微波合成ZnO微米"花"

以硝酸锌为锌源,乙醇胺为矿化剂,水为溶剂,微波加热20 min,合成了由微米棒自组装而成的ZnO微米"花" (1),其结构和形貌经X-射线衍射、场扫描电子显微镜和透射电子显微镜表征.结果表明,1由六棱柱形的微米棒自组装而成,微米棒长度1 μm～1.5 μm,直径300 nm～500 nm.     

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%.     

珊瑚状表面形貌聚苯胺亚微米颗粒的制备与表征

采用与传统制备方法不同的加料顺序,即将苯胺单体溶液滴加到过硫酸铵氧化剂溶液中,制备了具有珊瑚状表面形貌的聚苯胺亚微米级颗粒.扫描电子显微镜(SEM)表征表明这种聚苯胺颗粒的表面形貌非常的粗糙,并有大量纳米级的小凸起.使用3种不同的聚乙烯醇(PVA),即1799、1788和CP-1000,为稳定剂,得到的聚苯胺颗粒分别为PANI-1、PANI-2和PANI-3,均具有珊瑚状表面形貌.颗粒的平均尺寸分别为250,215和140 nm.颗粒的尺寸分布也随尺寸的降低而明显变窄.可见,稳定剂PVA在水中溶解性的好坏和分子量大小对聚苯胺颗粒的聚集程度和尺寸大小有很大的影响.通过傅里叶变换红外光谱(FTIR),热失重分析(TGA),粉末X-射线衍射(XRD),四探针电导率测试仪和N2吸脱附表征对得到的聚苯胺颗粒的化学结构、热稳定性、结晶结构、电性能和比表面积进行了全面的表征.聚苯胺颗粒的电导率可以达到2.7 S·cm-1.对珊瑚状表面形貌的形成机理进行了探讨.     

聚苯胺纳/微米结构薄膜的制备及对pH传感的影响

考察了溶液酸度对纳/微米结构聚苯胺生长的影响. 在0.1 mol/L硫酸、pH=4和pH=7的磷酸缓冲溶液及0.1 mol/L氨水中, 在冰冻条件下氧化聚合苯胺单体, 在溶液中和浸入反应溶液的玻璃基底上分别得到一系列不同形貌的聚苯胺, 如: 纳米仙人球、微米席子、微米片、微米花、三维网络、微米树状物和微米枝等. 各种形貌的形成机理归结为pH的影响和冰的晶体结构的模板作用. 另外, 浸入反应溶液的基底诱导作用和聚合物扩散受限生长导致基底上树状结构的形成. 基底上原位沉积的薄膜直接用于对pH缓冲溶液的响应研究, pH范围宽(pH=3~9), 反应灵敏.     

无模板法聚苯胺纳米管的制备及表征

以过硫酸铵(APS)为氧化剂,在无模板,无掺杂酸条件下,利用超声辅助合成了聚苯胺纳米管.通过透射电子显微镜、傅里叶红外光谱、紫外-可见光谱、X-射线衍射对产物的形貌、结构和性能进行了表征.研究表明,形成的聚苯胺纳米管内径约为10 nm,外径约为80 nm,长度约为26μm,且管径均匀.苯胺单体浓度越高,聚合速率越快.但是,聚苯胺的形貌与苯胺单体的浓度无关,而与苯胺和过硫酸铵的摩尔比有关.超声在纳米管的形成中起主要作用,它阻止球状胶束无规则团聚,使得在较高的苯胺浓度下(0.2 mol/L)也可形成纳米管.合成的聚苯胺电导率为5×10-3S·cm-1,结晶度不高.     

氢氧化镍微米棒的合成和表征

以NiCl₂为镍源,乙二醇(EG)为溶剂,采用溶剂热法成功地制备了β-Ni(OH)₂微米棒,制备方法简单、易行。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、傅立叶红外光谱(FTIR)和电感耦合等离子直读光谱仪(ICP)对产物的形貌和物质结构进行了表征,证实了反应中间体是Ni-EG配合物。利用扫描电子显微镜(SEM)考察了实验参数,如聚乙二醇200浓度、反应温度和反应时间,对产物形貌的影响,结果表明一维棒状β-Ni(OH)₂的形成经历了溶解-再结晶的过程。Ni-EG配合物经退火处理,可以得到由纳米线自组装的NiO微米管。     

水热法制备聚苯胺及其铁氧化物纳米复合材料

利用水热法与无模板自组装法相结合, 以三氯化铁为氧化剂、 掺杂剂和反应物, 制备了聚苯胺及其铁氧化物纳米复合材料. 结果表明, 通过改变三氯化铁的浓度可以调控产物的微观结构和组成. 当三氯化铁的浓度≤0.13 mol/L时, 产物组成为未掺杂的低聚苯胺与α-Fe₂O₃的复合纳米材料, 其微观结构为纳米颗粒组装成的椭球体和准立方体; 当三氯化铁的浓度≥0.20 mol/L时, 产物组成为掺杂态聚苯胺, 其微观结构为纳米片层结构组装成的微米级大丽花球; 并且产物的粒径随三氯化铁浓度的增大而增大. 利用扫描电子显微镜、 红外光谱、 紫外-可见光谱、 X光电子能谱及X射线衍射等手段对产物的微观结构和组成进行了表征, 并探讨了产物的形成机理.     

加热覆盖有ZnCl2溶液的锌片制备ZnO亚微米棒阵列

将表面覆盖有ZnCl2溶液的锌片加热到400 ℃反应1 h, 在锌片上生长出了ZnO亚微米棒阵列. 采用扫描电镜、透射电子显微镜和X射线衍射仪对所制备的产物进行了表征和分析. 结果表明产物为六方相纤锌矿单晶结构的ZnO亚微米棒, 其直径和长度分别为300～650 nm和6 μm, 提出了ZnO亚微米棒可能的生长机理. 在波长为300 nm光的激发下, 发现了ZnO亚微米棒阵列具有发光峰位于395 nm强的紫外光发光和位于490 nm弱的蓝绿光发光, 这两种发光分别起源于ZnO宽带隙带边发射和ZnO中相应的缺陷结构.     

基于MBA凝胶纤维的RAFT聚合制备聚合物微米管

以三乙二醇双丙烯酸酯(TEGDA)为共聚单体, 通过可逆加成-断裂链转移(RAFT)聚合反应, 将N,N'-亚甲基双丙烯酰胺(MBA)凝胶纤维直接转化为聚合物微米管. 用扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 红外光谱(FTIR)和元素分析等表征了聚合物微米管的结构和组成. 研究结果表明, TEGDA的加入可显著提高聚合物微米管的产率, 并使其具有自支撑性. 环境扫描电子显微镜(ESEM)原位表征结果表明, 聚合物微米管具有一定的溶剂溶胀性能. 采用流变仪测定了加入TEGDA前后的聚合物凝胶的机械性能, 相对于MBA凝胶, 聚合物凝胶的机械性能显著提高.     

由苯胺二聚体电化学制备聚苯胺的形貌可控性初探

以苯胺二聚体（N-phenyl-p-phenylenediamine）为起始单体,在1 mol·L^-1高氯酸水-乙腈混合液中,玻碳电极表面电化学制备聚苯胺. 实验结果表明,苯胺二聚体单体的聚合电位比苯胺单体的低约0.2 V,并且其聚合物具有更高的形貌可控性. 苯胺二聚体单体浓度分别为1、5和10 mmol·L^-1时,采用分步恒电流法可分别制备出形貌均一的聚苯胺纳米粒子（粒径30 nm）、超长的纳米线（> 5 μm 直径50 nm）和大面积纳米片（4 μm × 2 μm × 30 nm）.     

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.     

One-pot surfactantless route to polyaniline hollow nanospheres with incontinuous multicavities and application for the removal of lead ions from water

Polyaniline (PANI) hollow nanospheres with controllable incontinuous nanocavities ranging in size from 10 to 50 nm as a novel hollow nanostructure have been successfully fabricated by chemical polymerization of aniline with chloroaurate acid as the oxidant and citric acid as the doping acid. Experimental factors, such as concentration and kind of oxidant and doping acid, were investigated to illustrate their effect on morphology of PANI. According to experimental results and time-dependent investigations, a possible formation mechanism involved was then proposed. The adaptability of this route to hollow nanostructures with multicavities of other conducting polymer was also revealed. Furthermore, the adsorption properties of PANI hollow nanospheres toward lead ions in water were investigated.     

原位聚合法制备PANI/PET导电织物及其性能分析

在聚酯纤维基材及其织物表面,原位聚合形成厚度约1~2μm聚苯胺包覆层,制得聚苯胺(PANI)/聚酯(PET)导电织物.PANI层优异的导电性能使之成为有广阔发展前景的柔性电磁屏蔽材料.正交试验分析研究了苯胺单体浓度、氧化剂:苯胺摩尔比、掺杂酸浓度、反应时间对PANI包覆层外观形态、与基体结合牢度以及导电性的影响.实验表明:在经适当前处理的PET基材表面,以苯胺单体浓度为0.25mol/L、氧化剂与苯胺摩尔比为1∶1、掺杂酸浓度0.5 mol/L、反应时间60 min、反应温度为0~20℃时制备的PANI/PET导电织物方阻最小,导电性最好;掺杂酸酸性越强,导电性越好.SEM、FTIR及XRD测试表明涤纶织物表面有均匀连续的聚苯胺膜存在.分析表明聚苯胺分子链中氧化结构与还原结构含量基本相等,说明聚苯胺渗入纤维内部,使纤维无定形区面积增加,结晶度减小.     

Synthesis of PANI and Study of Morphology in the Process of Polymerization

The polyaniline micro/nanostructure was prepared by a self‐assembly process with molybdic acid as dopants in the presence of ammonium persulfate as the oxidant. It was found that the morphology of PANI micro/nanostructure was affected by the concentration of the dopant, that is, the morphology of PANI changed from nanofibers to co‐existence of nanofibers and microspheres as the molar ratio of molybdic acid to aniline varied from 0.01 to 1.5. Under the same condition it was also found that the conductivity value of PANI enhanced from 4.58×10^?3 S·cm^?1 to 3.8×10^?1 S·cm^?1. The structure of PANI was characterized by FTIR and XRD which confirmed the presence of the molybdic acid in the PANI. The electrochemical characteristics of the PANI nanofibers were investigated by means of cyclic voltammetry. The morphology of PANI in the process of polymerization was characterized by SEM. It was found that when the molar ratio of molybdic acid to aniline was 0.3, the morphology of PANI was co‐existence of nanofibers and microspheres and the formation of microspheres was ahead of the nanofibers.     

乳液聚合中聚苯胺膜形成的动力学研究

以(NH4)2S2O8(APS)为氧化剂,十二烷基苯磺酸(DBSA)同时为乳化剂和掺杂剂,采用乳液聚合方法制备聚苯胺膜(PANIfilm),用石英晶体微天平(QCM)实时监测聚苯胺膜的形成过程,并对其动力学过程进行研究.结果表明,聚苯胺成膜反应对APS是0.5级,对苯胺是1级,聚苯胺膜增长速率随温度的升高而增加,而聚苯胺膜的最终沉积量却减小,表观活化能Ea=41.15kJ/mol,与均相溶液聚合成膜法的结果相近;随着DBSA浓度的增加,聚苯胺膜增长速率减小,而最终的沉积量增大.     

Lipid nanotubes and microtubes: experimental evidence for unsymmetrical monolayer membrane formation from unsymmetrical bolaamphiphiles

Unsymmetrical bolaamphiphiles, omega- [N-beta-D-glucopyranosylcarbamoyl] alkanoic acids, with even-numbered oligomethylene chains (12, 14, 16, 18, and 20 carbons) self-assembled in water to form lipid nano- and microtubes. The tubular assemblies were separated by centrifugation and examined by transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy to study the molecular packing within the tubular membranes. The nanotubes encapsulated the staining reagent phosphotungstate, which revealed them to be hollow cylinders up to several hundred micrometers long with 30-43-nm outer diameters and 14-29-nm inner diameters. By comparing the membrane stacking periodicity obtained from powder X-ray diffraction analysis of the dehydrated tubes with the molecular packing within single crystals, we found that the nanotubes consist of an unsymmetrical monolayer lipid membrane (MLM) in which the molecules are packed in a parallel fashion. This suggests that the inner surface of the nanotubes is covered with carboxy headgroups and the outer surface with 1-glucosamide headgroups. The inner diameters of the lipid nanotubes could be controlled in the range 17.7-22.2 nm in steps of approximately 1.5 nm/two carbons by varying the oligomethylene spacer length. The microtubes had three types of molecular arrangements. The first type was a symmetrical MLM in which the molecules were packed in an antiparallel fashion. The other two types had unsymmetrical MLM stacking with head-to-head and head-to-tail motifs. Increasing the number of oligomethylene spacers stabilized the unsymmetrical MLM structure in both nano- and microtubes.     

有机化学接枝-电化学沉积聚合制备CNTs/PANI纳米复合材料

通过有机化学合成法先在碳纳米管表面接枝上苯胺单体,然后在不锈钢电极表面在硫酸溶液中采用循环伏安法电化学沉积聚合制得碳纳米管/聚苯胺(CNTs/PANI)纳米复合材料.扫描电子显微镜和傅立叶变换红外光谱表征所得材料的微观结构和基团,循环伏安和恒流充放电测试用于考察所得CNTs/PANI纳米复合材料的电化学性能.所得结果与...     

Polyaniline Microtubes with a Hexagonal Cross‐Section and pH‐Sensitive Fluorescence Properties

Polyaniline (PANI) microtubes with a hexagonal cross‐section are successfully synthesized by a self‐assembly process in the presence of 8‐hydroxyquinoline‐5‐sulfonic acid (HQS) as a dopant and FeCl₃ as an oxidant. The wall thickness of the PANI/HQS microtubes can be adjusted by the content of the oxidant. It is proposed that the aniline/HQS salts serve as a hard template for the formation of the hexagonal‐cross‐section microtubes. Moreover, PANI/HQS microtubes combined with ZnSO₄ show pH‐dependent fluorescence. PANI hexagonal‐cross‐section microtubes combined with a pH‐sensitive fluorescence may promise potential applications in fields such as chemical sensors and confined reaction vessels.

     

Micelle-assisted one-pot synthesis of water-soluble polyaniline-gold composite particles

A micelle-based method to synthesize dispersed polyaniline (PANI)-Au composite particles by direct oxidation of aniline using AuCl4- as the oxidant is presented. The obtained composite particles have a core-shell structure, where Au nanoparticles of 20 nm mean diameter are encapsulated by PANI of well-defined tetrahedron shape with 150 nm average edge length. The polaron band of the dispersed PANI-Au composite particles is centered at 745 nm and is rather narrow compared to the broad 835 nm absorption of PANI synthesized by the IUPAC procedure. The surface plasmon absorption of Au nanoparticles normally centered at around 520 nm is absent in the composite particles with oxidized PANI. Our results point to a strong electronic interaction between the encapsulated Au nanoparticles and the shell of oxidized PANI. Films and pellets produced from these composite particles show a twofold higher conductivity than IUPAC PANI.     

Polymerization of aniline on polyaniline membranes

When solutions of aniline hydrochloride and ammonium peroxydisulfate were separated by a semipermeable cellulose membrane, the reactants met at the membrane and produced a polyaniline (PANI) membrane at the interface. The oxidative polymerization of aniline then proceeded in situ on the PANI-cellulose composite membrane. PANI was produced entirely at the monomer side of the membrane; about 80% conversion of aniline to PANI was observed after 24 h. The oxidation of aniline with peroxydisulfate consists in the transfer of electrons from aniline to the oxidant; it is proposed that electrons pass through the PANI membrane, which is conducting, and electroneutrality is maintained by the simultaneous transfer of protons. The reaction between aniline and peroxydisulfate thus takes place without the need for both reactant molecules to be in physical contact. The residual aniline is located only at its original side of the membrane, but the product of ammonium peroxydisulfate conversion, ammonium hydrogen sulfate, was found on both sides of the membrane. Fourier-transform infrared spectroscopy has been used to analyze PANI, the reaction residues and byproducts, and to prove that PANI is protonated with counter-ions of the sulfate type. Using this technique, we have detected only small differences in the molecular structure of PANI prepared with the membrane-separated reactants and in the polymerization when reactants were mixed; also, the molecular weights differed only marginally. The conductivity of both types of PANI was about the same. The repeated polymerization of aniline on the earlier prepared PANI-cellulose membrane yielded similar results, thus confirming the proposed concept of coupled electron- and proton-transfer through the PANI membrane.