,纤维直径随着浓度的增加而增大,随着电压升高而减小,接收距离和溶剂类型对纤维直径的影响不大。将形态最好的纤维在240℃下进行活化处理,然后将活化处理过的纤维在氮气氛中煅烧,用FESEM观察了煅烧的纤维直径及形态的变化,红外（IR）分析了纤维化学结构的变化,证实了经900℃煅烧后的纤维为碳纳米纤维。     

Determination of optimal production parameters for polyacrylonitrile nanofibers

The object of this work is to determine the most suitable values of process and solution parameters for electrospinning of polyacrylonitrile (PAN) nanofibers including solution concentration, applied voltage, and working distance between the needle tip and the collector plate. To investigate the effects of those parameters on the fiber morphology, nanofiber mat samples were produced by changing the value of parameters systematically. The scanning electron microscope images of these samples were analyzed to realize the effects of these parameters on the nanofiber morphology. Our results demonstrate that the diameter of the fibers increases with increasing concentration. However, the diameter reduces as the applied voltage and working distance between needle tip and the collector increase up to a certain value. In addition to this, viscosity and applied voltage have a strong effect on the uniformity and morphology of the nanofibers. Moreover, a relationship between spinning distance, voltage supplied, solution concentration, charge density, bead formation, and the diameter of the electrospun PAN nanofiber were established in the study. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

ZIF衍生多孔碳纳米纤维用于高效电容去离子的研究

作为一种环保节能的新兴脱盐技术,电容去离子技术正在成为替代反渗透脱盐和电渗析脱盐的一项重要的脱盐技术。各种碳基材料被广泛地应用于电容去离子电极材料的研究,然而大多数碳基材料为粉末状材料,需要添加黏结剂,这必将导致电极材料电吸附能力的下降。利用静电纺丝技术,将ZIF纳米颗粒和聚丙烯腈混纺,并通过分段高温热处理过程,成功合成了具有柔性结构的整体性多孔碳纳米纤维。由于其具有孔道结构的分级分布和较强的亲水性等优良特性,所制得的多孔碳纳米纤维在1.2 V电压下于500 mg/L NaCl溶液中表现出良好的电吸附性能,脱盐量达到了19.92 mg/g,比普通碳纳米纤维提高了一倍以上。     

Fabrication and electrical characterization of electrospun polyacrylonitrile‐derived carbon nanofibers

Carbon nanofibers were produced from a polyacrylonitrile/N,N‐dimethylformamide precursor solution by an electrospinning process and later pyrolysis at temperatures ranging from 500 to 1100°C in an N₂ atmosphere for about 1 h. The morphological structure of the nanofibers was studied with scanning electron microscopy. Scanning electron microscopy images of carbonized polyacrylonitrile nanofibers without a gold coating showed that the carbonized polyacrylonitrile nanofibers possessed electrical properties. The thermal behavior of the nanofibers was studied with thermogravimetric analysis. An indirect four‐point‐probe method was used for the measurement of the conductivity of nanofiber mats. The conductivity increased sharply with the pyrolysis temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

纳米碳纤维的微观结构调控与催化作用

纳米碳纤维（CNF）是一种新型一维结构纳米炭材料,因其具有许多独特的性质而备受研究者关注。按照CNF基本结构单元石墨片层与生长轴的夹角不同,可以将CNF分为板式、鱼骨式和管式3种不同微观结构。采用催化化学气相沉积法合成CNF时,微观结构可以通过改变生长动力学进行调控。CNF微观结构的不同导致表面棱边与基面原子比例不同,进而影响着表面含氧基团分布等性质。当CNF用作催化剂载体时,利用这些性质的不同可以调控负载金属颗粒的形貌以及载体与金属作用力等性质,从而改变催化剂的性能。CNF自身具有催化活性,其活性主要来自表面杂原子基团,因此也与CNF的微观结构密切相关。     

低温螺旋纳米炭纤维的制备与表征

在250,280,310℃的低温条件下,以乙炔为碳源,纳米铜粒子作为催化剂,用CVD法制备螺旋纳米炭纤维,并对其表面形貌、元素组成和分布、晶体结构进行了研究。研究表明:在低能耗条件下,制备的螺旋状纳米炭纤维直径在100~300 nm,且产量丰富,可望实现工业化推广。螺旋状纳米炭纤维的C的原子数分数在85%以上,用XRD表征螺旋纳米炭纤维表明,螺旋纳米炭纤维是非晶体的,不是石墨态的,结构不完整。     

Grafting of polystyrene on carbon nanofibers by introducing a methacrylate unit

BACKGROUND: To overcome the self‐agglomeration of carbon nanofibers (CNFs), a number of studies have dealt with surface modification of CNFs to improve their wettability. In this work, a novel, simple and practical approach based on the introduction of methacrylate units to graft polymers onto the surface of CNFs is proposed. RESULTS: The functionalized CNF samples were characterized using Fourier transform infrared and Raman spectroscopy, thermal gravimetric analysis and transmission electron microscopy. The molecular weight of grafted polystyrene (PS) is influenced by the monomer feed ratio. The stabilities of various CNF dispersions were measured using an optical analyzer. When the content of grafted PS is 34.2%, the functionalized CNFs attain a stable dispersion in xylene. CONCLUSION: In the presence of methacrylate units, PS has been successfully grafted onto the surface of CNFs via an in situ polymerization. Moreover, the introduction of methacrylate units opens the functionalization of CNFs to other routes. Copyright © 2009 Society of Chemical Industry     

Polymer crystallization and precipitation‐induced wrapping of carbon nanofibers with PBT

Carbon nanofibers (CNFs) have attracted significant interest because of their excellent mechanical, electrical, and physical properties. Recent advances in chemical functionalization strategies are anticipated to extend their utility in various applications. In this study, noncovalent methods of CNF functionalization utilizing solution crystallization and precipitation techniques were used to create hybrid nanostructures consisting of CNFs and poly(butylene terephthalate) (PBT). Key to this study is the finding that o‐chlorophenol can be used as a suitable solvent to dissolve PBT to generate these nanostructures. PBT crystallization was documented via wide‐angle X‐ray analysis and differential scanning calorimetry and was due to the nucleation effect of the CNFs. The sizes of the PBT crystals could be manipulated by altering the polymer concentration. The solution crystallization and precipitation techniques provide an alternative strategy to alter and control the nanostructure/polymer interface. The resulting nanohybrid structures may potentially find use in a broad range of applications including electronic devices, sensors, and as reinforcing agents in a polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

纳米纤维纺织技术距实际应用还有多远

随着现代科学技术的发展,纳米技术离我们越来越近。科学家正试图在各个领域中应用纳米技术。本文介绍纳米技术在电纺织连续纳米纤维疗面取得的新进展。     

涂层浸渍法在Al2O3片上大面积合成碳纳米纤维

α-Al2O3颗粒经过压片高温焙烧制成多孔支撑体,然后采用涂层浸渍法在Al2O3片上沾涂Fe和Ni催化剂,以乙炔为碳源,采用化学气相沉积法成功合成出碳纳米纤维及少量管径很细的碳纳米管.碳纳米纤维以及碳纳米管的产量和直径与所沾涂的催化剂溶液浓度成正比;对于同样浓度的Fe、Ni催化剂,在Ni催化剂上生长的碳纤维直径要比在Fe催化剂上生长的纤维细.产品晶态结构完好,碳的石墨化程度较高.     

负载型非晶态合金催化剂Ni-Fe-Rh-P/CNFs的制备及其催化性能

研究了化学镀Ni-Fe-Rh-P非晶态合金镀层的工艺,考察了镀液成分和工艺参数对沉积速率和镀层质量的影响。利用优化的工艺配方在经过敏化、活化处理后的纳米碳纤维（CNFs）表面沉积了Ni-Fe-Rh-P合金镀层,分别利用能量色散X射线谱（EDS）、X射线衍射仪（XRD）及扫描电子显微镜（SEM）等手段对镀层的成分、结构、形貌进行了表征,采用液相硝基苯催化加氢反应表征了制备催化剂的催化活性。结果表明,利用化学镀技术可以在纳米碳纤维表面负载连续、均匀的Ni-Fe-Rh-P合金镀层,且镀层为非晶态结构;负载型非晶态合金催化剂Ni-Fe-Rh-P/CNFs具有很高的催化活性和良好的循环使用性能。     

Investigating the effect of PGA on physical and mechanical properties of electrospun PCL/PGA blend nanofibers

In the field of tissue engineering there is always a need for new engineered polymeric biomaterials which have ideal properties and functional customization. Unfortunately the demands for many biomedical applications need a set of properties that no polymers can fulfill. One method to satisfy these demands and providing desirable new biomaterials is by mixing two or more polymers. In this work, random nanofibrous blends of poly (ε‐caprolactone) (PCL) and polyglycolic acid (PGA) with various PCL/PGA compositions (100/0, 80/20, 65/35, 50/50, and 0/100) were fabricated by electrospinning method and characterized for soft‐tissue engineering applications. Physical, chemical, thermal, and mechanical properties of PCL/PGA blend nanofibers were measured by scanning electron microscopy (SEM), porosimetry, contact angle measurement, water uptake, attenuated total reflectance Fourier transform‐infrared spectroscopy (ATR‐FT‐IR), X‐ray diffraction (XRD), differential scanning calorimetric (DSC), dynamic mechanical thermal analysis (DMTA), and tensile measurements. Morphological characterization showed that the addition of PGA to PCL results in an increase in the average diameter of the nanofibers. According to these results, when the amount of PGA in the blend solution increased, the hydrophilicity and water uptake of the nanofibrous scaffolds increased concurrently, approaching those of PGA nanofibers. Differential scanning calorimetric studies showed that the PCL and PGA were miscible in the nanofibrous structure and the mechanical characterization under dry conditions showed that increasing PGA content results in a tremendous increase in the mechanical properties. In conclusion, the random nanofibrous PCL/PGA scaffold used in this study constitutes a promising material for soft‐tissue engineering. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hierarchically porous N-doped carbon nanofibers derived from ZIF-8/PAN composites for benzene adsorption

Coupling with electrospinning technique, metal–organic-frameworks (MOFs)-derived porous carbon fibers exhibit a great potential application in the adsorption of volatile organic compounds (VOCs) because of their huge surface area, high porosity, as well as sufficient heteroatom-doped active sites. In this work, the hierarchically porous N-doped carbon nanofibers are obtained after the pyrolysis of zeolite imidazole framework-8 and polyacrylonitrile (ZIF-8/PAN) composite fibers synthesized by electrospinning method. The N-doped carbon nanofibers fabricated in N₂ atmosphere (N-CF-N₂) present an enhanced adsorption capacity of 694 mg/g for benzene because of the synergistic effect of the hierarchically porous structure and the abundant N-species-containing active sites. It is also interesting that the N-doped hierarchical carbon nanofibers fabricated in Ar atmosphere (N-CF-Ar) exhibit a low benzene adsorption as compared with the N-CF-N₂, which can be attributed to the porous structure damage caused by the bombardment of heavy Ar atoms on the pore shells during the pyrolysis. These results not only show a promising application of the as-fabricated N-CF-N₂ in adsorption of VOCs for air purification due to its merit of cost-efficient, large-scale production, and excellent adsorption capacity, but also expand the potential of electrospinning technology and composite fibers in volatile organic gas adsorption.     

多孔纳米碳纤维作为质子交换膜燃料电池微孔层的性能

质子交换膜燃料电池膜电极中的微孔层结构对改善体系的水管理能力,提升膜电极的整体性能发挥重要作用。本文通过静电纺丝和后续热处理的方法制备了多孔纳米碳纤维（PCNF）,并以此构建膜电极的微孔层。与炭黑颗粒作为微孔层呈现出紧密堆积结构不同,由PCNF搭建的微孔层结构疏松呈现三维贯通状。膜电极的发电测试表明,以多孔纳米碳纤维作为微孔层（MPL-PCNF）的膜电极其最大功率密度达70.0mW/cm²,远高于炭黑颗粒为微孔层（MPL-CB）的膜电极（58.1mW/cm²）,而没有微孔层（Ref）结构的膜电极最大功率密度仅为27.7mW/cm²,显示出PCNF作为微孔层材料的明显优势。     

Non‐ionic surfactants for enhancing electrospinability and for the preparation of electrospun nanofibers

BACKGROUND: Electrospinning is widely used to produce nanofibers; however, not every polymer can be electrospun into nanofibers. To enhance electrospinability, much effort has been made in designing new apparatus, such as vibration‐electrospinning, magneto‐electrospinning and bubble‐electrospinning. RESULTS: A representative non‐ionic surfactant, TritonR X‐100, is used to enhance electrospinability. The surfactant is added to an electrospun poly(vinyl pyrrolidone) polymer solution, and a dramatic reduction in surface tension is observed. As a result, a moderate voltage is needed to produce fine nanofibers, which are commonly observed during the conventional electrospinning procedure only at elevated voltage. CONCLUSION: The novel strategy produces smaller nanofibers than those obtained without surfactants, and the minimum threshold voltage is much decreased. Copyright © 2008 Society of Chemical Industry     

Novel Pd-carrying composite carbon nanofibers based on polyacrylonitrile as a catalyst for Sonogashira coupling reaction

Novel Pd-carrying composite carbon nanofibers based on polyacrylonitrile were prepared by electrospinning and carbonization process. The catalytic activities of the composite nanofibers were tested with a Sonogashria coupling reaction of iodobenzene and phenylacetylene in liquid-phase. Transmission electron microscope and X-ray diffraction analyzer were used to characterize the nanofibers and the metal nanoparticles on the fibers; gas chromatograph and nuclear magnetic resonance spectroscopy were used to characterize the product of the testing reaction. The results first showed that the catalyst not only had a high catalytic activity, but also had good leaching-resistance, retrieval and reusability for the Sonogashira reaction.     

Electrospun porous carbon nanofibers derived from bio-based phenolic resins as free-standing electrodes for high-performance supercapacitors

Phenolic resins were employed to prepare electrospun porous carbon nanofibers with a high specific surface area as free-standing electrodes for high-performance supercapacitors. However, the sustainable development of conventional phenolic resin has been challenged by petroleum-based phenol and formaldehyde. Lignin with abundant phenolic hydroxyl groups is the main non-petroleum resource that can provide renewable aromatic compounds. Hence, lignin, phenol, and furfural were used to synthesize bio-based phenolic resins, and the activated carbon nanofibers were obtained by electrospinning and one-step carbonization activation. Fourier transform infrared and differential scanning calorimetry were used to characterize the structural and thermal properties. The results reveal that the apparent activation energy of the curing reaction is 89.21 kJ·mol^–1 and the reaction order is 0.78. The activated carbon nanofibers show a uniform diameter, specific surface area up to 1100 m²·g^–1, and total pore volume of 0.62 cm³·g^–1. The electrode demonstrates a specific capacitance of 238 F·g^–1 (0.1 A·g^–1) and good rate capability. The symmetric supercapacitor yields a high energy density of 26.39 W·h·kg^–1 at 100 W·kg^–1 and an excellent capacitance retention of 98% after 10000 cycles. These results confirm that the activated carbon nanofiber from bio-based phenolic resins can be applied as electrode material for high-performance supercapacitors.