聚吡咯/氧化铜纳米管的制备及其催化性能研究

聚吡咯/氧化铜纳米管(PPy/CuO-NTs)新型复合材料通过在氧化铜纳米管上原位聚合单体吡咯,以过硫酸铵为氧化剂、赖氨酸为表面修饰剂制备出来。通过FT-IR、XRD、SEM、TEM以及TGA对其结构和形貌进行了表征,并研究了其在超声条件下对罗丹明B的催化降解作用。结果表明:PPy/CuO-NTs对罗丹明B有很好的催化降解性能。     

Behavior of mixed multi-walled carbon nanotube/P3HT monolayer at the air/water interface

The sidewall structure of multi-walled carbon nanotubes (MWNTs) was successfully functionalized with poly(3-hexylthiophene) (P3HT) by a non-covalent bond method. P3HT plays an important role in dispersing MWNTs, and assists them to have a stable existence at the air/water interface. The behavior of mixed MWNT/P3HT monolayer at the air/water interface was investigated after obtaining a homogeneously dispersed solution. The effect of MWNT concentration on the mixed MWNT/P3HT monolayer was investigated using the pressure–area (π–A) isotherm, relaxation curve and transmission electron microscopy (TEM). The mixed MWNT/P3HT monolayer was transferred onto a solid substrate using the Langmuir–Blodgett (LB) technique with horizontal or vertical deposition. The multilayer film was delicately fabricated by repeated deposition of the ultra-thin film. Scanning electron microscopy (SEM) images revealed non-uniformity in morphology of the ultra-thin MWNT/P3HT films. The absorption intensity at 250 nm by UV/vis spectroscopy illustrates that a uniform formation of mixed MWNT/P3HT monolayer into multilayer film was successfully obtained by horizontal deposition. The current–voltage characteristic of the ultra-thin MWNT/P3HT film shows that the current increases linearly with the increasing voltage, which indicates that MWNT/P3HT film forms an ohmic contact with gold. And, the electric current was estimated to be mainly contributed by MWNTs.     

Carbon nanotube/polyaniline core-shell nanowires prepared by in situ inverse microemulsion

By the in situ inverse microemulsion, we prepared multi-walled carbon nanotubes/polyaniline composites (MWNTs/PANI). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. Fourier transform infrared (FT-IR) spectra suggested that the π-bonded surface of the carbon nanotubes (CNTs) interact strongly with the conjugated structure of the PANI shell layer. The thermal stability and electrical conductivity of the MWNTs/PANI composites were examined by thermogravimetric analysis (TGA) and conventional four-probe method. In comparison with the pure PANI, the decomposition temperature of the MWNTs/PANI (1 wt% MWNTs) composites increased from 360 to 400 °C and the electrical conductivity of MWNTs/PANI (1 wt% MWNTs) composites was increased by one order of magnitude.     

空心聚吡咯/V_2O_5复合材料的制备及其电化学性能

为改善晶态V2O5（c-V2O5）正极材料实际容量较低、循环性能较差等问题,制备了空心球聚吡咯/V2O5复合材料。利用导电吡咯单体（Py）在中空型V2O5层间发生原位氧化聚合反应制备聚吡咯（PPy）/中空型V2O5复合材料（HS-PPy/V2O5）。采用X射线衍射仪（XRD）、扫描电镜（SEM）、透射电镜（TEM）对样品进行表征,采用恒流充放电测试和电化学阻抗（EIS）测试样品的电化学性能。结果表明,Py单体已插入中空型V2O5层间,与纯中空型V2O5相比,制备的HS-PPY/V2O5复合材料比容量虽然有所减小,但是循环稳定性有较大的提高。     

Ag/AgCl-decorated polypyrrole nanotubes and their sensory properties

A facile method to prepare Ag/AgCl-decorated polypyrrole nanotubes (PPy/Ag–AgCl nanocomposites) has been demonstrated. PPy nanotubes were assembled on the reactive self-degraded template of a fibrillar complex of FeCl₃ and methyl orange (MO). By introducing PPy nanotubes into AgNO₃ solution, Ag and AgCl nanoparticles could be uniformly decorated onto the PPy nanotube surface in situ by the reaction of PPy and AgNO₃. The morphology and structure of the nanocomposites were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The possible application of PPy/Ag–AgCl nanocomposites as a vapor sensor has also been reported. The responses of these nanocomposites were observed to be reversible by monitoring the change in the resistance of the nanocomposites upon exposure to ammonia vapor. PPy/Ag–AgCl composite nanotubes sensors showed enhanced chemiresistor sensitivity compared with PPy nanotubes.     

多壁碳纳米管载镍对镁基合金储氢性能影响

采用化学法制备多壁碳纳米管载镍催化剂(Ni/MWNTs),并将其加入到镁粉中,结合氢化燃烧合成(HydridingCombustionSynthesis,HCS)和机械球磨(MechanicalMilling,MM),即HCS+MM复合技术制备Mg85-Nix/MWNTs15-x(x代表质量百分数,x=3,6,9,12)合金。通过X射线衍射仪、透射电子显微镜、扫描电镜以及气体反应控制器研究了材料的晶体结构、微观形貌和吸放氢性能。结果表明:Mg85-Ni9/MWNTs6合金具有最佳综合吸放氢性能,其在373K,吸氢量达到5.68%(质量分数,下同),且在100s内就基本达到饱和吸氢量;在523K,1800s内的放氢量达到4.31%。Ni/MWNTs催化剂的添加,不但起到催化的作用,而且MWNTs具有优异的纳米限制作用,使得催化剂的粒径限制在纳米级,有利于限制产物中Mg2NiH4颗粒的长大。另外Ni与MWNTs存在协同催化作用,当它们达到一定比例时,对合金的吸放氢促进作用达到最优化,明显改善了合金的吸放氢性能。     

Electrochemical synthesis of polypyrrole films over each of well-aligned carbon nanotubes

Polypyrrole (PPy) films were uniformly electropolymerized over each carbon nanotube of the well-aligned carbon nanotube arrays. For comparison, PPy films were also coated on flat metallic titanium (Ti) and platinum (Pt) substrates by the same technique. The synthesis and the redox performance of the PPy films were conducted by cyclic voltammetry (CV). The structural characterization including the thickness and uniformity of the PPy films was carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It is observed that the coating of the PPy film over carbon nanotubes is much faster than that on flat Ti/Pt surface. Furthermore, the redox performance of the PPy-coated carbon nanotube electrodes over flat Ti/Pt electrodes was significantly improved due to the high accessible surface area of the carbon nanotubes in the aligned arrays, especially in large film formation charge (Q_film). It is very promising that the electrode developed in this study could be used as high performance electrode in rechargeable batteries.     

Fabrication of Pt nanoparticles decorated PPy–MWNTs composites and their electrocatalytic activity for methanol oxidation

Here we report the synthesis and characterization of a catalyst material constituted of Pt, polypyrrole (PPy) and multi-walled carbon nanotubes (MWNTs). The catalyst supports (PPy–MWNTs nanocomposites) were synthesized via in situ chemical polymerization in advance, in which MWNTs were regarded as the matrix material. The supports were characterized by SEM & TEM, elemental analysis, XRD, FTIR and conductivity measurements. Then the catalysts were synthesized by a chemical reduction using sodium borohydride (NaBH₄) as reducing agent and acetic acid buffer (pH = 4) containing trace K₂C₂O₄ as reaction media. FTIR spectra showed that there existed relations between PPy and MWNTs during in situ polymerization. SEM and TEM micrographs of the catalyst samples exhibited that the existence of PPy layer which was evenly wrapped on the surface of MWNTs resulted in significant improvement in helping Pt particles well dispersed. XRD results showed that higher Pt(1 1 1) content in the catalyst deposited on PPy–MWNTs supports than that on MWNTs. The cyclic voltammetry (CV) tests of methanol electrocatalytic oxidation demonstrated that the electrode modified by Pt/PPy–MWNTs ternary composite catalyst showed higher catalytic stability than Pt/MWNTs binary catalyst, due to the synergic interaction between Pt and the carrier.     

Preparation and characterization of polyaniline micro/nanotubes with dopant acid mordant dark yellow GG

Polyaniline(PANI) micro/nanotubes doped with novel dopant acid mordant dark yellow GG (AMY GG) were prepared by soft template method in the presence of ammonium persulfate (APS) as an oxidant. It was found that the molar ratio of HCl to aniline and washing method of the products played key roles in the formation of PANI micro/nanotubes. Changing the molar ratio of HCl to aniline, the typical morphology of PANI could be changed from nanotubes to microtubes. In order to get the final product, different solvents were tried to wash away the by-products. After the by-products were removed by water/methonal/ether, the PANI micro/nanotubes appeared. The morphology of PANI micro/nanotubes was confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The chemical structure and thermal stability of PANI micro/nanotubes were examined by Fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) and the thermogravimetric analysis (TGA). The formation mechanism of PANI micro/nanotubes was also discussed.     

Synthesis of micromulti-prisms polypyrrole boxes in the presence of α-cyclodextrin

Polypyrrole (PPy) boxes with micromulti-prisms have been synthesized in aqueous solution via a self-assembled method using α-cyclodextrin (α-CD) as a dopant and FeCl₃ as an oxidant. The morphology and the micro-structure of the as-synthesized PPy boxes were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and Fourier-transform infrared (FTIR) spectrum. The formation mechanism of the PPy boxes structure was also discussed. And the congregated structure of dissociative pyrrole monomers with the inclusion complexes (between α-CD and pyrrole monomer) was proposed to play a significant role in forming the multi-prisms sectional PPy-CD boxes.     

Bio-based conductive composites: Preparation and properties of polypyrrole (PPy)-coated silk fabrics

Silk fabrics were coated with electrically conducting doped polypyrrole (PPy) by in situ oxidative polymerisation from an aqueous solution of pyrrole (Py) at room temperature, by using FeCl₃ as catalyst. The amount of polymer deposited on the fabrics increased with increasing the reaction time or the concentration of Py in the reaction system. PPy-coated silk fabrics were characterized by optical microscopy (OM) and scanning electron microscopy (SEM), Fourier transform-infrared (FT-IR) spectroscopy, and thermal analysis (differential scanning calorimetry (DSC), thermogravimetric (TG)). OM and SEM showed that PPy completely coated the surface of individual silk fibres and that the polymerisation process occurred only at the fibre surface and not in the bulk. FT-IR (attenuated total reflectance (ATR) mode) showed a mixed spectral pattern with bands typical of silk and PPy overlapping over the entire wavenumbers range. The intrinsic crystalline structure and the molecular conformation of silk were not affected by the polymerisation. PPy-coated silk fabrics attained a significantly higher thermal stability than untreated ones, owing to the protective effect of the PPy layer against thermal degradation. PPy-coated silk fabrics displayed excellent electrical properties. Current versus voltage curves showed a linear fit, with higher current increments at higher PPy amount. The resistance of PPy-coated silk fabrics decreased exponentially with increasing the reaction time or the concentration of Py in the reaction system. Due to the Joule effect, the temperature of PPy-coated silk fabrics increased as a function of the electrical potential applied and of the amount of PPy. The encouraging results reported in this study open new perspectives for future application of PPy-coated silk fabrics, from interactive and smart textiles to innovative bio-based conductive composites for biomedical end-uses.     

核壳型碳微球和碳纳米管的制备及其阻燃性能

为改善碳微球(CMSs)/碳纳米管(MWNTs)与聚对苯二甲酸乙二醇酯(PET)基体相容性,采用原位聚合法对CMSs和MWNTs分别进行表面修饰,制成核壳型结构的PET@CMSs(PCMSs)和PET@MWNTs(PMWNTs),并通过熔融共混法制备了PCMSs/PMWNTs/PET复合材料,对其阻燃性能进行探讨。使用TEM、SEM、FTIR、TGA、CONE等测试手段,表征了PCMSs与PMWNTs的结构及与PET基体的相容性,并测试了PCMSs/PMWNTs/PET的力学性能、阻燃性能、热稳定性和燃烧行为等。结果表明,与修饰前的CMSs/MWNTs相比,PCMSs/PMWNTs与PET基体具有更好的分散相容性,在PCMSs\PMWNTs添加的质量分数为1%,PCMSs与PMWNTs的质量比为1∶2时,PCMSs/PMWNTs/PET比CMSs/MWNTs/PET的抗拉强度提高的最大,可达26.1%;与纯PET、CMSs/MWNTs/PET相比,PCMSs/PMWNTs作为阻燃材料添加到PET中,具有较好的热稳定性、且有效延长了PET的点燃时间、增大FPI指数,从而降低火灾危险性,阻燃效果较好,其LOI值为28.1%,熔滴数为3 d/min,UL-94阻燃级别可达到V-0级。     

Preparation and magnetic property of multi-walled carbon nanotube/a-Fe2O3 composites

In order to attain new functional nanomaterials with good magnetic property, multi-walled carbon nanotubes/hematite (MWNTs/α-Fe₂O₃) composites were synthesized using the co-deposition method. MWNTs/α-Fe₂O₃ composites were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy(TEM), Raman spectroscopy and vibrating sample magnetometry (VSM). The experimental results show that the structure and magnetic properties of the MWNTs/α-Fe₂O₃ composites are related to the heat treatment temperature. MWNTs are modified by α-Fe₂O₃ nano-particles and α-Fe₂O₃ nanorods with a diameter of 10?50 nm after being treated at 450 °C. When the heat treatment temperature exceeds 600 °C, MWNTs are only modified by Fe₃O₄ particles. Furthermore, the MWNTs composites treated at 450 °C and 600 °C have good magnetic behaviour.     

Structural interpretations of deformation and fracture behavior of polypropylene/multi-walled carbon nanotube composites

The deformation and crack resistance behavior of polypropylene (PP) multi-walled carbon nanotube (MWNT) composites have been studied and their interrelation to the structural attributes studied by transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and polarization light microscopy has been discussed. The composites were produced from industrial available MWNT by extrusion melt-mixing and injection-molding. In stress–strain measurements a strong increase in the yield stress and the Young’s modulus at low MWNT contents has been observed, which was attributed to an efficient load transfer between the carbon nanotubes and polypropylene matrix through a good polymer–nanotube adhesion as indicated by SEM. The extent of enhancement in mechanical properties above 1.5 wt.% of MWNT decreased due to an apparently increased tendency of clustering of carbon nanotubes. Several theoretical models have been taken into account to explain the mechanical properties and to demonstrate the applicability of such models to the system under investigation. The crack resistance behavior has been studied with the essential work of fracture (EWF) approach based on post-yield fracture mechanics (PYFM) concept. A maximum in the non-essential work of fracture was observed at 0.5 wt.% MWNT demonstrating enhanced toughness compared to pure PP, followed by a sharp decline as the MWNT content was increased to 1.5 wt.% reveals a ductile-to-semi-ductile transition. Studies on the kinetics of crack propagation aspects have revealed a qualitative picture of the nature of such a transition in the fracture modes.     

碳纳米管/聚酰亚胺纳米复合材料的制备及动态力学性能和介电性能

依次用混强酸和SOCl2对多壁碳纳米管(MWNTs)进行改性,解决其在有机溶剂的溶解性和在基体聚酰亚胺中分散性问题,并采用光电子能谱(XPS)和透射电镜(TEM)对改性前后的MWNTs进行表征.以4,4'-二氨基二苯醚(ODA)和3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)为原料,以原位聚合法将改性碳纳米管掺杂聚酰亚胺(PI),制备MWNTs/PI纳米复合材料.通过热重分析(TGA)、动态力学分析(DMA)和电容测试对材料的热性能、动态力学和介电性能进行表征.结果表明:加入MWNTs后,材料仍有很好的热稳定性,材料的动态力学性能随MWNTs增加而增强,在50℃和10%(质量分数)MWNTs时储能模量为2.307 GPa,比纯聚酰亚胺(PI)提高23.1%;材料的介电常数随着MWNTs含量的增加明显提高,在IMHz和10%时介电常数为66.7,是纯PI的18.6倍.制备的碳纳米管/聚酰亚胺材料是一种具有优良的热学、动态力学力学和介电性能性能的纳米复合材料.     

CTAB/正己醇/水反胶束体系中合成PPy/TiO2纳米复合粒子

通过溶胶-凝胶法制备了TiO2纳米粒子,并用十六烷基三甲基溴化铵(CTAB)/正己醇/水反胶束体系作为微反应器合成了聚吡咯(PPy)/TiO2纳米复合粒子.利用透射电镜(TEM)、扫描电镜(SEM)、红外光谱仪(FTIR)、X-射线衍射仪(XRD)对纳米复合粒子进行了表征.实验结果表明,PPy/TiO2球形粒子的平均粒径为150～200 nm,在复合粒子中球形粒子占据优势,并有团聚的趋势.FTIR和XRD结果显示纳米复合材料由PPy和TiO2组成,无机复合粒子只有部分形成晶体.从该研究结果中可以看出,反胶束法可以有效地应用于有机-无机纳米复合材料的制备.     

Effect of multi-walled carbon nanotubes on tribological properties of lubricant

After purified by mixture of sulfuric acid and nitric acid, the multi-walled carbon nanotubes(MWNTs) were modified with stearic acid(SA). The modified carbon nanotubes as lubricant additive were utilized to prepare lubricant, and the effects of carbon nanotubes on the tribological properties were investigated by using a pin-on-plate wear tester. The surface structure of MWNTs was examined by transmission electron microscopy, Raman spectroscopy and infrared spectroscopy. The results show that the surfaces of MWNTs are coated with a modified layer of SA. Furthermore, the modified MWNTs as lubricant additive can effectively improve the friction-reduction and antiwear ability of lubricant. The friction coefficient of base lubricant decreases by about 10% and the wear loss of base lubricant decreases by 30%-40% when the concentration of modified MWNTs in lubricant is 0.45 %. In addition,the mass ratio of SA to MWNTs influences the friction-reduction and anti-wear ability of the modified MWNTs as lubricant additive. The optimum mass ratio of MWNTs to stearic acid is about 3 : 8 - 1 : 2.     

Electrospinning PVDF/PPy/MWCNTs conducting composites

Conducting PVDF/PPy composites (PPy composites) were prepared by using the highly porous electrospun (e-spun) nonwoven web as a host polymer. E-spun nonwoven web was made by electrospinning a solution of PVDF and CuCl₂·2H₂O in solvent of N,N-dimethylacetamide (DMAc). The PPy composites were fabricated by exposing a nonwoven web containing oxidant to pyrrole vapors. Field-emission scanning electron microscopy (FE-SEM) analysis was conducted to show the microstructure of the nonwoven webs and the uniform coating of PPy on the e-spun fiber surfaces of the PPy composite. The information of PPy on the e-spun fibers surface was confirmed by attenuated Fourier-transform infrared spectrometer (ATR FT-IR) and X-ray photoelectron spectroscope (XPS). The thermal property of PPy composites was also investigated by differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA). The electrical conductivity of the PPy composites was affected by the fabrication method and oxidant content in the nonwoven web. The electrical conductivity and mechanical strength of the PPy composites were improved when surface-modified multi-walled carbon nanotubes (MWCNTs) were added to the e-spun fibers. Energy-filtered transmission electron microscopy (EF-TEM) results confirmed that the MWCNTs were well arranged and embedded in the e-spun fibers. The observed conductivity of the conducting PPy-MWCNTs composite was 10^?1 S/cm.     

Electroless deposition of Cu on multiwalled carbon nanotubes

Copper has been deposited on the surface of multiwailed carbon nanombes （MWNTs） and inside MWNTs by electroless deposition. The as-prepared Cu-MWNT composite materials have been characterized by X-ray diffractometer （XRD）, transmission electron microscopy （TEM）, and electrochemical measurement. XRD analyses showed that Cu was a face-centered cubic （fcc） structure. The average size of Cu was calculated by Scherrer＇s formula from XRD data, and it was 11 nm. TEM revealed that Cu grains on the surface of MWNTs were uniform with the sizes of about 30-60 nm. The electrochemical measurement indicated that Cu-MWNT composite materials possessed fine electron conductivity.     

Two step novel chemical synthesis of polypyrrole nanoplates for supercapacitor application

Simple and inexpensive two step novel chemical method for the synthesis of polypyrrole (PPy) nanoplates has been reported. These PPy nanoplates are characterized with X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polypyrrole nanoplates exhibit amorphous nature as confirmed from XRD study. Based on SEM and TEM analysis, the formation of the spherical bunches of PPy nanoplates with average size of about 20 nm are inferred. The electrochemical performance of PPy electrode was evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge measurement. A high specific capacitance of 533 F g⁻¹ was obtained within the potential range of −0.4 to 0.6 V in 0.5 M H₂SO₄ solution. Moreover, PPy electrode exhibited high discharge/charge efficiency of 93% and the capacitance retention of 83% at a current density of 10 mA cm⁻² indicating good electrochemical reversibility and rate capability.