Functional multi-walled carbon nanotube/polyaniline composite films as supports of platinum for formic acid electrooxidation

Embedding of carbon nanotubes in conducting polymeric matrices for various nanocomposites material is now a popular area. In this article, a concise chemical method has been described for the preparation of homogeneous nanocomposite of multi-walled carbon nanotube (MWNT)/polyaniline (PANI) by electrochemical codeposition. For this we functionalized the MWNTs via the diazotization reaction. This helped to disperse the nanotubes in aniline. The composite films were dispersed Pt by electrodeposition technique. The presence of MWNTs and platinum in the composite films was confirmed by XRD analysis and transmission electron microscopy (TEM). Four-point probe investigations revealed that the MWNT/PANI composite films exhibited a good conductivity. Cyclic voltammograms (CV) showed that Pt-modified MWNT/PANI composite films perform higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formic acid oxidation. The results imply that the MWNT/PANI composite films as a promising support material improves the electrocatalytic activity for formic acid oxidation greatly.     

Humidity sensing properties of different single-walled carbon nanotube composite films fabricated by layer-by-layer self-assembly technique

Poly(diallyldimethylammonium chloride)/single-walled carbon nanotube (PDDA/SWNT) multilayered thin films were prepared on quartz crystal microbalance by layer-by-layer self-assembly technique, and their sensing properties to humidity were studied. The SWNTs were characterized by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The composite films were observed by field-emission scanning electron microscope. Two types of SWNT humidity sensors were fabricated using SWNTs and carboxyl (COOH) modified SWNTs as sensitive material, respectively. The results showed that the sensitivity of the PDDA/SWNT?CCOOH humidity sensor was 20.23?% higher than that of the PDDA/SWNT sensor. In contrast, the latter had a much superior hysteresis property, and the reason to cause this phenomenon was discussed.     

Surface modification of polyacrylonitrile film by anchoring conductive polyaniline and determination of uricase adsorption capacity and activity

Polyacrylonitrile (PAN) films were modified with chemical polymerization of conductive polyaniline (PANI) in the presence of potassium dichromate as an oxidizing agent. The effect of aniline concentration on the grafting efficiency and on the electrical surface resistance of PAN and (PAN/PANI)-1-3 composite film was investigated. The surface resistances of the conductive composite films were found to be between 6.32 and 0.97 kΩ/cm. As the amount of grafted PANI increased on the PAN films, the electrical resistance of composite film decreased. The PAN/PANI composite films were also characterized using SEM and FTIR. The changes in the surface properties of the films were characterized by contact angle measurements. As expected, the PAN, PAN/PANI and PAN/PANI-uricase immobilized films, exhibited different contact angle values and surface free energy due to different interactive functional groups of the films.The conductive films were well characterized and used for immobilization of uricase. The amount of adsorbed enzyme increases with the increase of surface concentration of grafted fibrous polyaniline polymer. The maximum amount of immobilized enzyme onto composite film containing 2.4% PANI was about 216 μg/cm² (i.e., PAN/PANI-3). The immobilized uricase was reused 24 times in batch wise assay in a day. Finally, the immobilized uricase enzyme system was successfully fabricated and applied to determine the uric acid level in human serum samples.     

Optical anisotropy in single-walled carbon nanotubes

Optical anistropy at optical communication wavelength was observed in films of vertically aligned single-walled carbon nanotubes (SWNTs). We report the control of both the polarization state and transmission of incoming light at 1550 nm by azimuthal and axial tilting of SWNT film about its aligned axis. The experiments reveal that the polarization state of light is susceptible to the azimuthal angle of the aligned direction of a SWNT having semiconductor characteristics and the intensity of the output beam after SWNT film shows cosine function dependence on the axial tilting angle.     

Charge‐transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E_laser = 1.17 eV suggest that a charge‐transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright © 2010 John Wiley & Sons, Ltd.     

Selection of isolated and individual single-walled carbon nanotube from a film and its usage in nanodevices

Individual and isolated single-walled carbon nanotubes (SWNTs) are important for fabricating relevant nanode- vices and studying the properties of the SWNT devices. In this work, we demonstrate that individual and isolated SWNT can be selected and obtained from a film containing a huge number of SWNTs. By using both the polymethyl-methacrylate (PMMA) as a negative resist and the electron beam lithography, the selected SWNT can be fixed on a substrate, while the other SWNTs in the film can lift off. The selected SWNT can be used to fabricate nanodevice and a gas sensor of oxygen is demonstrated in this work.     

Investigation of the influence factors of polyethylene molecule encapsulated into carbon nanotubes by molecular dynamics simulation

In this work, the influence factors, namely chirality, temperature, radius and surface chemical modification, of the interaction energy for polyethylene (PE) molecule encapsulated into single-walled carbon nanotubes (SWNTs) had been investigated by molecular mechanics (MM) and molecular dynamics (MD) simulation. The results showed that all these factors would influence the interaction energy between PE and SWNTs. The interaction energy between PE molecule and the armchair SWNTs is largest among eight kinds of chiral SWNTs. The interaction energy decreases with the increase of temperature or the SWNT radius. The methyl, phenyl, hydroxyl, carboxyl, -F, and amino groups, have been introduced onto the surface of the SWNTs by the simulation software and the influence of SWNT chemical modification has also been investigated. The interaction energy between PE and chemically modified SWNTs is larger than that between PE and pristine SWNTs, and increases with increasing the concentration of the modified groups monotonously. In addition, the group electronegativity and van der Waals force will affect the interaction energy between PE and chemically modified SWNTs greatly, which can be attributed to the electronic structures of the chemically modified groups. This study can provide some useful suggestions for the composite material design and drug transport.     

Electroless deposition of copper and fabrication of copper micropatterns on CVD diamond film surfaces

Electroless deposition of copper on as-grown and amino-modification diamond substrates was investigated. The compact and uniform copper films were successfully electrolessly deposited on as-grown and amino-modification diamond substrates after activation by Pd/Sn colloid nanoparticles. The adhesion interaction between copper films and diamond substrates was roughly estimated by the ultrasonic treatment. The results showed the higher adhesion interaction between copper films and amino-modification diamond substrates than that between the copper films and as-grown diamond substrates due to the greater attractive force between the Pd/Sn colloid nanoparticles and amino-modified diamond surface. The favorable copper micropatterns were successfully constructed on diamond film surfaces by means of the catalyst lift-off method and the copper lift-off method. Furthermore, the electrochemical behavior of copper-modified boron-doped diamond (BDD) was studied for glucose oxidation in 0.2 M sodium hydroxide solution by using cyclic voltammetry, and the result indicated that copper-modified BDD exhibited high catalytic activity to electrochemical oxidation of glucose in alkaline media.     

Comparative study on diameter distribution of single-walled carbon nanotubes using growth templates with different pore sizes: Zeolite-L,ZSM-5, and MCM-41

We report a comparative study on diameter distribution of single-walled carbon nanotubes (SWNTs) grown using nanoporous templates having different pore sizes, namely, zeolite-L, ZSM-5, and MCM-41. The change in the tube diameter based on catalytic film thickness and growth temperature was systematically investigated. We prepared very thin Fe catalyst films with nominal thicknesses of 0.5, 0.7, 1, and 2 Å, and the growth temperature was varied from 850 to 925 °C. We found that the SWNT mean diameter and size distribution width decreased with decreasing catalyst film thickness, growth temperature, and pore sizes of the templates. In addition, all SWNTs grown from the nanoporous templates have narrower diameter distribution compared to the SWNTs grown from SiO₂ planar surface. The obtained results are straightforward and suggest that the template growth has potential for SWNT growth with very narrow diameter distribution.     

Single-walled carbon nanotube fibers, films and balls

Well-defined fibers and films of single-walled carbon nanotubes (SWNTs) with high purity and narrow diameter distributions were obtained from the strand-like raw soot produced by a dc arc-discharge method. These architectures made up of SWNTs have very uniform smooth surfaces. When the strand-like product was placed on a silicon substrate, dipped into water, treated ultrasonically, and then dried in air, another interesting architecture, an SWNT ball, was obtained. This ball-like structure could also be found on the surface of purified SWNTs. We propose that the surface tension of water and the interaction between SWNTs and silica sphere played the key role in the ball (SWNTs outside and silica sphere inside) formation process.     

Assembly of single-walled carbon nanotubes on patterns of Au nanoparticles

We report on the assembly of single-walled carbon nanotubes (SWNTs) and gold nanoparticles (NPs) hybrid structure without any surface modification of SWNTs on patterns of Au nanoparticles (NPs). Microscale Au NP patterns were created on composite self-assembled monolayer (SAM) templates of octadecanethiol (ODT) and octanedithiol (OD) through self-assembly of Au NPs via the thiol-Au chemical bond onto the OD region. On such templates, we observed extensive adhesion and strong affinity of SWNTs on the Au NPs and no SWNT on ODT. We also examined systematically the adhesion of SWNTs on ODT with varying coverage of vapour-deposited Au. We observed little SWNT attachment even when there are high-density of Au clusters on the ODT SAM. Extensive adhesion of SWNTs is observed only when the coverage of ODT by Au is almost complete. Dynamic contact angle measurements of dichlorobenzene on the ODT/Au substrates revealed a direct correlation between the surface wettability and the SWNT assembly on a molecular template.     

Fabrication of patterned polyaniline microstructure through microcontact printing and electrochemistry

Polyaniline (PANI) microstructures on ITO glass surface were achieved by microcontact printing of self-assembled film and electrochemical polymerization in an aqueous monoaniline solution. The patterned microstructures of PANI were easily transferred to an adhesive tape surface, which could be applied in the area of plastic circuit application. Optical microscope, atomic force microscopy (AFM), lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to examine the topography and properties of patterned PANI films. Optical microscope and AFM results showed that the PANI microstructure has regular pattern and clear boundary, while LFM and XPS results implied that this microstructure was completely covered by PANI. The data suggested that the interfacial properties of the surface control the rate of electrochemical polymerization, and the polymerization rate on the modified ITO surface is higher than that on the bare ITO area. In our experiments, cyclic voltammetric method, potentiostatic method and chronopotentiometry method were employed to deposited patterned PANI films on octadecyltrichorosilane modified ITO substrate.     

Structure of single-wall carbon nanotubes purified and cut using polymer

Following on from our previous report that a monochlorobenzene solution of polymethylmethacrylate is useful for purifying and cutting single-wall carbon nanotubes (SWNTs) and thinning SWNT bundles, we show in this report that polymer and residual amorphous carbon can be removed by burning in oxygen gas. The SWNTs thus obtained had many holes (giving them a worm-eaten look) and were thermally unstable. Such severe damage caused by oxidation is unusual for SWNTs; we think that they were chemically damaged during ultrasonication in the monochlorobenzene solution of polymethylmethacrylate. Received: 28 March 2001 / Accepted: 2 August 2001 / Published online: 17 October 2001     

An active nano-supported interface designed from gold nanoparticles embedded on ionic liquid for depositing DNA

The use of an active nano-interface designed from gold nanoparticles embedded on ionic liquid for DNA damage resulted from formalehyde (HCHO) is reported in this article. The active nano-interface was fabricated by depositing gold nanoparticles on the ionic liquid 1-butyl-3-methylimidazolium tetrafluroborate ([bmim][BF₄]). A glassy carbon electrode modified by this composite film was fabricated to immobilize DNA for probing into the damage resulted from HCHO. The modifying process was characterized by X-ray photoelectron spectroscopy, atomic force microscopy and electrochemistry involving electrochemical impedance spectroscopy. It was found that the modified film performs effectively in studying the DNA damage by electrocatalytic activity toward HCHO oxidation.     

Au/TiN复合薄膜制备及其表面增强拉曼光谱研究

表面增强拉曼散射光谱(SERS)已用于环境监测、生物医药、食品卫生等领域,而高活性SERS基底是表面增强拉曼散射光谱技术应用的关键。TiN作为新型等离子材料具有较强的SERS性能,同时化学稳定性及生物相容性较好,但其SERS性能不如贵金属金强。该研究采用氨气还原氮化法和电化学沉积法,在TiN薄膜表面沉积贵金属Au纳米颗粒制备出Au/TiN复合薄膜。在Au/TiN复合薄膜中单质Au和TiN两种物相共存;随着电化学沉积时间延长,TiN薄膜表面单质金纳米颗粒数量逐渐增多,金纳米颗粒尺寸增大,颗粒间距减小。由于金与TiN两者的本征表面等离子共振耦合作用,Au/TiN复合薄膜的共振吸收峰发生了偏移。利用罗丹明6G为拉曼探针分子,对Au/TiN复合薄膜进行SERS性能分析,发现Au/TiN复合薄膜上的R6G探针分子的拉曼峰信号强度随沉积时间延长呈现先增大后减小的规律;当电化学沉积时间为5 min时,R6G拉曼信号峰较高,复合薄膜样品的SERS活性最大。将Au/TiN复合薄膜和Au薄膜分别浸泡在10-3,10-5,10-7,10-8及10-9 mol·L-1 R6G溶液5 min,进行检测限分析,发现Au/TiN复合薄膜检测极限达10-8 mol·L-1,增强因子达到8.82×105,与Au薄膜和TiN薄膜相比,Au/TiN复合薄膜上对R6G探针分子SERS活性最高。这得益于Au/TiN复合膜中表面等离子体产生的耦合效应,使得局域电磁场强度增强,从而引起R6G探针分子拉曼信号增强。通过2D-FDTD模拟电场分布发现Au/TiN,Au及TiN薄膜具有电场增强作用,其中Au/TiN复合薄膜的增强作用尤为显著,这也证实了氮化钛与金纳米颗粒之间存在耦合效应。另外发现TiN与Au之间可能存在电荷转移,促进了4-氨基苯硫酚氧化反应,进而证实了TiN与Au薄膜的协同作用。此外,Au/TiN复合薄膜均匀性较好,相对平均偏差仅为7.58%。由此可见,采用电化学沉积制备的Au/TiN复合薄膜具有作为SERS基底材料的应用潜力。     

Growth of single-walled carbon nanotubes on silicon nanowires

Single-walled carbon nanotubes (SWNTs) have been grown on silicon nanowires (SiNWs) by ethanol chemical vapor deposition (CVD) with Co catalysts. We have found that a surface SiO_x layer of SiNWs is necessary for the formation of active Co catalysts. In fact, the yield of the SWNT/SiNW heterojunctions gradually decreases as the thickness of the surface SiO_x layer decreases. Since thin SiNWs are transparent to an electron beam, the Co nanoparticles on SiNWs can be easily observed as well as SWNTs by TEM. Therefore, the relationship between the diameters of each SWNT and its catalyst nanoparticle has been investigated. The diameters of SWNTs are equal to or slightly smaller than those of the catalyst nanoparticles.     

Single-Walled Carbon Nanotubes Acting as Controllable Transport Channels

The motion and equilibrium distribution of water molecules adsorbed inside neutral and negatively charged singlewalled carbon nanotubes (SWNTs) have been studied using molecular dynamics simulations (MDSs) at room temperature based on CHARMM (Chemistry at HARvard Molecular Mechanics) potential parameters. We find that water molecules have a conspicuous electropism phenomenon and regular tubule patterns inside and outside the charged tube wall. The analyses of the motion behaviour of water molecules in the radial and axial directions show that by charging the SWNT, the adsorption efficiency is greatly enhanced, and the electric field produced by the charged SWNTs prevents water molecules from flowing out of the nanotube. However, water molecules can travel through the neutral SWNT in a fluctuating manner. This indicates that by electrically charging and uncharging the SWNTs, one can control the adsorption and transport behaviour of polar molecules in SWNTs for using as a stable storage medium or long transport channels. The transport velocity can be tailored by changing the charge on the SWNTs, which may have a further application as modulatable transport channels.     

Exciton localization of single-walled carbon nanotubes revealed by femtosecond excitation correlation spectroscopy

Photoluminescence (PL) dynamics in single-walled carbon nanotubes (SWNTs) has been studied by the femtosecond excitation correlation method with a 150 fs time resolution. The SWNT samples were synthesized by different methods and suspended in gelatin films or D2O solutions. The PL dynamics of SWNTs depends on the local environment surrounding the SWNTs rather than the synthesis methods. The very weak temperature dependence of tauPL and the environment-dependent tauPL reveal that the PL relaxation process is dominated by the interplay between free excitons and weakly localized excitons.     

Synthesis and electrochemical characterization of nitrogen-doped and nitrogen–phosphorus-doped multi-walled carbon nanotubes

Nitrogen-doped and nitrogen–phosphorus-doped multi-walled carbon nanotubes (N-MWCNTs and N–P-MWCNTs, respectively) were fabricated by chemical vapor deposition and characterized using scanning electron microscopy and transmission electron microscopy in combination with energy dispersive X-ray spectroscopy and Raman spectroscopy. The electrochemical response of N-MWCNTs and N–P-MWCNTs towards ferrocyanide/ferricyanide was initially studied. The findings exhibit weakening of electrochemical response and sensitivity of nanotubes with phosphorus doping, and thus, within the composite films tested, those consist exclusively of N-MWCNTs exhibit the greatest electrocatalytic activity. N–P-MWCNT film was further applied for individual electrochemical analysis of ascorbic acid (AA), uric acid (UA), and dopamine (DA), and lower limits of detections of 11.6, 7.8, and 1.9 μM were estimated, respectively. The findings demonstrate that AA does not interfere with UA, but considerable interference of AA in analysis of DA was observed. Thus, the simultaneous analysis of AA, UA, and DA on N–P-MWCNTs appears to be restricted.     

Controlling growth and Raman spectra of individual suspended single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) were prepared with ethanol chemical vapor deposition (CVD) on SiO₂ flat and pillar-patterned Si substrates. The effect of CVD temperatures from 600 to 800 °C on SWNTs yields was investigated. By virtue of its unperturbed environment, an individual suspended SWNT grown between two different SiO₂ pillars provides a possibility to study the phonon band structure of SWNT itself at a single-nanotube level. Raman spectra of individual SWNTs grown between pillars were investigated systematically.