手性聚苯胺纳米纤维的电化学制备

采用恒电位电聚合法制备了樟脑磺酸(CSA)掺杂的旋光异构性聚苯胺(PANI)纳米纤维. 用扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 紫外-可见吸收光谱(UV-Vis)和圆二色光谱(CD)对PANI纳米纤维的形貌和光学性质进行表征, 结合电聚合溶液胶束平均粒径和ζ电位的测定, 研究了具有旋光异构性PANI纳米纤维的形成机理和具有增强旋光异构性的原因. 所制备的PANI纳米纤维具有无双螺旋结构, 其形貌不随着苯胺浓度的改变而变化. 不同手性樟脑磺酸掺杂制备的PANI纳米纤维具有镜像对称的旋光异构性, 且具有较高的椭圆偏振率. 这种手性PANI纳米纤维的颜色和旋光性均可通过化学掺杂/去掺杂或电化学掺杂改变氧化还原态而呈现可逆变化.     

界面扩散聚合法制备樟脑磺酸掺杂聚苯胺纳米管或纳米纤维及其电化学电容行为研究

利用界面扩散聚合法制得了樟脑磺酸掺杂聚苯胺纳米管或纳米纤维.扫描电镜(SEM )和透射电镜(TEM)表明所生成的聚苯胺纳米管径与樟脑磺酸浓度成反比,且低浓度的苯胺和掺杂剂有利于管状及纤维状聚苯胺的形成.充放电测试结果表明,聚苯胺纳米管在5mA放电时电容值可达2 4 9F g ,比相同条件下聚苯胺纳米纤维的比电容高14 . 7% ,而比聚苯胺粉末的比电容高4 1 .5 % .     

低温合成樟脑磺酸掺杂聚苯胺微管的电化学电容行为

在低温条件下合成了长约为2-3 μm, 外径约为300-400 nm 的樟脑磺酸掺杂聚苯胺微管. 扫描电镜(SEM)和透射电镜(TEM)显示, 生成的聚苯胺微管管径受樟脑磺酸浓度的影响, 高浓度的掺杂剂有利于管状聚苯胺的形成. 采用交流阻抗、循环伏安、恒流充放电等测试技术对不同产物的电化学电容行为进行了研究, 结果表明, 苯胺单体与樟脑磺酸的摩尔比为1:1时所得掺杂态聚苯胺电极具有较好的循环稳定性, 单电极比电容达到522 F·g-1.     

羧甲基壳聚糖掺杂聚苯胺的制备及其在盐酸溶液中对碳钢的缓蚀性能研究

选用结构中同时带有羟基、羧基和氨基的羧甲基壳聚糖为掺杂酸,通过改变掺杂酸与苯胺单体的比例实现了产物从纳米纤维(直径为100nm)到空心微米小球(直径为200nm)的转变.傅立叶红外(FTIR)和紫外可见光谱(UV)表征结果表明,纳米纤维和空心微米小球均为掺杂态聚苯胺.另外,采用电化学交流阻抗技术和动电位极化方法研究了所得聚苯胺在0.5mol/L盐酸溶液中对碳钢的缓蚀作用.结果表明,聚苯胺的加入量为40mg/L时,其对碳钢的缓蚀效率高达91.6%～92.3%.     

不同掺杂酸对纤维聚苯胺电化学性能的影响

采用界面聚合法通过不同质子酸掺杂分别制备了平均直径约为50,62,95nm的纤维聚苯胺。通过傅里叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、透射电镜(TEM)对其化学组成和微观形貌进行了表征,采用循环伏安、恒流充放电和交流阻抗研究了不同质子酸掺杂纤维聚苯胺的超级电容器电容行为,并利用X射线衍射(XRD)、氮气吸脱附及X射线光电子能谱(XPS)等方法对纤维聚苯胺的微观结构进行了深入研究。结果表明:高氯酸(HClO4)掺杂制备的聚苯胺在0.5A/g电流密度下的比容量可以达到397F/g,高于盐酸(HCl,334F/g)和樟脑磺酸(HCSA,383F/g)掺杂聚苯胺的测试结果,纤维的电化学性能主要受其规整度、孔隙率及掺杂度的影响。     

氯化铁氧化掺杂的聚苯胺纳米纤维团簇

没有外加质子酸的条件下,以氯化铁为氧化剂和掺杂剂,在界面体系中由苯胺(An)采用“无模板”的方法成功地制备了电导率为10-2～10-1S/cm的聚苯胺纳米纤维(d=20～30nm).实验证明FeCl3同时起到氧化剂和掺杂剂的双重作用,从而进一步简化了导电聚苯胺纳米纤维的合成条件.与使用过硫酸铵为氧化剂的传统聚合方法相比,FeCl3较小的氧化/还原电位使产物具有较小的直径和较高的结晶性.同时发现聚苯胺的形貌和电导率均与[FeCl3]/[An]的比例有关.FTIR,UV-Vis,XRD结构表征证实所得的聚苯胺纳米纤维为掺杂态.     

蒙脱土基氮掺杂多孔碳@聚苯胺复合材料的制备及电化学性能

分别在盐酸和樟脑磺酸-盐酸混酸溶液中,在蒙脱土基新型氮掺杂多孔碳表面原位聚合苯胺,以制备氮掺杂多孔碳@聚苯胺复合电极材料,采用红外光谱(FTIR)、X射线衍射(XRD)和扫描电子显微镜(SEM)表征复合材料的组成和形貌。 盐酸掺杂的复合材料呈短棒状形貌,樟脑磺酸-盐酸掺杂材料形貌呈颗粒状及交联片状,樟脑磺酸-盐酸掺杂的结晶性能优于盐酸掺杂。 电化学测试结果表明,樟脑磺酸-盐酸掺杂的复合材料在0.5 A/g电流密度下的质量比电容为412.5 F/g,比盐酸掺杂的(332.4 F/g)高24.1%,等效串联电阻(R_s)和电荷迁移电阻(R_ct)小;但盐酸掺杂的复合材料在大电流下电容保持率为81.4%,高于混酸掺杂的58.4%。     

四种方法合成单一手性聚苯胺纳米纤维研究

以过硫酸铵或2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）为氧化剂,单一手性樟脑磺酸作为诱导酸及掺杂剂,在有机溶剂、水-有机溶剂和水溶剂体系中,采用四种不同方法分别进行了单一手性聚苯胺纳米纤维合成研究。通过扫描电子显微镜（SEM）、紫外可见光谱（UV-VIS）、X射线衍射（XRD）和圆二色谱（CD）等手段对自组装法、界面聚合法、低聚物辅助法与二次掺杂法等四种方法制备得到聚苯胺纳米纤维的形貌、结构及光学活性进行表征,对比分析后发现四种方法合成的掺杂态聚苯胺纳米纤维形貌、结构相似,但溶剂体系会影响最终产物的光学活性：水溶剂、有机溶剂体系中,得到的聚苯胺纳米纤维光学活性相反。     

聚苯胺/顺丁橡胶复合导电膜的制备与性能(Ⅱ)

采用再掺杂方法制得了樟脑磺酸掺杂的聚苯胺(PAn-CSA),用溶液共混法制备PAn／BR导电复合膜．研究了聚苯胺与顺丁橡胶(BR)复合膜在间甲酚二次掺杂前后电导率的变化。实验表明:CSA对聚苯胺有较好的掺杂作用;二次掺杂使PAn复合膜电导率明显提高,其导电渗滤阈值略有降低,使卷曲的二次掺杂PAn链展开并通过分子链间的相互作用而自行组成导电通路．     

高能球磨法固相掺杂制备樟脑磺酸掺杂聚苯胺

通过高能球磨方法引发樟脑磺酸(CSA)对本征态聚苯胺(PANI)的固相掺杂反应, 制备了樟脑磺酸掺杂聚苯胺(PANI-CSA)粉末. 采用SEM, XRD, FT-IR等分析方法对所得的PANI-CSA进行了形貌和结构表征, 采用四点探针法对电导率进行了测定. FT-IR图谱的变化反映了聚苯胺的质子化过程, 而XRD谱图表明, 聚苯胺分子链在外力诱导下形成了有利于电荷传导的取向排列. 系统地研究了球磨时间对掺杂率和电导率的影响规律. 结果表明, 固相掺杂具有较高的掺杂速率, 其电导率和掺杂率均随球磨时间先增大后减小, 其最高电导率可达到3.25 S/cm, 对应掺杂率为0.31.     

Polyaniline nanofibers: chemical synthesis using surfactants

Nanofibers of doped polyaniline.HCSA having diameters 1-2 nm are observed in TEM images of bath sonicated aqueous dispersions of larger nanofibers (30-50 nm diameter) synthesized by surfactant-assisted chemical oxidative polymerization of aniline in dilute aqueous organic acids.     

The stabilization of electrospun chitosan nanofibers by reversible acylation

Chitosan nanofibers fabricated by electrospinning are contaminated by acidic anions from the acid spinning solution, leading to instability of the nanofibers in aqueous solutions, and the traditional fiber treatment method will also lead to the deterioration of the nanostructure. Here we demonstrate a novel approach to removing the acidic anions with full preservation of the nanofibrous structure. The as-spun nanofibers are first protected (stabilized) by reversible acylation. Second, contaminants are then eliminated by hydrolysis; finally, acylation is reversed. Chemical analysis showed the removal of the acidic anions and the graft and removal of acyl groups. Morphological analysis showed that the reversibly acylated fibers had diameters <150 nm and nanofiber structure was maintained after immersion in aqueous solution. The membranes also were compatible with bone cells in culture. The resultant pure chitosan nanofibers show excellent stability in aqueous solution and exhibit broad potential in biomedical applications.     

Spectral characteristics of polyaniline nanostructures synthesized by using cyclic voltammetry at different scan rates

The polyaniline nanofibers with different sizes were synthesized by using cyclic voltammetry at different potential scan rates, in the presence of ferrocenesulfonic acid. The potential scan rate controlled the formation and growth of polyaniline nuclei, which plays a key role in controlling nanofiber sizes. The average diameters of nanofibers decreased from about 130 nm to about 80 nm as the potential scan rate increased from 6 to 60 mV s (-1). We first observed an ordered change in the following spectra with the nanofiber sizes of polyaniline. The spectra of the X-ray diffraction indicated that the partially crystalline form existed in the polyaniline nanofibers and that the crystallinity of polyaniline increased with decreasing diameter of polyaniline nanofibers. The ESR spectra revealed the fact that the decrease in the intensity of the ESR signal was accompanied by the increase in the value of the peak-to-peak line width Delta H pp as the diameter of polyaniline nanofibers decreased. The (1)H NMR spectra showed that a peak in a triplet caused by the +/- NH free radical was split into two peaks with different intensities and that their relative intensity also changed with the diameter of the polyaniline nanofibers.     

Study on Nanofibers of Polyaniline via Interfacial Polymerization

Uniform polyaniline nanofibers were prepared by interfacial polymerization. The nanofibers had a diameter of 80 nm and a length of about 1μm. The effect of centrifugal force on the morphology of the nanofibers is discussed. In situ UV‐Vis spectra indicated that the interfacial polymerization process was similar to the solution polymerization process. An “expanded‐partly doped” stage of interfacial polymerization was observed for the first time in the in situ UV‐Vis spectra.     

Electric field sensitivity of conducting hydrogels with interpenetrating polymer network structure

In this article, we reported the synthesis, structure and electric field sensitivity of polyacrylate/polyaniline (PAA/PANI) and poly(2-acrylamido-2-methyl propylsulfonic acid-acrylic acid)/polyaniline [P(AMPS-AA)/PANI] conducting hydrogels with an interpenetrating polymer network (IPN) structure. Scanning electron microscope showed that the conducting hydrogels presented porous structures consisting of PANI nanofibers. The results of Fourier-transform infrared and X-ray diffraction revealed that the PANI was in its conductive emeraldine state and partial crystallization. The unique morphology and molecular structure of the conducting hydrogels were expected to show unusual electric field responses. The conducting hydrogels were subjected to an electric field in NaCl solution for bending behaviors. It was demonstrated that the electric field response was improved by increasing aniline dosage, applied voltage and concentration of aqueous NaCl solution. The bending mechanism was attributed to polyelectrolyte hydrogel matrix and emeraldine PANI nanofibers.     

2,3-二氨基丙酸钴(Ⅱ)配合物的可逆氧合性能

通过UV-Vis光谱和氧电极实验证明2,3-二氨基丙酸(DAPA)钴(Ⅱ)配合物在水溶液中具有良好的吸氧性能和吸氧-放氧可逆性. 根据配合物光谱随pH值变化的pH-A曲线可知, 该配合物在pH值高于6.5后发生氧合反应, 在pH=7.0~10.0范围内生成稳定的形态; 在pH=8时用等摩尔比法及量气法对氧合配合物的组成比进行了测定, 得出n(Co)∶n(DAPA)∶n(O₂)=1∶2∶1; 在波长384 nm和pH=7.0条件下, 利用UV-Vis光谱考察了配合物在室温、 水溶液中的吸氧-放氧反应动力学, 结果表明, 该配合物在85 h内连续吸氧-放氧可逆循环150次后仍具有5%的氧合能力.     

Bicomponent aligned nanofibers of N-carboxyethylchitosan and poly(vinyl alcohol)

Bicomponent nanofibers of N-carboxyethylchitosan (CECh) and poly(vinyl alcohol) (PVA) were obtained by electrospinning of mixed aqueous solutions. The electrospinning of CECh-containing nanofibers was enabled by the ability of PVA to form an elastically deformable entanglement network based on hydrogen bonds. The average diameters of the bicomponent fibers were in the range 100-420 nm. Water-resistant nanofibrous mats were obtained by thermal crosslinking at 100 °C for 10 h. Nanofibrous materials with 1D-, 1D-transversery or 3D fiber alignment were obtained depending on the type of the collector used.     

水性聚苯胺纳米线超级电容器电极材料

使用"假高稀"方法,分别以过硫酸铵、硝酸铁和三氯化铁为氧化剂,含有1个乙氧基基团的酸性磷酸酯为质子酸,经过原位聚合制备了直径分别为78～90 nm、18～30 nm和16～25 nm水分散性聚苯胺纳米线.聚苯胺膜的电导率分别为18,32和35 S cm-1,比表面积为65,70和82 m2g-1.该聚苯胺纳米线能够很好地分散在水中,是一种环境友好型超级电容器电极材料.该电极材料在1 mol L-1四乙基氟硼酸/碳酸丙烯酯非水性电解液中,在-1～1 V扫描范围内,以0.4 A g-1的放电速率下,分别得到了110,140和152 F g-1的比容,比电容与材料的比表面积和电导率有关,随着比表面积以及电导率的增大而增大.聚苯胺纳米线电极材料有较高的充放电效率(大于98%),表明了它们有很好的电化学可逆性.     

A practical way to prepare thin polyaniline nanofibers with ferric nitrate as an oxidant

A practical approach to prepare thin fibrillar polyaniline was developed using ferric nitrate as an oxidant without any external dopants and templates. Doped polyaniline was directly obtained with iron (III) nitrate anion connected to imine atoms in the polyaniline backbone. The diameter and conductivity of the polyaniline nanofibers were 15～28 nm and Ca. 10^?1 S/cm, respectively and they were strongly affected by the molar ratio of ferric nitrate to aniline. The formation mechanism of the nanofibers was proposed to be aniline oligomerical micellar self-assembly.