Antenna Chemistry with Metallic Single-Walled Carbon Nanotubes

We show that, when subjected to microwave fields, surfactant-stabilized single-walled carbon nanotubes (SWNTs) develop polarization potentials at their extremities that readily drive electrochemical reactions. In the presence of transition metal salts with high oxidation potential (e.g., FeCl3), SWNTs drive reductive condensation to metallic nanoparticles with essentially diffusion-limited kinetics in a laboratory microwave reactor. Using HAuCl4, metallic particles and sheaths deposit regioselectively at the SWNT tips, yielding novel SWNT−metal composite nanostructures. This process is shown to activate exclusively metallic SWNTs; a degree of diameter selectivity is observed using acceptors with different oxidation potentials. The reaction mechanism is shown to involve Fowler−Nordheim field emission in solution, where electric fields concentrate at the SWNT tips (attaining ∼109 V/m) due to the SWNT high aspect ratio (∼1000) and gradient compression in the insulating surfactant monolayer. Nanotube antenna chemistry is remarkably simple and should be useful in SWNT separation and fractionation processes, while the unusual nanostructures produced could impact nanomedicine, energy harvesting, and synthetic applications

Dielectrophoresis Field Flow Fractionation of Single-Walled Carbon Nanotubes

We report a study on Dielectrophoresis Field Flow Fractionation of Single-Wall Carbon Nanotubes (SWNTs). SWNTs, individually suspended in 1% SDBS solution, were separated by type when they passed a dielectrophoresis field flow fractionation device where 1 MHz AC voltage was supplied and the field strength was well below 1 V per μm. Furthermore, we uniquely observed enrichment of semiconductive SWNTs based on their band gap. In addition to Raman spectrum, UV−vis absorption and NIR fluorescence spectra were used for solution samples for characterization

Synthesis of High Aspect-Ratio Carbon Nanotube “Flying Carpets” from Nanostructured Flake Substrates

We present a robust method for synthesis of aligned, single-walled carbon nanotube (CNT) “flying carpets” from nanostructured alumina flakes. Roll-to-roll e-beam deposition is utilized to produce the flakes, and hot filament chemical vapor deposition is utilized to grow dense, aligned carbon nanotubes from the flakes with remarkably high CNT yields. The flakes are captured inside a mesh cage and freely suspended in the gas flow during growth. Optical characterization indicates the presence of high quality, small diameter single-walled carbon nanotubes

Stable Luminescence from Individual Carbon Nanotubes in Acidic, Basic, and Biological Environments

Aqueous surfactant suspensions of single walled carbon nanotubes (SWNTs) are very sensitive to environmental conditions. For example, the photoluminescence of semiconducting SWNTs varies significantly with concentration, pH, or salinity. In most cases, these factors restrict the range of applicability of SWNT suspensions. Here, we report a simple strategy to obtain stable and highly luminescent individualized SWNTs at pH values ranging from 1 to 11, as well as in highly saline buffers. This strategy relies on combining SWNTs previously suspended in sodium dodecylbenzene sulfonate (SDBS) with biocompatible poly(vinyl pyrrolidone) (PVP), which can be polymerized in situ to entrap the SWNT-SDBS micelles. We present a model that accounts for the photoluminescence stability of these suspensions based on PVP morphological changes at different pH values. Moreover, we demonstrate the effectiveness of these highly stable suspensions by imaging individual luminescent SWNTs on the surface of live human embryonic kidney cells (HEK cells)

Isotropic−Nematic Phase Transition of Single-Walled Carbon Nanotubes in Strong Acids

We present the first quantitative assessment of the maximum amount of nanotubes that can exist in the isotropic phase ( ) of single-walled carbon nanotubes (SWNTs) in Brønsted−Lowry acids. We employ a centrifugation technique in conjunction with UV−vis−nIR spectroscopy to quantify , which is also the critical concentration of the isotropic−nematic transition of SWNTs in strong acids. Centrifugation of biphasic dispersions of SWNTs, that is, acid dispersions consisting of an isotropic phase in equilibrium with an ordered nematic liquid crystalline phase, results in a clear phase separation, where the isotropic phase is supernatant. Dilution of the isotropic phase with a known amount of acid followed by UV−vis−nIR absorbance measurements yields , that is, the maximum concentration of SWNTs that can exist in the isotropic phase in a given acid for a given SWNTs' length distribution. At low SWNT concentration (below 200 ppm) in superacids, light absorbance in the range from 400 to 1400 nm scales linearly with concentration. This Beer's law behavior yields calibration curves for measuring SWNTs' concentration in acids. We find that the critical concentration of the isotropic−nematic transition increases with acid strength in accordance with the previously proposed sidewall protonation mechanism for dispersing SWNTs in acids

Efficient Transfer of a VA-SWNT Film by a Flip-Over Technique

A transfer of a VA-SWNT film onto a conductive surface has been achieved using a novel “flip-over” technique. The top surface of a VA-SWNT film was covered by entangled bundles in an as-grown sample. When a VA-SWNT film was flipped over, an optically flat surface consisting of the tips of very well aligned, clean bundles from the bottom of the film are exposed while the top of the film is well contacted to the substrate. Thus, we expect this technique to provide us with means to prepare carbon nanotube electrodes for device applications such as super capacitors, thermo-electric devices, fuel cells, and field emission filaments

Diameter-Dependent Solubility of Single-Walled Carbon Nanotubes

We study the solubility and dispersibility of as-produced and purified HiPco single-walled carbon nanotubes (SWNTs). Variation in specific operating conditions of the HiPco process are found to lead to significant differences in the respective SWNT solubilities in oleum and surfactant suspensions. The diameter distributions of SWNTs dispersed in surfactant solutions are batch-dependent, as evidenced by luminescence and Raman spectroscopies, but are identical for metallic and semiconducting SWNTs within a batch. We thus find that small diameter SWNTs disperse at higher concentration in aqueous surfactants and dissolve at higher concentration in oleum than do large-diameter SWNTs. These results highlight the importance of controlling SWNT synthesis methods in order to optimize processes dependent on solubility, including macroscopic processing such as fiber spinning, material reinforcement, and films production, as well as for fundamental research in type selective chemistry, optoelectronics, and nanophotonics

Amplification of Single-Walled Carbon Nanotubes from Designed Seeds: Separation of Nucleation and Growth^†

Single-walled carbon nanotubes (SWNTs) may be grown from designed seeds containing an SWNT and the catalyst required for continued growth. Dodecyl side-walled functionalized SWNTs (DD-SWNTs) are end-functionalized with 4-hydroxypyridine via dicyclohexylcarbodiimide coupling to allow covalent coordination of an inorganic cluster pro-catalyst (FeMoC). DD-SWNT-py-FeMoC on spin-on glass was exposed to H2/CH4 at 800 °C, resulting in 3-fold growth in the length of 40% of the seed SWNTs. Only ∼1% of the procatalyst alone nucleate SWNTs under the same conditions, suggesting effective separation of the nucleation and growth processes

Overcoming the “Coffee-Stain” Effect by Compositional Marangoni-Flow-Assisted Drop-Drying

Attempts at depositing uniform films of nanoparticles by drop-drying have been frustrated by the “coffee-stain” effect due to convective macroscopic flow into the contact line. Here, we show that uniform deposition of nanoparticles in aqueous suspensions can be attained easily by drying the droplet in an ethanol vapor atmosphere. This technique allows the particle-laden water droplets to spread on a variety of surfaces such as glass, silicon, mica, PDMS, and even Teflon. Visualization of droplet shape and internal flow shows initial droplet spreading and strong recirculating flow during spreading and shrinkage. The initial spreading is due to a diminishing contact angle from the absorption of ethanol from the vapor at the contact line. During the drying phase, the vapor is saturated in ethanol, leading to preferential evaporation of water at the contact line. This generates a surface tension gradient that drives a strong recirculating flow and homogenizes the nanoparticle concentration. We show that this method can be used for depositing catalyst nanoparticles for the growth of single-walled carbon nanotubes as well as to manufacture plasmonic films of well-spaced, unaggregated gold nanoparticles

Overcoming the “Coffee-Stain” Effect by Compositional Marangoni-Flow-Assisted Drop-Drying

Attempts at depositing uniform films of nanoparticles by drop-drying have been frustrated by the “coffee-stain” effect due to convective macroscopic flow into the contact line. Here, we show that uniform deposition of nanoparticles in aqueous suspensions can be attained easily by drying the droplet in an ethanol vapor atmosphere. This technique allows the particle-laden water droplets to spread on a variety of surfaces such as glass, silicon, mica, PDMS, and even Teflon. Visualization of droplet shape and internal flow shows initial droplet spreading and strong recirculating flow during spreading and shrinkage. The initial spreading is due to a diminishing contact angle from the absorption of ethanol from the vapor at the contact line. During the drying phase, the vapor is saturated in ethanol, leading to preferential evaporation of water at the contact line. This generates a surface tension gradient that drives a strong recirculating flow and homogenizes the nanoparticle concentration. We show that this method can be used for depositing catalyst nanoparticles for the growth of single-walled carbon nanotubes as well as to manufacture plasmonic films of well-spaced, unaggregated gold nanoparticles