Large-scale fabrication of aligned single-walled carbon nanotube array and hierarchical single-walled carbon nanotube assembly

Aligned single-walled carbon nanotubes (SWNTs) and hierarchical SWNT assembly were fabricated by electrospinning. The high fiber elongation and high DC electric field applied during the electrospinning process result in the orientation of the SWNTs along the axial direction of the fiber. The alignment of the electropsun composite fiber transfers this local SWNT orientation to macroscopically aligned SWNTs. After removing the polymer component from the aligned composite fiber, we produced large area aligned SWNTs. The results show that the directional control of SWNT alignment and debundling of SWNTs into individual tubes can be simultaneously realized.     

A comparative study of single-walled carbon nanotube purification techniques using Raman spectroscopy

Raman spectroscopy has been utilized to show the increase of single-walled carbon nanotubes (SWCNTs) content in commercial grade samples synthesized by the chemical vapour deposition (CVD) technique with a minimization of impurities using both hydrochloric acid treatment and surfactant purification. Surfactant purification methods proved to be the most effective, resulting in a three-fold increase in the percentage of SWCNTs present in the purified product as determined by Raman spectroscopy.     

Electronic properties of single-walled carbon nanotube networks

We present a study on the electronic behavior of films of as-prepared and purified single-walled carbon nanotubes (SWNTs) and demonstrate the important role that chemical functionalization plays in modifying their electronic properties, which in turn throws further light on the mechanism of action of SWNT-based sensors. Films of electric arc SWNTs were prepared by spraying, and optical spectroscopy was used to measure the effective film thickness. The room-temperature conductivities (sigma(RT)) of thin films deposited from as-prepared and purified SWNTs are in the range sigma(RT) = 250-400 S/cm, and the nonmetallic temperature dependence of the conductivity indicates the presence of tunneling barriers, which dominate the film conductivity. Chemical functionalization of SWNTs with octadecylamine (ODA) and poly(m-aminobenzenesulfonic acid) (PABS) significantly decreases the conductivity; sigma(RT) = 3 and 0.3 S/cm for SWNT-ODA and SWNT-PABS, respectively.     

Hydrogen-bonded and physisorbed CO in single-walled carbon nanotube bundles

Fourier transform infrared spectroscopy is used to study CO adsorption in single-walled carbon nanotubes. Evidence for adsorption in endohedral and groove/external surface sites is presented through displacement studies involving both CO and CO2. Blue-shifted CO stretching frequencies also indicate that CO hydrogen bonds to hydroxyl functionalities created on the nanotubes by acid purification steps. N2 surface area measurements are used to further understand the porosity of the nanotube samples and to help explain the spectroscopic results.     

Constrained iron catalysts for single-walled carbon nanotube growth

The diameter of single walled carbon nanotubes (SWNTs) determines the electronic properties of the nanotube. The diameter of carbon nanotubes is dictated by the diameter of the catalyst particle. Here we describe the use of iron nanoparticles synthesized within the Dps protein cage as catalysts for the growth of single-walled carbon nanotubes. The discrete iron particles synthesized within the Dps protein cages when used as catalyst particles gives rise to single-walled carbon nanotubes with a limited diameter distribution.     

Light-controlled single-walled carbon nanotube dispersions in aqueous solution

We have succeeded in dispersing single-walled carbon nanotubes (SWNTs) into an aqueous solution of poly(ethylene glycol)-terminated malachite green derivative (PEG-MG) through simple sonication. It was found that UV exposure caused reaggregation of these predispersed SWNTs in the same aqueous medium, as adsorbed PEG-MG photochromic chains could be effectively photocleavaged from the nanotube surface. The observed light-controlled dispersion and reaggragation of SWNTs in the aqueous solution should facilitate the development of SWNT dispersions with a controllable dispersity for potential applications.     

Human fibrinogen adsorption onto single-walled carbon nanotube films

The adsorption behavior of human fibrinogen (Hfg) on single-walled carbon nanotube (SWNT) films was investigated using scanning electron microscopy (SEM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was shown in the SEM images that fibrinogen was adsorbed strongly on the surface of SWNT when the samples were incubated in the Hfg solutions for 10 min. The dependence of adsorption on the concentration of fibrinogen was also investigated and it was found that adsorption increased with increasing concentration. In order to further explore the adsorption of fibrinogen on SWNT surface, NEXAFS spectra were obtained at the N K-edge and the C K-edge. The results confirmed the conclusion regarding the dependence of adsorption on fibrinogen concentration. It is demonstrated that, due to its high sensitivity to the surface elements, NEXAFS spectroscopy is a powerful tool to investigate the adsorption of fibrinogen on SWNT films.     

Light-induced dielectric transparency in single-walled carbon nanotube films

Light-induced difference THz spectroscopy was used to investigate the dielectric response of free-stand single-walled carbon nanotubes (SWCNTs) films in THz region. We observed an enhanced transmission of the peak-signal of THz wave through SWCNTs films under 800 nm pump. In frequency domain, the transparency came from 0.5 to 2.1 THz and the absorption was in 2.1–3.0 THz region. The pump power dependency of the transmission showed this was a nonlinear effect. The dielectric constant response of the SWCNTs films was analyzed theoretically. The analysis suggests that the nonlinear optical properties stem from two factors, which are Drude and Lorentz term for metallic and semiconducting SWCNTs, respectively.     

Layer-by-layer fabrication and characterization of DNA-wrapped single-walled carbon nanotube particles

Carbon nanotubes have been proposed as support materials for numerous applications, including the development of DNA sensors. One of the challenges is the immobilization of DNA or other biological molecules on the sidewall of carbon nanotubes. This paper introduces a new fabrication of DNA-carbon nanotubes particles using the layer-by-layer (LBL) technique on single-walled carbon nanotubes (SWCNTs). Poly(diallyldimethylammonium) (PDDA), a positively charged polyelectrolyte, and DNA as a negatively charged counterpart macromolecule are alternatively deposited on the water-soluble oxidized SWCNTs. Pure DNA/PDDA/SWCNTs particles can be prepared and separated by simple unltracentrifugation. The characterization of DNA/PDDA/SWCNTs particles was carried out by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy, Raman spectroscopy, and thermogravimetric analysis (TGA). An electrode modified by the DNA/PDDA/SWCNTs particles shows a dramatic change of the electrochemical signal in solutions of tris(2,2'-bipyridyl)ruthenium(II) ((Ru(bpy)(3)2+) as a reporting redox probe. A preliminary application of the DNA-modified carbon nanotubes in the development of DNA sensors used in the investigation of DNA damage by nitric oxide is presented.     

Adsorption and diffusion of carbon dioxide and nitrogen through single-walled carbon nanotube membranes

We have used atomically detailed simulations to examine the adsorption and transport diffusion of CO2 and N2 in single-walled carbon nanotubes at room temperature as a function of nanotube diameter. Linear and spherical models for CO2 are compared, showing that representing this species as spherical has only a slight impact in the computed diffusion coefficients. Our results support previous predictions that transport diffusivities of molecules inside carbon nanotubes are extremely rapid when compared with other porous materials. By examining carbon nanotubes as large as the (40,40) nanotube, we are able to compare the transport rates predicted by our calculations with recent experimental measurements. The predicted transport rates are in reasonable agreement with experimental observations.     

Electrochemical impedance spectroscopy at single-walled carbon nanotube network ultramicroelectrodes

Electrochemical impedance spectroscopy (EIS), coupled with chemical vapour deposition (CVD) grown single-walled carbon nanotube (SWNT) network disk-shaped ultramicroelectrodes (UMEs), gives stable, very well-defined and highly reproducible EIS responses for electrolysis of a simple outer sphere redox couple (FcTMA^+/2+). The resulting EIS data can be fitted accurately using a simple electrical circuit model, enabling information on double-layer capacitance, diffusion coefficient of the electroactive species and the rate constant of ET (k⁰) to be extracted in a single EIS experiment. These values are replicated for a range of mediator concentrations and UME sizes (in the range 25–100 μm diameter) demonstrating the robustness of the method. These initial studies bode well for impedance based electroanalysis using SWNT network UMEs.     

Free-standing highly conductive transparent ultrathin single-walled carbon nanotube films

Transparent and conductive single-walled carbon nanotube (SWNT) films are of great importance to a number of applications such as optical and electronic devices. Here, we describe a simple approach for preparing free-standing highly conductive transparent SWNT films with a 20-150 nm thickness by spray coating from surfactant-dispersed aqueous solutions of SWNTs synthesized by an improved floating-catalyst growth method. After the HNO(3) treatment, dipping the SWNT films supporting on glass substrates in water resulted in a quick and nondestructive self-release to form free-standing ultrathin SWNT films on the water surface. The obtained films have sufficiently high transmittance (i.e., 95%), a very low sheet resistance (i.e., ～120 Ω/sq), and a small average surface roughness (i.e., ～3.5 nm for a displayed 10 × 10 μm area). Furthermore, the floating SWNT films on the water surface were easily transferred to any substrates of interest, without intense mechanical and chemical treatments, to preserve their original sizes and network structures. For example, the transferred SWNT films on poly(ethylene terephthalate) films are mechanically flexible, which is a great advantage over conventional indium-tin oxide (ITO) and therefore strongly promise to be "post ITO" for many applications.     

Changes in single-walled carbon nanotube chirality during growth and regrowth

A simple model for joining two single-walled carbon nanotubes (SWNTs) with different, arbitrary chiralities is used to systematically label junction structures which contain pentagon-heptagon pairs. The model is also used, together with density functional theory, to study the energetics of diameter and chirality changes of thin SWNTs during catalyzed growth or regrowth. We choose zigzag and armchair SWNTs attached to a Ni(55) cluster for our case studies.     

Charge transfer from metallic single-walled carbon nanotube sensor arrays

This paper explores the possibility of using arrays of metallic carbon nanotubes as sensors. Unlike their semiconducting counterparts, single-walled carbon nanotube arrays or networks that are dominated by metallic conduction pathways have not been investigated for their environmental sensitivity. In this work, we demonstrate transduction of molecular adsorption via charge transfer through predominantly metallic single-walled carbon nanotubes. Raman spectroscopy and electric field dependent transport confirm that signal transduction takes place through primarily large diameter metallic nanotubes. This unique signal transduction mechanism might have implications for novel sensors. The scaling of the signal with array impedance is well described using an irreversible binding model developed previously. The arrays have several advantages including a simple, two-electrode fabrication, rapid regeneration, and a responsivity that scales predictably and linearly with the number of adsorption sites. An array-assisted hydrolysis of reactive analytes is found to regenerate the nanotube surface from hydrolyzable species which include important organophosphate nerve agents.     

Synthesis and characterization of water soluble single-walled carbon nanotube graft copolymers

Poly(aminobenzene sulfonic acid) (PABS) and polyethylene glycol (PEG) were covalently attached to single-walled carbon nanotubes (SWNTs) to form water-soluble graft copolymers. Quantitative near-IR (NIR) spectroscopic studies of these SWNT graft copolymers indicate a water solubility of about 5 mg/mL, and atomic force microscopy studies show a fairly uniform length and diameter. On the basis of thermogravimetric analysis, the loading of SWNTs in the graft copolymers is estimated to be 30% for SWNT-PABS and 71% for SWNT-PEG. NIR spectroscopic studies of SWNT-PABS show that this graft copolymer has a ground state that is a hybrid of the electronic structures of the isolated PABS and SWNT macromolecules.     

Controlled confinement and release of gases in single-walled carbon nanotube bundles

A simple procedure is described that locks small quantities of SF6, CO2, and 13CO2 into opened single-walled carbon nanotube (SWNT) bundles and keeps the gas in the SWNTs above the desorption temperature of these molecules. The technique involves opening the SWNTs with ozonolysis at 300 K followed by vacuum-annealing at 700 K. Gases are then cryogenically adsorbed into the opened SWNTs and locked into the SWNT pores by functionalizing the sample with a low-temperature ozone treatment. The low-temperature ozone treatment functionalizes the entry ports into the SWNT pores, which in turn create a physical barrier for gases trying to desorb through these functionalized ports. The samples are stable under vacuum for periods of at least 24 h, and the trapped gases can be released by vacuum-heating to 700 K. Reduced quantities of the trapped gases remain in the SWNTs even after exposure to room air. Fourier transform infrared spectroscopy is used to monitor the functionalities resulting from the ozone treatment and to detect the trapped gas species.     

In situ optical spectroelectrochemistry of single-walled carbon nanotube thin films

A detailed study is presented on the optical absorption of thin films of single-walled carbon nanotubes (SWNT) under electrochemical conditions. The procedure for the preparation of free-standing semitransparent films of SWNT is used for the fabrication of a working electrode for transmission optical spectroelectrochemistry. The analysis of the potential dependent spectroscopic response of the SWNT film benefits from the widest possible electrochemical window, in which the charging of SWNT can safely be investigated. This electrochemical window is not limited by parasitic electrochemistry and/or galvanic breakdown reactions occurring at supporting electrode materials such as indium–tin oxide conducting glass or semitransparent Pt film, which were employed in earlier studies. Electrochemical doping of SWNT is observable at the optical absorptions, which are assigned to allowed electronic transitions between van Hove singularities in the density of states of SWNT. Furthermore, the spectral response of counterions, balancing the charging of the nanotube skeleton, is traceable at certain conditions. The latter effect is monitored here through the overtones of C–H stretching vibrations from tetrabutylammonium cations.     

Direct fabrication of single-walled carbon nanotube macro-films on flexible substrates

We employed a floating chemical vapor deposition technique and applied a liquid (solution)-free precursor system for the fabrication of single-walled carbon nanotube macro-films on various flexible substrates from metallic foils to polymer films.