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...     

PVA/GA/β-CD纳米纤维的制备及染料吸附性能

利用静电纺丝技术,以六氟异丙醇(HFIP)和水为溶剂,制备了环糊精(β-CD)含量为70%(质量分数)的聚乙烯醇(PVA)/β-CD纳米纤维,并经戊二醛(GA)交联处理得到了可用于染料吸附的PVA/GA/β-CD纳米纤维.通过红外光谱和扫描电子显微镜研究了交联反应前后纳米纤维组成和形貌的变化;考察了PVA/GA/β-CD纳米纤维对7种水溶性染料的吸附性能.结果表明,PVA/GA/β-CD纳米纤维对孔雀石绿、甲基紫和刚果红的吸附效果较好,最大吸附量分别为124.71,121.14和127.39 mg/g,4次吸附-解吸附循环后,染料去除率仍保持80%左右,在染料废水处理中具有良好的应用前景.     

AOPAN@PAN同轴纳米纤维的制备及吸附性能

将盐酸羟胺与聚丙烯腈(PAN)反应得到偕胺肟化聚丙烯腈(AOPAN)溶液,随后采用同轴静电纺丝技术,制备了以AOPAN为壳,PAN为芯的同轴纳米纤维(AOPAN@PAN).通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)和红外光谱(FTIR)等对纤维的形貌、组成和力学性能进行了表征.结果表明,随着PAN用量的增加,AOPAN@PAN同轴纳米纤维的强度逐渐变大,当芯层与壳层质量比为1∶3时,纳米纤维的抗拉伸强度和断裂伸长率分别为3.677 MPa和18.03%;对Cu~(2+),Pb~(2+),CrO_4~(2-)和甲基橙(MO)的最大吸附量分别为135.1,151.2,120.48和43.45 mg/g;使水中Cu~(2+),Pb~(2+),CrO_4~(2-)和MO的浓度分别降低到0.17,0.03,0.06和0.91 mg/L.     

聚丙烯腈纳米纤维的高效制备及结晶取向性能

分别采用传统静电纺丝装置和自行搭建的离心-静电纺丝装置制备出聚丙烯腈(PAN)纳米初生纤维,并在热空气浴中和一定外力作用下进行牵伸,牵伸后使其伸长至原长的1倍到3倍.通过广角X射线衍射(WAXD)、扫描电子显微镜(SEM)等方法对2种纺丝方法制备的PAN纳米初生纤维及经过热空气浴牵伸后的PAN纳米纤维的晶态结构、取向及形貌等进行了表征.研究表明:(1)离心-静电纺丝效率远高于静电纺丝,可达静电纺丝的120倍(离心-静电纺丝纺丝液流速为2 m L/min,静电纺丝纺丝液流速1 m L/h);(2)无论是离心纺丝还是静电纺丝制得的纳米初生纤维结晶度均很低(离心纺丝为25%,静电纺丝为10.1%),但离心纺丝制得的纳米初生纤维有一定的取向(60.5%),而静电纺丝基本没有;(3)经过热空气浴牵伸后,2种纺丝方式制得的纳米纤维结晶度均有所提高(分别为45.8%和36.2%),取向度也有所提高(分别为72.5%和59.8%),随着牵伸温度的提高和牵伸应力的增大,纤维的平均直径不断减小(离心纺丝由675 nm降至510 nm,静电纺丝由460 nm降至355 nm).纳米纤维在制备过程晶态结构及取向的效果有限,但通过热空气浴牵伸可以使晶态结构及取向得到进一步完善.     

羧甲基-β-环糊精功能化的四氧化三铁磁性纳米复合物对罗丹明B的吸附性能

基于S_N2取代反应制备了羧甲基-β-环糊精(CM-β-CD),采用层层组装法将其成功修饰在Fe₃O₄磁性纳米粒子表面(MNPs),得到了CM-β-CD功能化的磁性纳米复合物(CM-β-CD-MNPs),通过透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)及振动样品磁强计(VSM)等技术手段进行了表征,考察了其对染料罗丹明B(RhB)的吸附性能。 结果表明,CM-β-CD-MNPs呈球形,分散均匀,平均粒径为16 nm,饱和磁化率为54 emu/g,呈超顺磁性。 吸附动力学符合准二级动力学模型,且吸附1 h达到平衡。 吸附等温线符合Langmuir等温吸附模型,最大吸附量为135.1 mg/g。     

β-环糊精修饰的壳聚糖对氯酚吸附的动力学和热力学

制备了β-环糊精(β-CD)修饰的壳聚糖(CS)—β-环糊精-6-壳聚糖(CS-CD), 并用傅里叶变换红外(FT-IR)光谱仪, 扫描电镜(SEM), X 射线衍射(XRD)仪和比表面分析仪(BET)进行了表征. 详细研究了其对2-氯酚(2-CP)、2,4-二氯酚(DCP)和2,4,6-三氯酚(TCP)的吸附行为和机理. 研究表明其吸附较好地满足Langmuir 和Freundlich 吸附模型, β-环糊精的引入能够较大地提高吸附效率, 2-CP、DCP和TCP在CS-CD上吸附的最大吸附量分别为14.51、50.68和74.29 mg·g^-1. 动力学研究表明其吸附速率快, 在1 h内能达到吸附平衡, 并符合假二级动力学模型. 计算出了热力学参数ΔG⁰、ΔH⁰和ΔS⁰的值, ΔG⁰为负值表明吸附剂对氯酚的吸附是一个自发的过程. 电解质和溶液pH值对吸附的影响说明在吸附过程中主要是氯酚与吸附剂之间形成了氢键, 并进一步讨论了可能的吸附机理. 改性吸附剂易重复利用, 重复使用六次后的质量和吸附效率与初次相比分别保持在90%和82%以上, 然而CS的质量有较大的损失, 吸附效率也明显降低.     

聚丙烯腈纳米纤维载银复合膜绿色制备及其催化性能

采用静电纺丝技术和化学镀方法相结合的方法,用聚丙烯腈(PAN)纳米纤维作为载体,以绿色环保的胺化改性替代化学镀传统的敏化、活化前处理,再化学镀银制备胺化聚丙烯腈纳米纤维载银复合膜(Ag/APAN).SEM、XPS、XRD、FTIR等结果表明,银离子能够吸附在经胺化处理后的PAN纳米纤维表面,且能够在纤维表面生成少量单质银;单质银作为催化活性中心,有效地促进化学镀银的进行,在PAN纳米纤维表面生成均匀致密的银纳米粒子层,制备出了以PAN纳米纤维为核,银层为壳的核壳结构复合膜.银纳米粒子附着在纳米纤维表面,可以使银纳米粒子的催化性能得到充分发挥.通过对催化邻-硝基苯胺与硼氢化钠之间氧化还原反应的研究表明,所制备的Ag/APAN纳米纤维复合膜具有很好的催化效果,且不会造成反应体系的二次污染.     

AOPAN/PA-66复合纳米纤维膜的制备及对金属离子的吸附性能

采用双喷头电纺丝技术,将尼龙(PA-66)纤维增强的聚丙烯腈(PAN)纳米纤维膜(PAN/PA-66)与盐酸羟胺进行偕胺肟化反应,制备了一种偕胺肟化聚丙烯腈/尼龙复合纳米纤维膜(AOPAN/PA-66).通过红外光谱及扫描电子显微镜等方法研究了偕胺肟化前后纳米纤维膜的组成、形貌和力学性能;并考察了AOPAN/PA-66复合纳米纤维膜对铜离子和铅离子的吸附性能.结果表明,AOPAN/PA-66复合纳米纤维膜的抗拉伸强度及断裂伸长率分别为4.73 MPa和30.76%,对Cu(Ⅱ)及Pb(Ⅱ)的吸附量分别为67.5和75.4 mg/g.     

Ag/AgCl复合纳米粒子/聚丙烯腈纳米纤维膜的制备及可见光催化降解甲基橙

通过电纺丝法结合原位还原及原位氧化反应, 成功制备了均匀负载Ag/AgCl复合纳米粒子/聚丙烯腈(PAN)复合纳米纤维膜. 首先利用电纺丝技术制备了PAN/AgNO₃复合纳米纤维, 然后用乙二醇将硝酸银还原成银纳米粒子, 最后采用三氯化铁溶液对材料进行原位氧化. 所得纤维膜材料可以作为高效的可见光催化剂, 具有高可见光利用率, 优异的柔性和高光催化动力学等特性.     

α-氯丙酸乙酯对映体与β-环糊精的主客体相互作用

运用量子力学PM3方法模拟α-氯丙酸乙酯((R/S)-ECPA)与β-环糊(β-CD)的主客体相互作用, 探讨(R/S)-ECPA在β-CD上的手性识别机理. 结果表明, (R/S)-ECPA对映体与β-CD形成稳定结合物的结合方式完全不同, (R)-ECPA位于β-CD空腔宽口端, 形成缔合物; (S)-ECPA插入β-CD空腔内形成包结物. 而且, (S)-ECPA与β-CD的结合稳定能低于(R)-ECPA与β-CD的结合稳定能. 在(R/S)-ECPA与β-CD结合物中, (R/S)-ECPA中的手性碳接近葡萄糖单元的C2和C3. (R/S)-ECPA与β-CD之间的手性识别与葡萄糖单元的C2和C3所提供的手性环境和(R/S)-ECPA与β-CD结合的紧密程度密切相关.     

Functionalized electrospun carbon nanofibers for removal of cationic dye

Electrospun carbon nanofibers (ECNFs) have attracted significant attention in recent years as relatively inexpensive alternative to carbon nanotubes for adsorption organic pollutants. In this study, ECNFs were fabricated from polyacrylonitrile (PAN) using an electrospinning technique, followed by carbonization and oxidation via treatment with a H₂SO₄/HNO₃ mixture. The prepared oxidized electrospun carbon nanofibers (O-ECNFs) were characterized using scanning and transmission electron microscopy (SEM and TEM), Fourier transform infrared (FT-IR), Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The O-ECNFs were used as nano-adsorbents for the adsorption of methylene blue (MB) from aqueous solution. The adsorption of MB by the O-ECNFs was studied as a function of pH, time, adsorbent dosage, MB concentration, and temperature. ECNF functionalization enhanced the adsorption capacity towards MB dye compared pristine ECNFs. Detailed analysis of the adsorption kinetics showed that the adsorption process followed a pseudo-second-order model. The adsorption isotherm was best fit by the Langmuir model. The thermodynamic results showed that MB adsorption onto the O-ECNFs was endothermic and spontaneous.     

Preparation of amidoxime-modified polyacrylonitrile (PAN-oxime) nanofibers and their applications to metal ions adsorption

Polyacrylonitrile (PAN) nanofibers were applied to metal adsorption. PAN nanofibers (prepared by an electrospinning technique) were chemically modified with amidoxime groups, which are suitable for metal adsorption due to their high adsorption affinity for metal ions. The adsorption of the amidoxime-modified PAN (PAN-oxime) (25% conversion) nanofibers followed Langmuir isotherm. The saturation adsorption capacities for Cu(II) and Pb(II) of 52.70 and 263.45 mg/g (0.83 and 1.27 mmol/g), respectively, indicating that the monolayer adsorption occurred on the nanofiber mats. In addition, over 90% of metals were recovered from the metal-loaded PAN-oxime nanofibers in a 1 mol/L HNO₃ solution after 1 h.     

Decoration of electrospun polyacrylonitrile nanofibers with ZnO nanoparticles and their application for removal of Pb ions from waste water

The adsorption behavior of lead (II) from aqueous solutions utilizing ZnO/polyacrylonitrile (PAN) nanofibers was studied. ZnO/PAN nanofibers were prepared by electrospinning method. The changes of the parameters of adsorbent amount, pH, contact time, and temperature were tested in the adsorption experiments. The adsorption was well described by the Langmuir adsorption isotherm model. The thermodynamic parameters indicate that the adsorption process is exothermic. The dynamic behavior of the lead (II) ions adsorption by PAN/ZnO nanofibers was well described by the pseudo-second-order kinetic model. The adsorbent can be regenerated by suitable desorption processes for multiple uses without significant loss of its adsorption capacity.     

The preparation and adsorption properties of electrospun aramid nanofibers

The focus of this work is the preparation of aramid nanofibers via electrospinning technology and the study of their adsorption properties. In this article, aramid nanofibers were prepared by electrospinning aramid fibers solution with the addition of lithium chloride (LiCl). It showed a good adsorption capacity when methylene blue (MB) was used as the model target. There were much larger adsorption amounts and faster kinetics of uptaking target species of electrospun aramid nanofibers to MB than that of electrospun polyethersulfone (PES) nanofibers. Compared with activated carbon, aramid nanofibers also have a much faster adsorption rate to MB. Aramid nanofibers were subsequently used to effectively remove endocrine disruptors such as bisphenol A (BPA), phenol (Phe), and p‐hydroquinone (BPhe) from their aqueous solutions. Additionally, molecule imprinted technology enhances aramid nanofibers with much higher adsorption amounts and special adsorption property for endocrine disruptors. These results showed that aramid nanofibers have the potential to be used in environmental applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

基于MCM-41模板制备β-MnO_2纳米纤维及其催化降解亚甲基蓝染料

以介孔氧化硅材料MCM-41为模板,硝酸锰为锰源,通过浸渍、450℃焙烧4 h得到Mn-MCM-41,用NaOH溶液溶解除去氧化硅模板得到锰氧化物,采用XRD,HRTEM和N2吸附-脱附等测试技术对产物进行了表征.结果表明,所得产物是纯相的β-MnO2纳米纤维,直径小于3 nm.纳米纤维之间有序排列组成类似MCM-41模板的介孔结构,其比表面积达到136.5 m2/g.将所制备的β-MnO2纳米纤维用于催化过氧化氢氧化分解质量浓度为60 mg/L的亚甲基蓝(MB)模拟染料废水,经100 min反应后,亚甲基蓝水溶液脱色率达到97.59%.所制备的催化剂对降解处理高浓度亚甲基蓝溶液,具有降解脱色率高和反应速度快等优点.     

Phosphorylated polyacrylonitrile‐based electrospun nanofibers for removal of heavy metal ions from aqueous solution

The phosphorylated polyacrylonitrile‐based (P‐PAN) nanofibers were prepared by electrospinning technique and used for removal of Cu²⁺, Ni²⁺, Cd²⁺, and Ag⁺ from aqueous solution. The morphological and structural properties of P‐PAN nanofibers were characterized by scanning electron microscope and Fourie transform infrared spectra. The P‐PAN nanofibers were evaluated for the adsorption capacity at various pH, contact time, and reaction temperature in a batch system. The reusability of P‐PAN nanofibers for the removal of heavy metal ions was also determined. Adsorption isotherms and adsorption kinetics were also used to examine the fundamental adsorption properties. It is found that the P‐PAN nanofibers show high efficiency, and the maximal adsorption capacities of metal ions as calculated from the Langmuir model were 92.1, 68.3, 14.8, and 51.7 mg/g, respectively. The kinetics of the heavy metal ions adsorption were found to follow pseudo‐second‐order rate equation, suggesting chemical adsorption can be regarded as the major factor in the adsorption process. Sorption/desorption results reveal that the obtained P‐PAN nanofibers can remain high removal efficiency after four cycles.     

Polyacrylonitrile/Aminated Polymeric Nanosphere Nanofibers as Efficient Adsorbents for Cr(VI) Removal

In this work, polyacrylonitrile/aminated polymeric nanosphere (PAN/APN) nanofibers were prepared by electrospinning of monodispersed aminated polymeric nanospheres (APNs) for removal of Cr(VI) from aqueous solution. Characterization results showed that obtained PAN/APNs possessed nitrogen functionalization. Furthermore, the adsorption application results indicated that PAN/APN nanofibers exhibited a high adsorption capacity of 556 mg/g at 298 K for Cr(VI) removal. The kinetic data showed that the adsorption process fits the pseudo-second order. A thermodynamic study revealed that the adsorption of Cr(VI) was spontaneous and endothermic. The coexisting ions Na⁺, Ca²⁺, K⁺, Cl⁻, NO₃⁻ and PO₄³⁻ had little influence on Cr(VI) adsorption, while SO₄²⁻ in solution dramatically decreased the removal performance. In the investigation of the removal mechanism, relative results indicated that the adsorption behavior possibly involved electrostatic adsorption, redox reaction and chelation. PAN/APN nanofibers can detoxify Cr(VI) to Cr(III) and subsequently chelate Cr(III) on its surface. The unique structure and nitrogen functionalization of PAN/APN nanofibers make them novel and prospective candidates in heavy metal removal.     

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.     

不同直径改性PAN纳米纤维膜与Fe3+的配位反应及其配合物对有机染料降解的催化性能

使用静电纺丝技术和偕胺肟反应制备了三种不同直径的改性聚丙烯腈(PAN)纳米纤维膜,然后将它们作为配体分别与Fe3+进行配位反应制备改性PAN纳米纤维膜铁配合物,重点研究了三种改性PAN纳米纤维膜与Fe3+配位反应的动力学特性及其温度和Fe3+初始浓度的影响.最后将其作为非均相Fenton反应催化剂应用于染料降解反应中,考察了改性PAN纳米纤维膜直径对其催化活性的影响.结果表明,在所涉及的温度和浓度范围内,改性PAN纳米纤维膜与Fe3+之间配位反应不仅符合Langmuir和Freundlich吸附等温式,而且可理想地使用Lagergren准二级动力学方程进行描述,反应速率常数随着Fe3+初始浓度的增加而逐渐降低.在相同反应条件下,较小直径的纤维膜更容易与Fe3+发生配位反应,且反应速率常数和Fe3+配合量均随着纤维直径的降低而增大.不同直径改性PAN纳米纤维膜铁配合物在暗态条件下对染料的氧化降解反应表现出很好的催化活性,且在辐射光下其催化活性得到加强.改性PAN纳米纤维膜铁配合物的催化作用受到纤维直径的显著影响,由中等直径纳米纤维构成的配合物表现出最高的催化活性.