Electrocatalytic oxidation of formaldehyde on platinum well-dispersed into single-wall carbon nanotube/polyaniline composite film

Single-walled carbon nanotubes (SWNTs)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dissolved SWNTs. The composite films were dispersed Pt by electrodeposition technique. The presence of SWNTs and platinum in the composite film was confirmed by XRD analysis and scanning electron microscopy (SEM). Four-point probe investigation and electrochemical impedance spectroscopy (EIS) revealed that the well arrangement of PANI coated SWNTs in these films enhanced electric conductivity and facilitated the charge-transfer of the composite films. Cyclic voltammogram (CV) and chronoamperogram showed that Pt-modified SWNT/PANI composite film performs higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formaldehyde oxidation. The results imply that the SWNT/PANI composite film as a promising support material improves the electrocatalytic activity for formaldehyde oxidation greatly.     

Preparation and characteristic of platinum catalyst deposited on boron-doped carbon nanotubes

In this work, boron doped multi-walled carbon nanotubes (BMWNTs) were introduced as a Pt catalyst support due to their unique physicochemical properties. The effect of BMWNTs on methanol oxidation was investigated with different Pt loading contents. The surface and structural properties of the modified MWNT supports were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. The Pt loading contents in the catalysts were confirmed by inductive coupled plasma-mass spectrometer (ICP-MS) and the morphological structures of the catalysts were analyzed by transmission electron microscopy (TEM). The electrocatalytic activity of Pt/MWNTs was investigated by cyclic voltammetry measurement. As a result, the boron oxide vapor reacted with MWNTS to form BMWNTs, which led to enhancing the properties, such as graphitization and electrochemical behaviors. Moreover, Pt deposited on BMWNTs exhibited better electrocatalytic activity than on MWNTs for methanol oxidation. Consequently, it was found that partial boron doped MWNTs could influence on the properties of the MWNTs, resulting in enhancing the electrocatalytic activity of the catalysts for DMFCs.     

Broadband optical limiting performance of polymer-wrapped carbon nanotubes in the orange-NIR region

Soluble multi-walled carbon nanotubes (MWNTs) have been obtained by noncovalent modification with poly [2-methoxy,5-(2′-ethyl-hexyloxy)-p-phenylene vinylene] (MEH-PPV). For the composite MWNT/MEH-PPV, there is π-π interaction between the MEH-PPV and MWNTs in addition to the wrapping of the polymer. The nonlinear optical transmittance was measured using a nanosecond optical parametric oscillator pumped with a Nd:YAG system. Excellent optical limiting performance of the composite MWNT/MEH-PPV was observed both in the visible region of 590-680 nm and at the wavelength of 1064 nm. By means of time-correlated single-photon counting fluorescence measurement, an explanation based on the nonlinear absorption of MWNT dominated by the intermolecular energy transfer was proposed.     

Raman spectroscopy and field-emission properties of CVD-grown carbon-nanotube films

Carbon-nanotube films are very efficient cathodes for field-emission devices. This study presents a comprehensive comparison between structural, spectroscopic and field-emission properties of films of aligned and non-aligned multi-wall nanotubes (MWNTs) which are grown by thermal chemical vapour deposition. Three types of films are investigated: vertically aligned MWNTs with clean and coated nanotube side walls as well as non-aligned MWNT films. Raman spectra taken on the aligned MWNT films consist of many lines of first-, second- and third-order signals. Several lines are reported here for the first time for MWNTs. The presence of the surface coating leads to a decrease and broadening of the higher-order signals as well as an increase in the disorder-induced contributions in the first-order regime. The aligned MWNT films have excellent field-emission properties with very high emission current densities and low turn-on and threshold fields. The presence of a surface coating has no impact on the efficiency of the field-emission process. Films of non-aligned MWNTs show considerably reduced electron-emission current densities and larger critical fields. Received: 25 April 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

浓硝酸处理前后多壁碳纳米管的荧光特性研究

对浓硝酸处理前后多壁碳纳米管的荧光特性进行了研究,结果发现多壁碳纳米管在浓硝酸处理前后都能产生荧光;与浓硝酸处理前相比,浓硝酸处理后的多壁碳纳米管的荧光有所增强,且荧光谱峰向短波长方向发生蓝移。碳纳米管产生的荧光与碳纳米管在其缺陷处捕获激发光的能量以及最低空轨道和最高占有轨道之间的能隙有关。多壁碳纳米管在浓硝酸处理前后都有缺陷,因而都能在其缺陷处捕获激发光能量而产生荧光;浓硝酸处理引起多壁碳纳米管的缺陷增多、捕获激发光能量增加因而荧光也随之增强。碳纳米管的最低空轨道和最高占有轨道之间的能隙随其长度减小而增大,浓硝酸处理引起多壁碳纳米管被削短导致其最低空轨道和最高占有轨道之间的能隙增大,因而引起多壁碳纳米管的荧光谱峰向短波方向蓝移。     

Carbon nanotube/polyaniline nanocomposites and their electrorheological characteristics under an applied electric field

A conducting polyaniline (PANI) was synthesized via an oxidative dispersion polymerization technique, using poly(vinyl alcohol) (PVA) as a polymeric stabilizer, in the presence of multi-walled carbon nanotubes (MWNT) purified in acidic solution, and dispersion stability of the MWNT in an aqueous solution of PVA was studied for different PVA concentrations. Their morphology was confirmed by a scanning electron microscope. Its electrorheological (ER) characteristics were also investigated by dispersing the PANI/MWNT composite particles in an insulating silicone oil. Its ER properties were examined using a rotational rheometer under varying applied DC electric field strengths, in which the ER fluid is generally composed of a suspension of conducting particles dispersed in an insulating fluid, which shows a rapid and reversible change in shear viscosity with an applied electric field. Synthesized PANI/MWNT composite particles are observed to enhance interparticular interactions, since the degree of polarization of PANI/MWNT composite particle increases with applied electric field strengths. The shear stresses of the PANI/MWNT nanocomposite based ER fluid increase with the electric field strength for a broad range of shear rates.     

Effects of additives on palladium nanocrystals supported on multiwalled carbon nanotubes and their electrocatalytic properties toward formic acid oxidation

Carbon nanotubes are believed to be powerful materials for constructing novel hybrid composites with desirable functionalities and applications in many fields. Therefore, a better understanding of the functionalization of multiwalled carbon nanotubes (MWCNTs) holds the key to a better performance of the hybrid properties. In this paper, with a series of aromatic bifunctional molecule additives, modified MWCNTs were used as composite supports for synthesizing nanostructured palladium catalysts for formic acid oxidation. The additives contain anthranilic acid, o-phenylenediamine, salicylic acid, catechol, and phthalic acid. The influence of the different bifunctional groups (such as –NH₂, –OH, –COOH, and their mixed groups) on the morphologies, particle sizes, and electrical properties of Pd nanocrystals was intensively studied. Transmission electron microscopy measurement demonstrates that the palladium nanoparticles were well dispersed on the surface of MWCNTs with a relatively narrow particle size distribution in the presence of the additives. Cyclic voltammetry and chronoamperometry tests demonstrate that the functional groups of the additives play an important role in electrocatalytic activity and stability for formic acid oxidation, and the influence law of various functional groups on electrocatalytic activity and stability is also investigated in this paper. We hope it can provide certain theoretical guidance meaning and practical reference value in future studies.     

Synthesis, field emission and glucose-sensing characteristics of nanostructural ZnO on free-standing carbon nanotubes films

Free-standing multiwall carbon nanotubes (MWNTs) films were coated, using chemical vapor deposition method, with a thin layer of nanostructural ZnO. The morphology and crystal structure of the as-grown products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman scattering analyses. Field emission (FE) results demonstrated that the needle-like and spherical ZnO-MWNTs composite structure films possessed good performance with a turn-on field of 1.3, 2.2 V μm⁻¹ and a threshold field of 2.6, 4.5 V μm⁻¹, respectively. The glucose-sensing characteristic has also been studied. The multi-layer electrode (PDDA/GOx/ZnO/MWNTs) exhibited significant electrocatalysis to the oxidation and reduction of H₂O₂ than the PDDA/GOx/MWNTs electrode, which provided wide potential applications in clinical, environmental, and food analysis.     

Highly dispersed Pd nanoparticles on chemically modified graphene with aminophenyl groups for formic acid oxidation

A novel electrode material based on chemically modified graphene (CMG) with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the aminophenyl groups of p-phenylenediamine. Palladium nanoparticles with an average diameter of 4.2 nm are deposited on the CMG by a liquid-phase borohydride reduction. The electrocatalytic activity and stability of the Pd/CMG composite towards formic acid oxidation are found to be higher than those of reduced graphene oxide and commercial carbon materials such as Vulcan XC-72 supported Pd electrocatalysts.     

Tubular composite of doped polyaniline with multi-walled carbon nanotubes

We report on the synthesis of tubular composite of doped polyaniline (PANI) with carboxylic groups contained multi-walled carbon nanotube (MWNTs) by in situ polymerization. Based on the interaction between aniline monomers and c-MWNTs , aniline molecules were adsorbed and polymerized on the surface of c-MWNTs . The structural characterization showed that tubular composites are core (c-MWNTs )-shell (doped-PANI) structures with diameters of several tens of nanometers, and lengths of up to several hundreds of nanometers. The conductivities of these tubular composites are several times higher than that of PANI without MWNT, which will offer new application possibilities. PACS 81.05.Qk; 81.05.Tp     

Enhanced mechanical properties and morphological characterizations of poly(vinyl alcohol)-carbon nanotube composite films

Tensile tests were carried out on free-standing composite films of poly(vinyl alcohol) (PVA) and multiwall carbon nanotubes (MWNTs) for different loading levels. Results show that overall mechanical properties of the composite were greatly improved as compared to the neat PVA film. For PVA-based materials at significant high loading level such as 9.1 wt.% MWNTs, considerable increases in Young's modulus, tensile strength and toughness by factors of 4.5, 2.7 and 4.1, respectively, were achieved. Raman, SEM, TEM, and DSC techniques were used to evaluate the PVA/MWNTs composite system. Strong acid-modification of the pristine MWNTs and the subsequent ultrasonication processing allowed good distribution of the nanotubes in the matrix. SEM together with DSC result shows apparent good wetting of the nanotubes by the PVA matrix, which are supportive of good interfacial bonding between the modified carbon nanotubes and the hosting polymer matrix.     

Preparation of Pt–CeO2/MWNT nano-composites by reverse micellar method for methanol oxidation

We report the preparation of Pt–CeO₂ nanoparticles on the multi-walled carbon nanotubes (MWNTs) by a reverse micellar method. Transmission electron microscopy (TEM) analysis indicated that well-dispersed small Pt–CeO₂ nanoparticles were formed on the MWCNTs. X-ray diffraction (XRD) analysis confirmed the formation of the Pt–CeO₂ nanoparticles on the MWNTs. Cyclic voltammetry (CV) results demonstrated that the Pt–CeO₂/MWNT exhibited a higher methanol oxidation than did the Pt/MWNT catalyst. The CO stripping test showed that CeO₂ can make CO stripped at a lower potential, which is helpful for CO and methanol electro-oxidation.     

Functional multi-walled carbon nanotube/polysiloxane composite films as supports of PtNi alloy nanoparticles for methanol electro-oxidation

We demonstrate the use of molecular monolayers to enhance the nucleation of electrocatalytically active PtNi alloy nanoparticles onto the multi-walled carbon nanotubes (MWCNTs). After the siloxane was polymerized on the nanotube surfaces, the carbon nanotubes were embedded within the polysiloxane shell with a hydrophilic amino group situated outside. Subsequent deposition of PtNi nanoparticles led to high density of 3-10 nm diameter PtNi alloy nanoparticles uniformly deposited along the length of the carbon nanotubes. The presence of MWCNTs and PtNi in the composite films was confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersion X-ray spectra analysis (EDS). The electrocatalytic activity of the PtNi-modified MWCNT/polysiloxane (PtNi/Si-MWCNT) composite electrode for electro-oxidation of methanol was investigated by cyclic voltammetry (CV), and excellent electrocatalytic activity can be observed.     

Supercritical fluid-assisted synthesis of a carbon nanotubes-grafted biocompatible polymer composite

A nanocomposite consisting of multi-wall nanotubes (MWNTs) grafted with a biocompatible polymer poly(2-hydroxyethyl methacrylate) was prepared by in situ polymerization in supercritical carbon dioxide. The surface of the MWNTs was first surface modified with hydroxyl groups in the solution of KMnO₄ and a phase-transfer catalyst. MWNT-OH was then functionalized with vinyl groups using a silane coupling agent, γ-methacryloxypropyltrimethoxysilane. The silane groups can improve the dipersion of MWNTs in supercritical carbon dioxide, while the terminal vinyl groups help fabricate polymer chains on the MWNT surface. The as-synthesized products were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermo-gravimetric analysis. The SEM and TEM images showed that the nanotubes were well coated with the polymer shell. The composite had higher thermal stability than the pure polymer and dispersed well in methanol. This biocompatible polymer composite was prepared using a green method and is expected to be useful as a biomaterial composite with potential applications in the biological field.     

Electron field emission properties of conducting polymer coated multi walled carbon nanotubes

The present work describes the field emission characteristics of conducting polymer coated multi walled carbon nanotubes (MWNTs) field emitters fabricated over flexible graphitized carbon cloth. Nanocomposites involving the combination of MWNTs and conducting polymers polyaniline (PANI) and polypyrrole (PPy) have been prepared by in-situ polymerization method and have been characterized using scanning electron microscopy and transmission electron microscopy. Using spin coating method, field emitters based on PANI/MWNTs and PPy/MWNTs over flexible graphitized carbon cloth have been prepared. The field emission characteristics have been studied using an indigenously fabricated set up in a vacuum chamber with a base pressure of 2 × 10⁻⁵ Pa and the results are discussed. Our results display that the field emission performance of the emitters depends strongly on the work function of the emitting material. Low turn on emission field of 2.12 V/μm at 10 μA/cm² and high emission current density of 1 mA/cm² at 3.04 V/μm have been observed for PANI/MWNTs field emitter.     

Preparation of highly conductive CNTs/polyaniline composites through plasma pretreating and in-situ polymerization

In this study, carbon nanotubes (CNTs) were pretreated by plasma, and further in-situ polymerized with aniline to achieve uniform CNTs/polyaniline (PANI) composites with high conductivity. The highest conductivity (2.946 S/cm) of CNTs/PANI composites under optimum plasma treating parameters is much higher than those without CNTs pretreatment or premodified by acid oxidation method. The scanning electronic microscope (SEM) pictures indicate that smooth surfaces of pristine CNTs (diameter: 20-40 nm) changes into rough structures and the size increases to around 90 nm, which is further proved by the X-ray diffraction (XRD), the Fourier transform infrared spectroscopy (FTIR), and the Raman measurements. Thermogravimetric analysis (TGA) results reveal that the thermal stability of CNTs/PANI composite is better than that of pure PANI.     

Fabrication and Properties of Carbon Nanotube and Poly(vinyl alcohol) Composites

Dispersion of carbon nanotubes in a polymer matrix is one of the most critical issues in carbon nanotube/polymer composites. In this paper we discuss the considerable improvement in the dispersion of multiwalled carbon nanotubes (MWNTs) in poly(vinyl alcohol) (PVA) matrix that was attained through gum arabic treatment. The mechanical properties of these MWNT/PVA composites show that only 2 wt% nanotube loading increases the tensile modulus by more than 130%.     

磁场辅助热处理金属化碳纳米管场发射性能

利用化学镀方法对多壁碳纳米管(multi-walled carbon nanotubes,MWNTs)表面金属化镀镍(MWNTs/Ni),采用丝网印刷制备MWNTs/Ni场发射阴极,并在磁场辅助下热处理所得阴极,研究磁场辅助热处理对MWNTs/Ni阴极的场发射性能的影响,经300mT磁场辅助热处理的MWNTs/Ni的场发射阴极开启场强约为0.80V·μm~(-1),场增强因子β约为16068,对单根MWNTs/Ni在磁场中的受力情况进行建模分析,实验结果表明:磁场辅助热处理有助于提高MWNTs/Ni在阴极表面的直立分布,提高了MWNTs/Ni的场发射性能。     

Electron field emission from magnetic nanomaterial encapsulated multi-walled carbon nanotubes

The present work describes the field emission characteristics of nanoscale magnetic nanomaterial encapsulated multi-walled carbon nanotubes (MWNTs) fabricated over flexible graphitized carbon cloth. Ni/MWNTs, NiFe/MWNTs and NiFeCo/MWNTs have been synthesized by catalytic chemical vapor decomposition of methane over Mischmetal (Mm)-based AB₃ (MmNi₃, MmFe_1.5Ni_1.5 and MmFeCoNi) alloy hydride catalysts. Metal-encapsulated MWNTs exhibited superior field emission performance than pure MWNT-based field emitters over the same substrate. The results indicate that a Ni-filled MWNT field emitter is a promising material for practical field emission application with a lowest turn-on field of 0.6 V/μm and a high emission current density of 0.3 mA/cm² at 0.9 V/μm.     

Control of one-dimensional transport in multi-wall carbon nanotubes by wall destruction

We have investigated the damage in multi-wall carbon nanotubes (MWNTs) destroyed by electrical breakdown and focused ion beam bombardment (FIBB). The transport properties of a MWNT destroyed by electrical breakdown have been compared with those of a MWNT destroyed by FIBB. Also the Tomonaga–Luttinger transport (TLT) model has been applied to each type of destroyed MWNT. The MWNT destroyed by FIBB showed TLT behavior because of the weak destruction of the remaining walls. However, in the case of MWNTs destroyed by electrical breakdown, three-dimensional variable-range hopping (VRH) was observed in the low temperature transport. This suggests that the local damage has been caused by strong breakdown. There exists a clear difference between the effects of electrical breakdown and FIBB. Wall destruction by FIBB could be applied to control the one-dimensional transport of MWNTs.