Comparative measures of single-wall carbon nanotube dispersion

Model composites of DNA-wrapped single-wall carbon nanotubes in poly(acrylic acid) are used to evaluate metrics of nanotube dispersion. By varying the pH of the precursor solutions, we introduce a controlled deviation from ideal behavior. On the basis of small-angle neutron scattering, changes in near-infrared fluorescence intensity are strongly correlated with dispersion, while optical absorption spectroscopy and resonant Raman scattering are less definitive. Our results represent the first systematic comparison of currently accepted measures of nanotube dispersion.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

Spontaneous dissolution of a single-wall carbon nanotube salt

Upon reduction with alkali metals, single-wall carbon nanotubes (SWNTS) are shown to form polyelectrolyte salts that are soluble in polar organic solvents without any sonication, use of surfactants, or functionalization whatsoever, thus forming true thermodynamically stable solutions of naked SWNTs.     

Temperature dependence of the Breit–Wigner–Fano Raman line in single-wall carbon nanotube bundles

The G band in Raman spectra of single-wall carbon nanotube (SWNT) bundles is studied between 3 and 500 K. The G band is best fit with five Lorentzian lines and one Breit–Wigner–Fano (BWF) line, indicating coupling of phonons to the electronic continuum of metallic SWNTs. It is found that the line width of the BWF line decreases with increasing temperature. This temperature-dependent behavior is contrary to that of the Lorentzian lines, where the line width increases with increasing temperature. The coupling constant 1/q of the BWF line is also found to decrease with increasing temperature. These temperature-dependent behaviors of BWF line provide evidence that it is the bundling effect of SWNTs that greatly enhances the BWF coupling.     

Electrochemistry at chemically assembled single-wall carbon nanotube arrays

Single-wall carbon nanotubes (SWNTs) chemically assembled on gold substrates were employed as electrodes to investigate the charge transfer process between SWNTs and the underlying substrates. Cyclic voltammetry (CV) indicates that the assembled SWNTs allow electron communication between a gold electrode and the redox couple in solution, though the SWNTs are linked directly onto the insulating monolayer of 11-amino-n-undecanethiol (AUT) on the Au substrate. An electron transfer (ET) mechanism, which contains an electron tunneling process across the AUT monolayer, is proposed to explain the CV behavior of Au/AUT/SWNT electrodes. Electrochemical measurements show that the apparent electron tunneling resistance, which depends on the surface density of assembled SWNTs, has apparent effects similar to those of solution resistance on CV behavior . The theory of solution resistance is used to describe the apparent tunneling resistance. The experimental results of the dependence of ET parameter psi on the potential scan rate upsilon are in good agreement with the theoretical predictions. Kinetic studies of the chemical assembly of SWNTs by atomic force microscopic (AFM), electrochemical, and Raman spectroscopic methods reveal that two distinct assembly kinetics exist: a relatively fast step that is dominated by the surface reaction, and a successive slow step that is governed by bundle formation.     

The characteristic size of carbon nanotube bundles

The dependence of the size of a carbon nanotube bundle on the size of catalytic particles and separate nanotubes was calculated. The size of bundles was shown to be determined by the distortions of van der Waals bonds between nanotubes in the vicinity of a catalytic particle and nanotube bending in the bundle. Both effects increased as the thickness of the bundle grew. The calculated bundle sizes were compared with the experimental data on growing nanotubes obtained by the chemical vapor deposition, arc, and laser methods. Original Russian Text ? N.I. Alekseev, N.A. Charykov, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 7, pp. 1327–1332.     

Raman studies of solutions of single-wall carbon nanotube salts

Polyelectrolyte solutions of Na-doped single-wall carbon nanotube (SWNT) salts are studied by Raman spectroscopy. Their Raman signature is first compared to undoped SWNT suspensions and dry alkali-doped SWNT powders, and the results indicate that the nanotube solutions consist of heavily doped (charged) SWNT. Raman signature of doping is then used to monitor in situ the oxidation reaction of the nanotube salt solutions upon exposure to air and to an acceptor molecule (benzoquinone). The results indicate a direct charge-transfer reaction from the acceptor molecule to the SWNT, leading to their gradual charge neutralization and eventual precipitation in solution. The results are consistent with a simple redox titration process occurring at the thermodynamical equilibrium.     

Functional single-wall carbon nanotube nanohybrids--associating SWNTs with water-soluble enzyme model systems

We succeeded in integrating single-wall carbon nanotubes (SWNTs), several water-soluble pyrene derivatives (pyrene(-)), which bear negatively charged ionic headgroups, and a series of water-soluble metalloporphyrins (MP(8+)) into functional nanohybrids through a combination of associative van der Waals and electrostatic interactions. The resulting SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8+) were characterized by spectroscopic and microscopic means and were found to form stable nanohybrid structures in aqueous media. A crucial feature of our SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8)(+) is that an efficient exfoliation of the initial bundles brings about isolated nanohybrid structures. When the nanohybrid systems are photoexcited with visible light, a rapid intrahybrid charge separation causes the reduction of the electron-accepting SWNT and, simultaneously, the oxidation of the electron-donating MP(8)(+). Transient absorption measurements confirm that the radical ion pairs are long-lived, with lifetimes in the microsecond range. Particularly beneficial are charge recombination dynamics that are located deep in the Marcus-inverted region. We include, for the first time, work devoted to exploring and testing FeP(8)(+) and CoP(8)(+) in donor-acceptor nanohybrids.     

Flexible transparent conducting single-wall carbon nanotube film with network bridging method

Hollow ZrO(2) microspheres with mesoporous shells have been synthesized by a novel hydrothermal reaction of zirconium oxychloride in the presence of urea, hydrochloric acid, and ethanol. The morphology and shell thickness of the hollow microspheres can be controlled by varying synthesis conditions. After calcination at high temperature, the morphologies of the hollow microspheres are essentially preserved. Pt catalyst supported on the hollow calcined ZrO(2) microspheres exhibits more excellent catalytic performance in CO oxidation than those on ZrO(2) powders derived from conventional precipitation methods.     

Carbon nanotube salts. Arylation of single-wall carbon nanotubes

[reaction: see text] Carbon nanotube salts prepared by treating single-wall carbon nanotubes (SWNTs) with lithium in liquid ammonia react readily with aryl iodides to give SWNTs functionalized by aryl groups.     

Electrochemical and conductivity measurements of single-wall carbon nanotube network electrodes

The electrochemical response of two-dimensional networks of pristine single-wall carbon nanotubes (SWNTs) has been investigated. SWNTs were grown by catalyzed chemical vapor deposition on an insulating SiO2 substrate, and then electrically contacted by lithographically defined Au electrodes. Subsequent insulation of the contact electrodes enabled the electrochemical properties of the SWNT network to be isolated and directly studied for the first time. The electrochemical activity of the SWNT network was found to be strongly dependent on the applied potential. For the same SWNT electrode, the limiting current for the oxidation of 5 mM Fe(phen)32+ was found to be much greater than expected based on the signal for the reduction of 5 mM Ru(NH3)63+. Simultaneous conductance and electrochemical measurements demonstrated decreasing conductance as the potential was scanned negative (versus Ag/AgCl) with the minimum conductance at around the reduction potential for Ru(NH3)63+. These results are consistent with the presence of both metallic and semiconducting SWNTs in the SWNT network electrode. Moreover, these results show that through appropriate choice of mediator and electrode potential, metallic SWNTs can be electrochemically addressed independently of semiconducting SWNTs.     

Elemental analysis of a single-wall carbon nanotube candidate reference material

A material containing single-wall carbon nanotubes (SWCNTs) with other carbon species, catalyst residues, and trace element contaminants has been prepared by the National Institute of Standards and Technology for characterization and distribution as Standard Reference Material SRM 2483 Carbon Nanotube Soot. Neutron activation analysis (NAA) and inductively coupled plasma mass spectrometry (ICP–MS) were selected to characterize the elemental composition. Catalyst residues at percentage mass fraction level were determined with independent NAA procedures and a number of trace elements, including selected rare earth elements, were determined with NAA and ICP–MS procedures. The results of the investigated materials agreed well among the NAA and ICP–MS procedures and good agreement of measured values with certified values was found in selected SRMs included in the analyses. Based on this work mass fraction values for catalyst and trace elements were assigned to the candidate SRM.     

Water-soluble full-length single-wall carbon nanotube polyelectrolytes: preparation and characterization

HiPco single-wall carbon nanotubes (SWNTs) have been noncovalently modified with ionic pyrene and naphthalene derivatives to prepare water-soluble SWNT polyelectrolytes (SWNT-PEs), which are analogous to polyanions and polycations. The modified nanotubes have been characterized with UV-vis-NIR, fluorescence, Raman and X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The nanotube-adsorbate interactions consist of pi-pi stacking interactions between the aromatic core of the adsorbate and the nanotube surface and specific contributions because of the substituents. The interaction between nanotubes and adsorbates also involves charge transfer from adsorbates to SWNTs, and with naphthalene sulfonates the role of a free amino group was important. The ionic surface charge density of the modified SWNTs is constant and probably controlled by electrostatic repulsion between like charges. The linear ionic charge density of the modified SWNTs is similar to that of common highly charged polyelectrolytes.     

用羟基磷灰石和单壁碳纳米管制备葡萄糖传感器的研究

在滴涂法制得单壁碳纳米管(SWNTs)修饰电极的基础上,采用电化学方法沉积纳米羟基磷灰石(HA)涂层,进而利用分子组装技术将葡萄糖氧化酶(GOD)固定到该电极上,制得的修饰电极的循环伏安测量结果表明,GOD发生了直接的电子传递.GOD-HA-SWNTs/GC修饰电极对不同浓度的葡萄糖呈现两个良好的线性响应范围,有望开发...     

NaDDBS as a dispersion agent for multiwalled carbon nanotubes in capillary EKC separation of nucleotides

A novel pseudostationary phase (PSP) of multiwalled carbon nanotubes (MWCNTs) dispersed with sodium dodecylbenzenesulfonate (NaDDBS) was used for the EKC separation of nucleotides. NaDDBS has a long hydrophobic chain and a benzylsulfonate group. It suspends more MWCNTs (about 100-fold) than SDS, and the π-π interaction between the benzene ring of NaDDBS and MWCNTs prolongs the slurry suspension time. Using NaDDBS as a surfactant can reduce the required amount of MWCNTs and decrease the baseline noise. To produce a stable suspension, the optimum ratio (w/w) of MWCNTs to NaDDBS was investigated with turbidimetry. In this context, several parameters affecting EKC separation were studied, including buffer pH, composition, concentration, and the organic modifier. Use of NaDDBS (8 mg/L)/MWCNTs (0.8 mg/L) as the PSP in a phosphate buffer (30 mM, pH 8) yielded complete resolution of seven geometric isomers of a nucleoside monophosphate. In stacking mode, with 10% MeOH in the sample plug, the mixture of nucleoside mono-, di-, and tri-phosphates was satisfactorily separated in phosphate buffer (50 mM, pH 9). The results indicate that nucleotides with bases containing more electron-withdrawing groups interact more strongly with MWCNTs. The system has been used to separate oligonucleotides, and to analyze nucleotides in a complex matrix sample.     

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.     

Titanium coverage on a single-wall carbon nanotube: molecular dynamics simulations

The minimum energy structures of Ti covered (8,0) single-wall carbon nanotube (SWNT) have been investigated theoretically. Using available experimental data and the results of density functional theory calculations, we first parametrized a reliable empirical many-body potential energy function (PEF) for the CTi binary system. The PEF used in the calculations includes two- and three-body atomic interactions. Then performing molecular dynamics simulations at 1 and 300 K, we obtained the minimum-energy configurations for Ti covered (8,0)-SWNT. The configurations reported here include low and high coverage of Ti on nanotubes. We have found that one layer of Ti did not distort the nanotube significantly, whereas two-layer coverage showed an interesting feature: the second layer of Ti pushed the first layer inside the wall of nanotube, but the general shape of the nanotube was not affected so much.