二次掺杂制备聚苯胺/石墨烯/碳纳米管复合材料及其防腐性能EI北大核心CSCD

在高氯酸体系中通过原位聚合将苯胺(ANI)单体分别与还原氧化石墨烯(RGO)、碳纳米管(CNTs)制备了一次掺杂态产物PANI/RGO和PANI/CNTs,产物分别经氨水解掺杂后,在高氯酸体系中经二次掺杂制备得到二次掺杂态聚苯胺/石墨烯/碳纳米管(Redoped PANI/RGO/CNTs)复合材料。通过扫描电镜、透射电镜、傅里叶变换红外光谱和紫外光谱对其不同产物形貌和结构进行表征,通过电化学工作站测试了不同产物在3.5%NaCl溶液的防腐蚀性能。结果表明,在RGO与ANI质量比为1:20、CNTs与ANI质量比为1:20时,二次掺杂态产物中聚苯胺纳米纤维可分别在RGO和CNTs上均匀生长并形成网状结构,纤维长度达到850 nm,形貌均一,其防腐蚀性能最优异,缓蚀效率可达81.79%。通过二次掺杂将PANI/RGO和PANI/CNTs复合制备Redoped PANI/RGO/CNTs材料,可有效避免石墨烯和碳纳米管在制备复合材料过程中的团聚,得到结构规整、防腐性能更优异的复合材料。     

石墨烯/聚苯胺/四氧化三锰纳米复合材料的制备

成功制备了石墨烯/聚苯胺/四氧化三锰(RGO/PANI/Mn_3O_4)纳米复合材料。首先,以过硫酸铵(APS)为氧化剂,在氧化石墨烯(GO)片层上氧化聚合苯胺单体,制备氧化石墨烯/聚苯胺(GO/PANI),再通过水热法将GO还原并热解Mn(Ac)_2·4H_2O从而制得RGO/PANI/Mn_3O_4复合材料。形貌和结构表征结果表明Mn_3O_4纳米颗粒均匀生长在以PANI为导电连接层的RGO片层上。     

SnO2/还原氧化石墨烯/聚苯胺三元复合物的合成及电化学性能

采用两步法成功构筑SnO2/还原氧化石墨烯/聚苯胺(SnO2/RGO/PANI)三元复合材料。首先制备出均匀分散的SnO2/还原氧化石墨烯(SnO2/RGO)二元复合物,然后再以二元复合物为载体,通过苯胺(An)单体的化学氧化聚合获得终端产物。利用傅里叶红外光谱(FT-IR)、X射线衍射(XRD)和场发射扫描电镜(FESEM)对复合材料的结构和形貌等物理性质进行表征,利用循环伏安测试、恒电流充放电测试和交流阻抗测试对复合材料的电化学电容性能进行研究,并讨论了PANI的含量对复合材料的结构和性能的影响。结果表明,所合成的三元复合材料的比电容随PANI含量的增加而增大,最大达到424.8F/g,其电容性能的增强源于SnO2、RGO与PANI三者的相互协同作用。     

二次掺杂聚苯胺的合成及其导电性能的研究

掺杂态的聚苯胺(PANI)合成是采用快速直接法合成盐酸/PANI,用氨水水解掺杂态,得到本征态PANI,再用对甲苯磺酸对PANI进行二次掺杂。在不同反应摩尔比、不同反应时间、不同反应温度下合成的对甲苯磺酸/PANI,用于测量电导率,得出优化条件。采用透射电镜(TEM)观察其形貌,并利用红外光谱和紫外光谱对其结构进行了表征。     

以氧化石墨烯为氧化介质制备石墨烯/聚苯胺导电复合材料

采用超声辅助Hummers法制得厚度约为1 nm的氧化石墨烯, 以其为氧化介质与苯胺反应合成了石墨烯/聚苯胺(RGO/PANI)导电复合材料。利用AFM、SEM、XRD和FTIR对反应所得产物进行了表征。结果表明: 苯胺在略高于室温的酸性水溶液中可以对氧化石墨烯(GO)进行还原, 而苯胺自身则被氧化石墨烯中大量的含氧基团氧化并发生聚合反应, 最终生成RGO/PANI导电复合材料, 当苯胺用量为1 mL, 氧化石墨烯用量为0.1 g, 在水浴温度为70 ℃下剧烈搅拌24 h时, 获得的RGO/PANI复合材料导电性最佳, 约为10 S/cm。     

羟丙基壳聚糖掺杂聚苯胺在0.5mol/L盐酸中对碳钢的缓蚀性能

目前,将廉价的羟丙基壳聚糖(HPCS)与掺杂态聚苯胺(PANI)联合用作金属缓蚀剂鲜见研究。以羟丙基壳聚糖、苯胺(An)为原料,采用化学氧化法合成了羟丙基壳聚糖掺杂态聚苯胺(HPCS-PANI),利用傅里叶变换红外光谱(FTIR)对合成产物进行表征,表明合成产物是HPCS-PANI。用失重法、电化学法研究了HPCS-PANI在0.5 mol/L HCl中对Q235碳钢的缓蚀性能。结果表明:合成的HPCS-PANI为吸附型缓蚀剂,在Q235碳钢表面的吸附服从Langmuir吸附等温式,在浓度50 mg/L时对Q235碳钢在0.5 mol/L HCl中的缓蚀效率最大,达88.94%。     

聚苯胺与丙烯酸树脂共混研究及复合导电膜的制备

采用溶液聚合法制备了掺杂态聚苯胺(PANI)的二甲苯溶液,研究了掺杂态PANI与几种丙烯酸树脂共混体系的导电性能.并分别以丙烯酸树脂和掺杂态PANI/丙烯酸树脂为成膜基质,添加导电填料,制备出复合导电涂膜.探讨了PANI的加入对导电性能的影响,并采用SEM手段,分析了涂膜表面微观形貌的变化.     

石墨烯-聚苯胺复合氨敏膜的制备及应用

以石墨烯和苯胺为原料,采用原位自组装技术制备了石墨烯-聚苯胺(PANI)复合氨敏膜。利用紫外-可见光谱、扫描电镜对薄膜结构、微观形貌进行了表征;测试了基于复合薄膜的氨气传感器的响应性能;分析了薄膜与氨气分子的作用机理,并研究了石墨烯掺杂量和制备工艺对薄膜性能的影响。结果表明,石墨烯-聚苯胺复合薄膜对氨气具有良好的响应,其气敏特性明显优于单一的石墨烯薄膜和石墨烯/聚苯胺分层薄膜,分析认为石墨烯不仅为苯胺聚合提供了基体(成核模板),增大复合薄膜的比表面积,同时对聚苯胺具有掺杂作用,在复合薄膜中形成了π-π共轭结构。     

管状MnO2氧化制备聚苯胺纳米管及其超级电容性能

以管状二氧化锰(MnO2)为氧化剂和模板剂在酸水体系中化学氧化制备了聚苯胺(PANI)纳米管。采用能谱仪、扫描电镜、透射电镜、红外光谱、循环伏安、恒流充放电及交流阻抗谱等测试手段对其结构和电化学性能进行测试;研究不同苯胺单体(ANI)的用量对PANI结构和电化学性能的影响。结果表明,制备的聚苯胺为内径约90nm,外径约350nm,长约2μm的纳米管;在m(MnO2)∶m(ANI)=9∶25时,合成的PANI管状结构比较丰富,在1mol/L H2SO4电解液中比电容达到473F/g。     

管状MnO2氧化制备聚苯胺纳米管及其超级电容性能

以管状二氧化锰(MnO2)为氧化剂和模板剂在酸水体系中化学氧化制备了聚苯胺(PANI)纳米管。采用能谱仪、扫描电镜、透射电镜、红外光谱、循环伏安、恒流充放电及交流阻抗谱等测试手段对其结构和电化学性能进行测试;研究不同苯胺单体(ANI)的用量对PANI结构和电化学性能的影响。结果表明,制备的聚苯胺为内径约90nm,外径约350nm,长约2μm的纳米管;在 m(MnO2)∶m(ANI)=9∶25时,合成的PANI管状结构比较丰富,在1mol/L H2SO4电解液中比电容达到473F/g。     

Electrical conductive and graphitizable polymer nanofibers grafted on graphene nanosheets: Improving electrical conductivity and flame retardancy of polypropylene

Polyaniline (PANI) nanofibers grafted reduced graphene oxide (PANI–RGO) is prepared using the “grafting-from” strategy and then is incorporated into polypropylene (PP) matrix by way of the master batch-based melt mixing method. Grafted PANI nanofibers can improve the dispersion and electrical conductivity of reduced graphene oxide (RGO). The electrical conductivity of the modified RGO and its composites is not impaired by the grafted polymer, due to the conductive characteristics of PANI. The barrier action of PANI–RGO can greatly inhibit the release of flammable pyrolysis products of PP. PANI–RGO exhibits a marked flame retardancy effect on PP. The smoke release of the composites is slightly retarded. Transmission electron microscopy image and Raman spectrum of the char residue for PANI–RGO based composite indicate the formation of carbon nanofibers during combustion. The in situ formed carbon nanofibers on graphene nanosheets can enhance barrier performance against heat and mass transfer, resulting in enhanced flame retardancy.     

三维聚苯乙烯/聚苯胺/石墨烯复合微粒的制备及电化学性能

为扩展石墨烯的宏观应用,制备性能优异的三维聚苯乙烯/聚苯胺/石墨烯(PS/PANI/graphene)复合微粒具有重要意义.以聚苯乙烯微粒为模板,通过2种浓度苯胺单体的原位生长得到2种聚苯乙烯/聚苯胺复合微粒,再利用氧化石墨烯与苯乙烯/聚苯胺微粒间的静电、共轭相互作用制备三维PS/PANI/graphene复合微粒.利用红外光谱(FTIR)、扫描电镜(SEM)、X射线衍射(XRD)、热重分析(TG)对其微观形貌、结构进行表征,利用电化学测试对三维复合微粒电化学性能进行测试.结果表明,复合材料保持了聚合物微粒的基本形貌,具有三维结构,并有优异的比电容(578 F/g)和循环稳定性(循环900次,容量保持81.5%),其电性能远优于单纯石墨烯和聚苯胺.     

Morphology and conductivity of polyaniline sub-micron fibers prepared by electrospinning

Sub-micron fibers of pure polyaniline (PANI) doped with sulfuric acid or hydrochloric acid were prepared by electrospinning PANI with suitable molecular weight dissolved in hot sulfuric acid. A modified electrospinning setup was employed with a coagulation bath as a collector, where dilute sulfuric acid was used as coagulation bath. The factors influencing the morphology and conductivity of the synthesized PANI fibers were investigated, including the concentration of dilute H₂SO₄ solution in the coagulation bath, the doped PANI concentration in H₂SO₄ solution, the type of doping acid and the voltage applied to the solution. The morphologies of doped PANI fibers were characterized by scanning electron microscope (SEM). The structure of the resulting fibers was analyzed by Fourier transform infrared spectroscopy and UV–vis spectrometer. The conductivity of PANI fibers were characterized by I–V characteristics. Homogeneous PANI fibers with a diameter of 370 nm and a high conductivity of 52.9 S/cm were prepared. The possible mechanisms of different morphology formation and conductivity of PANI fibers were also discussed.     

石墨烯-铁酸铋纳米晶复合材料的制备及其催化性能研究

BiFeO₃(BFO)是一种新型可回收光响应催化剂, 但较高的光生电子/空穴对复合率和较低的量子产率限制了其实际应用。本研究通过水热法制备出还原氧化石墨烯-BFO(RGO-BFO)纳米晶复合材料, 表征与测试结果表明, 相比于BFO颗粒, 复合材料的禁带宽度E_g为2.0 eV, 降低约10%; 40 min对亚甲基蓝吸附-催化效率接近100%, 远高于BFO颗粒(28%), 这主要由于复合体系中光生电子/空穴对复合率更低。通过本征磁性回收并重复利用6次后, 复合材料仍保持89.1%催化效率, 表现出优异催化性能。     

改性石墨烯/聚苯胺的制备及其环氧涂层的防腐蚀性能

为了改善环氧树脂防腐蚀涂料存在的孔洞缺陷,以改性石墨烯/聚苯胺复合材料作填料来提高环氧涂料的防腐蚀性能。首先采用改进的Hummers法制备了氧化石墨烯(GO),再利用对苯二胺还原GO得到改性石墨烯(PGO),进一步制备出改性石墨烯/聚苯胺(PGO/PANI)复合材料。通过拉曼光谱仪、场发射扫描电镜等研究了PGO/PANI的结构和微观形貌,利用盐雾试验、Tafel曲线和电化学阻抗谱研究了 PGO/PANI的防腐蚀性能。结果表明:PGO/PANI涂层的腐蚀等级由空白环氧涂层的10级提高到5级;PGO与PANI有良好的协同作用,PGO与苯胺单体质量比为0.10时,所制备的PGO/PANI复合涂层的防腐蚀效果较好,腐蚀电压为-194.59mV (vs SCE)、腐蚀电流密度为2.12×10^-9A/cm^2.     

High-performance asymmetric supercapacitors based on reduced graphene oxide/polyaniline composite electrodes with sandwich-like structure

The sandwich-like structure of reduced graphene oxide/polyaniline(RGO/PANI) hybrid electrode was prepared by electrochemical deposition. Both the voltage windows and electrolytes for electrochemical deposition of PANI and RGO were optimized. In the composites, PANI nanofibers were anchored on the surface of the RGO sheets, which avoids the re-stacking of neighboring sheets. The RGO/PANI composite electrode shows a high specific capacitance of 466 F/g at 2 m A/cm~2 than that of previously reported RGO/PANI composites. Asymmetric flexible supercapacitors applying RGO/PANI as positive electrode and carbon fiber cloth as negative electrode can be cycled reversibly in the high-voltage region of 0–1.6 V and displays intriguing performance with a maximum specific capacitance of 35.5 m F cm~(-2). Also, it delivers a high energy density of 45.5 m W h cm~(-2) at power density of 1250 m W cm~(-2). Furthermore, the asymmetric device exhibits an excellent long cycle life with 97.6% initial capacitance retention after 5000 cycles.Such composite electrode has a great potential for applications in flexible electronics, roll-up display,and wearable devices.     

一步合成还原氧化石墨烯/MnO2复合材料及其电化学性能

通过水热法, 利用氧化石墨烯(GO)和二价锰盐, 一步合成了还原氧化石墨烯/MnO₂(RGO/M)复合电极材料。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼光谱(RS)、傅里叶红外光谱(FTIR)和场发射扫描电镜(FESEM)等测试电极材料的物性, 通过循环伏安、交流阻抗和恒流充放电等方法研究电极材料的电化学性能。结果表明, 在一定水热反应条件下, 通过控制GO与二价锰盐配比, 可以调节RGO/M的结构及其电化学性能。在1 A/g电流密度下, 所得RGO/M复合电极的比电容可达277 F/g, 经过500次循环后, 保持率达到98%。     

Hierarchical architecture of ultrashort carbon nanotubes/polyaniline nanocables coated on graphene sheets for advanced supercapacitors

Multilayer super-short carbon nanotubes (SSCNTs) could be prepared by tailoring raw multiwalled carbon nanotubes (MWCNTs) with mechanical-stirring and ultrasonic oxidation-cut method. The SSCNTs/polyaniline/reduced graphene oxide (SSCNTs/PANI/RGO) ternary hybrid composite was fabricated by reducing SSCNTs/PANI/GO precursor prepared by self-assembly from the complex dispersion of graphene oxide (GO) and the as-prepared SSCNTs/PANI nanocables, followed by redoping and reoxidation of the reduced PANI to restore the conducting structure of PANI in the ternary composite. The microscope images indicated that SSCNTs/PANI nanocables could uniformly distribute in the conductive network of graphene sheets and prevent the agglomeration of graphene. Such the hierarchical structure perfectly facilitates the contact between PANI for faradaic energy storage and electrolyte ions, and efficiently utilizes the double-layer capacitance of SSCNTs and graphene sheets at the electrode–electrolyte interfaces. The maximum specific capacitance of the SSCNTs/PANI/RGO composite achieved 845 F g^?1, which was much higher than that of pure PANI and SSCNTs/PANI nanocables. Moreover, the ternary composite also showed the good cycling stability, retaining about 96% of its initial capacitance after 1000 cycles because of the synergistic effect and conductive network of SSCNTs/PANI nanocables and graphene sheets. Therefore, the combined effects between SSCNTs/PANI nanocables and graphene sheets taking advantage of both charging and faradaic processes could readily explain the excellent electrochemical performance for supercapacitors.     

Zn2+掺杂对电化学合成聚苯胺膜耐蚀性能的影响

为提高聚苯胺（PANI）膜的耐蚀性,在苯胺-硫酸电解液体系中,采用电化学恒电流法在不锈钢表面合成了PANI膜,利用电化学测试技术、SEM和XRD研究了Zn²⁺掺杂对电化学合成PANI膜耐蚀性能的影响。结果表明：Zn²⁺的掺杂使PANI膜微观形貌由不规则片状转变为规则的纤维状形貌;掺杂改性后PANI膜的交流阻抗明显增大,腐蚀电位向正方向移动,腐蚀电流减小;掺杂Zn²⁺的PANI膜经质量分数为10% 的HCl点滴实验测试,腐蚀时间达320 s;经中性盐雾实验48 h后,PANI膜未见锈蚀。