As-produced Single-walled Carbon Nanotubes Research Articles

Sensitivity enhancement of SWCNT gas sensors by nitrogen plasma treatment

Single-walled carbon nanotubes (SWCNTs) hold promise for detecting toxic and chemically aggressive gases due to their unique 1D structure. However, the limited sensitivity of as-produced SWCNT films hampers their practical application as gas sensors. To enhance sensitivity, various functionalization methods, including nitrogen doping, have been explored. In this study, we investigated the impact of low-frequency nitrogen plasma treatment on SWCNT films for sensing reducing and oxidizing air pollutants—specifically, NO2 and NH3—at concentrations ranging from 10 to 50 ppm. TEM and UV-vis-NIR unveiled the etching of the SWCNT structure, and Raman spectroscopy showed the formation of defects following nitrogen plasma treatment. XPS analysis confirmed the presence of amine, pyridinic, and quaternary N-containing defects within the graphitic structure. Upon treating pristine SWCNT films with a 32 W·h dose of plasma, the average chemiresistive response to 50 ppm analyte (in air) at room temperature increased significantly by 100x, rising from 0.2% to 20% (NO2) and from 0.05% to 17% (NH3). Density functional tight-binding modeling corroborated the experimental findings, revealing a correlation between plasma dose and sensor signal. Moreover, the modeling suggested that analyte molecule adsorption on defects is favored over basal plane adsorption.

Multi-nucleation of single-walled carbon nanotubes in floating catalyst chemical vapor deposition

Floating-catalyst CVD (FCCVD) is a highly promising technique for the scalable synthesis of single-walled carbon nanotubes (SWCNTs). The number concentration (NC) of catalyst particles is one of the process parameters which mainly influences yield of as-produced SWCNTs. In the conventional FCCVD methods, catalyst particles are usually synthesized by thermal decomposition of organometallic compounds inside the FCCVD reactor. Being in-situ catalyst formation in conventional FCCVD, it is an open question that how many SWCNTs a single catalyst particle can grow? Herein, we employed our novel spark discharged based FCCVD technique which decouples the formation of catalyst particles and SWCNTs synthesis into two subsequent process to investigate effects of catalyst NC on SWCNTs synthesis. The NC of both catalyst particles and SWCNTs in gas-phase were quantitatively compared using differential mobility analyzer (DMA). The DMA measurements corroborated with atomic force microscopy and X-rays photoelectron spectroscopy revealed that under carefully chosen reaction conditions in FCCVD, a single catalyst particle can grow more than one SWCNTs. We propose that after the growth of 1st SWCNT, the catalyst particle detach itself to start nucleating 2nd SWCNT and this process continues as long as the catalyst remains in the growth region of the FCCVD reactor.

Degradable Fluorene- and Carbazole-Based Copolymers for Selective Extraction of Semiconducting Single-Walled Carbon Nanotubes

Among the solution-based purification methods of as-produced single-walled carbon nanotubes (SWCNTs), conjugated polymer sorting is one of the most promising approaches to obtain semiconducting SWCNTs (s-SWCNTs) with high purity. In order to meet the demand for pure polymer-free s-SWCNTs after polymer wrapping, we synthesized several degradable fluorene- and carbazole-based copolymers for selective extraction of s-SWCNTs. The copolymers are interlinked by imine bonds, and thus, the cleavage can be easily accomplished by acid treatment. The polymer/SWCNT complex dispersions were prepared with as-produced HiPco SWCNTs in toluene and characterized with absorption, photoluminescence excitation and emission mapping, and Raman spectroscopy. Among the synthesized polyimines, fluorene-carbazole copolymers show extremely high separation yield toward s-SWCNTs and high separation purity, while the fluorene–fluorene and fluorene-p-phenylene copolymers show lower yield but higher selectivity to s-SWCNT with specific pairs of (n,m) indices. Quantitative removal of the polymer after acid-triggered degradation was confirmed by X-ray photoelectron spectroscopy. Moreover, the released dispersant-free s-SWCNTs can be further rewrapped by different polymers. Our results pave the way toward the use of dispersant-free semiconducting carbon nanotubes (CNTs) to develop the next generation of CNT devices.

Separation of Semiconducting Carbon Nanotubes Using Conjugated Polymer Wrapping.

In the past two decades, single-walled carbon nanotubes (SWNTs) have been explored for electronic applications because of their high charge carrier mobility, low-temperature solution processability and mechanical flexibility. Semiconducting SWNTs (s-SWNTs) are also considered an alternative to traditional silicon-based semiconductors. However, large-scale, as-produced SWNTs have poor solubility, and they are mixtures of metallic SWNTs (m-SWNTs) and s-SWNTs, which limits their practical applications. Conjugated polymer wrapping is a promising method to disperse and separate s-SWNTs, due to its high selectivity, high separation yield and simplicity of operation. In this review, we summarize the recent progress of the conjugated polymer wrapping method, and discuss possible separation mechanisms for s-SWNTs. We also discuss various parameters that may affect the selectivity and sorting yield. Finally, some electronic applications of polymer-sorted s-SWNTs are introduced. The aim of this review is to provide polymer chemist a basic concept of polymer based SWNT separation, as well as some polymer design strategies, influential factors and potential applications.

Trajectory of the Selective Dissolution of Charged Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes (SWCNTs) are typically produced as a mixture of different lengths and electronic types. Methods for sorting these as-produced mixtures typically require damaging and unscalable techniques to first overcome the strong bundling forces between the nanotubes. Previously, it has been shown that negatively charging SWCNTs can lead to their thermodynamically driven, gentle dissolution in polar solvents, and moreover that this process can selectively dissolve different SWCNT species. However, there are several conflicting claims of selectivity that must be resolved before the full potential of this method for scalably postprocessing SWCNTs can be realized. Here we carefully investigate dissolution as a function of charge added to the as-produced SWCNT sample, using a range of complementary techniques. We uncover a far richer dependence on charge of SWCNT dissolution than previously imagined. At low values of charge added, amorphous carbons preferentially dissolve, followed sequentia...

Spiral Countercurrent Chromatography Enrichment, Characterization, and Assays of Carbon Nanotube Chiralities for Use in Biosensors.

Single-walled carbon nanotubes (SWCNTs) are synthetic materials that hold great promise for electronics that are smaller and more versatile than the current silica-based technologies. But as-produced SWCNTs are generally a mixture of nanotubes with different structures that have vastly different properties. Separating these SWCNTs from multiwalled and metallic carbon nanotubes is vital to explore their individual properties and commercial utility ranging from optics to semiconductors. Compounding the problem of commercial investigation is that the semiconducting SWCNTs are also a mixture of different diameters and/or chiralities with different properties. Analyzing properties of enriched semiconducting SWCNT chiralities has only recently been possible through separation techniques such as aqueous two-phase solvent systems. Our study illustrates a semipreparative spiral countercurrent chromatography (CCC) separation of a commercial mixture of SWCNTs into distinct enriched fractions. A new mixer–settler spiral disk rotor was applied in this study, in which we compare the enriched SWCNTs for their effectiveness in biosensors with a high-throughput model assay, followed by antibody-mediated detection of Escherichia coli. Our results demonstrate that CCC-enriched responsive SWCNTs for biosensors can be used in our model assay, as well as for the detection of E. coli. To date, we believe that this is the first study along with Liu et al. [Chirality-controlled synthesis of single-wall carbon nanotubes using vapour-phase epitaxy. Nat. Commun.2012, 3, 119923149724] to demonstrate a specific utility of separated SWCNT species.

Tethered anthracene pair as molecular tweezers for post-production separation of single-walled carbon nanotubes

As-produced single-walled carbon nanotubes (SWNTs) are metallic and semiconducting mixtures. An anthracene mono-derivative with a long alkyl tail and a molecule with a tethered pair of anthracene species (bis-anthracene) in a “molecular tweezers”-like configuration were synthesized and evaluated for the separation of SWNTs. While the mono-derivative was incapable of the noncovalent functionalization–solubilization, the bis-anthracene was found to be very effective. The results suggest that molecular tweezers of a tethered pair of planar aromatic species can be coupled with the selection of a suitable solvent or solvent mixture for effective and efficient post-production separation of metallic and semiconducting SWNTs.

Highly Efficient and Scalable Separation of Semiconducting Carbon Nanotubes via Weak Field Centrifugation.

The identification of scalable processes that transfer random mixtures of single-walled carbon nanotubes (SWCNTs) into fractions featuring a high content of semiconducting species is crucial for future application of SWCNTs in high-performance electronics. Herein we demonstrate a highly efficient and simple separation method that relies on selective interactions between tailor-made amphiphilic polymers and semiconducting SWCNTs in the presence of low viscosity separation media. High purity individualized semiconducting SWCNTs or even self-organized semiconducting sheets are separated from an as-produced SWCNT dispersion via a single weak field centrifugation run. Absorption and Raman spectroscopy are applied to verify the high purity of the obtained SWCNTs. Furthermore SWCNT - network field-effect transistors were fabricated, which exhibit high ON/OFF ratios (105) and field-effect mobilities (17 cm2/Vs). In addition to demonstrating the feasibility of high purity separation by a novel low complexity process, our method can be readily transferred to large scale production.

Highly Selective Photothermal Therapy by a Phenoxylated-Dextran-Functionalized Smart Carbon Nanotube Platform.

Near-infrared (NIR) photothermal therapy using biocompatible single-walled carbon nanotubes (SWNTs) is advantageous because as-produced SWNTs, without additional size control, both efficiently absorb NIR light and demonstrate high photothermal conversion efficiency. In addition, covalent attachment of receptor molecules to SWNTs can be used to specifically target infected cells. However, this technique interrupts SWNT optical properties and inevitably lowers photothermal conversion efficiency and thus remains major hurdle for SWNT applications. This paper presents a smart-targeting photothermal therapy platform for inflammatory disease using newly developed phenoxylated-dextran-functionalized SWNTs. Phenoxylated dextran is biocompatible and efficiently suspends SWNTs by noncovalent π-π stacking, thereby minimizing SWNT bundle formations and maintaining original SWNT optical properties. Furthermore, it selectively targets inflammatory macrophages by scavenger-receptor binding without any additional receptor molecules; therefore, its preparation is a simple one-step process. Herein, it is experimentally demonstrated that phenoxylated dextran-SWNTs (pD-SWNTs) are also biocompatible, selectively penetrate inflammatory macrophages over normal cells, and exhibit high photothermal conversion efficiency. Consequently, NIR laser-triggered macrophage treatment can be achieved with high accuracy by pD-SWNT without damaging receptor-free cells. These smart targeting materials can be a novel photothermal agent candidate for inflammatory disease.

Enhanced Electrical Conductivity in Extruded Single-Wall Carbon Nanotube Wires from Modified Coagulation Parameters and Mechanical Processing.

Single-wall carbon nanotubes (SWCNTs) synthesized via laser vaporization have been dispersed using chlorosulfonic acid (CSA) and extruded under varying coagulation conditions to fabricate multifunctional wires. The use of high purity SWCNT material based upon established purification methods yields wires with highly aligned nanoscale morphology and an over 4× improvement in electrical conductivity over as-produced SWCNT material. A series of eight liquids have been evaluated for use as a coagulant bath, and each coagulant yielded unique wire morphology based on its interaction with the SWCNT-CSA dispersion. In particular, dimethylacetamide as a coagulant bath is shown to fabricate highly uniform SWCNT wires, and acetone coagulant baths result in the highest specific conductivity and tensile strength. A 2× improvement in specific conductivity has been measured for SWCNT wires following tensioning induced both during extrusion via increased coagulant bath depth and during solvent evaporation via mechanical strain, over that of as-extruded wires from shallower coagulant baths. Overall, combination of the optimized coagulation parameters has yielded acid-doped wires with the highest reported room temperature electrical conductivities to date of 4.1-5.0 MS/m and tensile strengths of 210-250 MPa. Such improvements in bulk electrical conductivity can impact the adoption of metal-free, multifunctional SWCNT materials for advanced cabling architectures.

Efficient Chemical Modification of Carbon Nanotubes with Metallacarboranes.

As-produced single-walled carbon nanotubes (SWCNTs) tend to aggregate in bundles due to π-π interactions. Several approaches are nowadays available to debundle, at least partially, the nanotubes through surface modification by both covalent and noncovalent approaches. Herein, we explore different strategies to afford an efficient covalent functionalization of SWCNTs with cobaltabisdicarbollide anions. Aberration-corrected HRTEM analysis reveals the presence of metallacarboranes along the walls of the SWCNTs. This new family of materials presents an outstanding water dispersibility that facilitates its processability for potential applications.

Chirally selective growth and extraction of single-wall carbon nanotubes via fullerene nano-peapods

Single-wall carbon nanotubes (SWCNTs) grown from C60 and C70 inside SWCNTs with diameters of 1.5 ± 0.1 nm are investigated. The as-produced SWCNTs have been extracted, separated, and characterized. The products from C70 are dominated by (7,6) and (9,4) SWCNTs, whereas those from C60 are dominated by (6,5) SWCNTs.

Catalyst Design Using Nanoporous Iron for the Chemical Vapor Deposition Synthesis of Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes (SWNTs) have been synthesized via a novel chemical vapor deposition (CVD) approach utilizing nanoporous, iron-supported catalysts. Stable aqueous dispersions of the CVD-grown nanotubes using an anionic surfactant were also obtained. The properties of the as-produced SWNTs were characterized through atomic force microscopy and Raman spectroscopy and compared with purified SWNTs produced via the high-pressure CO (HiPCO) method as a reference, and the nanotubes were observed with greater lengths than those of similarly processed HiPCO SWNTs.

Response of Soil Microorganisms to As-Produced and Functionalized Single-Wall Carbon Nanotubes (SWNTs)

The use of single-wall carbon nanotubes (SWNTs) in manufacturing and biomedical applications is increasing at a rapid rate; however data on the effects of a potential environmental release of the materials remain sparse. In this study, soils with either low or high organic matter contents as well as pure cultures of E. coli are challenged with either raw as-produced SWNTs (AP-SWNTs) or SWNTs functionalized with either polyethyleneglycol (PEG-SWNTs) or m-polyaminobenzene sulfonic acid (PABS-SWNTs). To mimic chronic exposure, the soil systems were challenged weekly for six weeks; microbial activities and community structures for both the prokaryote and eukaryote community were evaluated. Results show that repeated applications of AP-SWNTs can affect microbial community structures and induce minor changes in soil metabolic activity in the low organic matter systems. Toxicity of the three types of SWNTs was also assessed in liquid cultures using a bioluminescent E. coli-O157:H7 strain. Although decreases in light were detected in all treated samples, low light recovery following glucose addition in AP-SWNTs treatment and light absorption property of SWNTs particles suggest that AP-SWNTs suppressed metabolic activity of the E. coli, whereas the two functionalized SWNTs are less toxic. The metals released from the raw forms of SWNTs would not play a role in the effects seen in soil or the pure culture. We suggest that sorption to soil organic matter plays a controlling role in the soil microbiological responses to these nanomaterials.

Facile and Effective Post-Production Separation of Single-Walled Carbon Nanotubes with Paired Aromatic Molecules: A Molecular Tweezers Approach

As-produced single-walled carbon nanotubes (SWNTs) are mostly metallic and semiconducting mixtures. The population of semiconducting SWNTs in the as-produced mixtures is generally much higher than that of their metallic counterparts. Therefore, postproduction separation of metallic and semiconducting SWNTs is important to many potential uses of the nanotubes, especially those demanding higher electrical conductivity yet lower optical absorption. Because planar aromatic species are known to have somewhat different interactions with metallic and semiconducting SWNTs, in this work a molecule with a pair of planar aromatic moieties was specifically designed and synthesized to exaggerate the difference in its noncovalent functionalization and solubilization of the two types of nanotubes. As demonstrated, the molecule exhibited significant selectivity toward semiconducting SWNTs in the solubilization to allow the convenient harvesting of bulk metallic and semiconducting fractions in high purities. The results suggest that molecules with paired aromatic species or essentially molecular tweezers may represent a new class of agents for more effective and also relatively simple postproduction bulk separation of metallic and semiconducting SWNTs.

Chirality-enriched semiconducting carbon nanotubes synthesized on high surface area MgO-supported catalyst

Single-walled carbon nanotubes (SWCNTs) with a narrow diameter distribution were synthesized by radio frequency-Catalytic Chemical Vapor Deposition (RF-CCVD) through the pyrolysis of CH4. Fe–Co bimetallic catalytic nanoclusters were supported on high-surface area MgO nanopowders and used in the nanotube synthesis process. Nanolog absorption fluorescence analysis was used to characterize the chiralities of the as-produced SWCNTs over this nanostructural catalyst. In the final SWCNT sample, the (7,5) semiconducting carbon nanotube species were found to be dominant, with a low chirality variation.

Efficient Solubilization of Single-Walled Carbon Nanotubes Using Tea Solutions

Here we describe the finding that oolong tea and black tea act as excellent carbon nanotube solubilizers to produce individually dissolved single-walled carbon nanotubes (SWNTs), which have been revealed using visible-near IR absorption, photoluminescence and Raman spectroscopy as well as AFM study. The oolong tea solution has a tendency to individually dissolve metallic SWNTs that can be detected by 514 nm-excition, and in solution, the (11,3)SWNTs enriched and (11,0)SWNTs that are contained in as-produced SWNTs were very few. Black tea solution shows similar tendency, while the separation performance was weaker compared to that of the oolong tea. We also used epigallocatechin gallate to solubilize the SWNTs and shed light on the mechanism of the SWNT dissolution. Tea contains numerous components with antioxidant activities; therefore biological and biomedical applications using the present soluble nanotubes might be of interest.

Carbon Nanotube: The Inside Story

Carbon nanotubes (CNTs) were serendipitously discovered as a byproduct of fullerenes by direct current (DC) arc discharge; and today this is the most-wanted material in the nanotechnology research. In this brief review, I begin with the history of the discovery of CNTs and focus on CNTs produced by arc discharge in hydrogen atmosphere, which is little explored outside my laboratory. DC arc discharge evaporation of pure graphite rod in pure hydrogen gas results in multi-walled carbon nanotubes (MWCNTs) of high crystallinity in the cathode deposit. As-grown MWCNTs have very narrow inner diameter. Raman spectra of these MWCNTs show high-intensity G-band, unusual high-frequency radial breathing mode at 570 cm(-1), and a new characteristic peak near 1850 cm(-1). Exciting carbon nanowires (CNWs), consisting of a linear carbon chain in the center of MWCNTs are also produced. Arc evaporation of graphite rod containing metal catalysts results in single-wall carbon nanotubes (SWCNTs) in the whole chamber like macroscopic webs. Two kinds of arc method have been developed to produce SWCNTs: Arc plasma jet (APJ) and Ferrum-Hydrogen (FH) arc methods. Some new purification methods for as-produced SWCNTs are reviewed. Finally, double-walled carbon nanotubes (DWCNTs) are also described.

A comprehensive scenario for commonly used purification procedures of arc-discharge as-produced single-walled carbon nanotubes

The purification of single-walled carbon nanotube (SWCNT) samples was analysed using a multi-technique approach, with structural as well as spectroscopic probes, in order to characterize the samples and to identify important factors for improvement of SWCNT sample quality. The first dry oxidation step (air at 365 °C) is shown to have only a weak selectivity for the removal of the amorphous carbon or weakly organized graphitic species as well as resulting in a partial consumption of the SWCNTs. The functionalization of the SWCNTs is highly specific with formation of carboxyl, hydroxyl and carbonyl groups. On the other hand this oxidation step is highly efficient for the oxidation of the catalytic impurities (Ni, Y) which can be easily removed by subsequent acid treatment. A final high temperature treatment indicates some incomplete restoration of the quality of the SWCNT surface.

Impact of nanometal catalysts on the laser vaporization synthesis of single wall carbon nanotubes

The effects of catalyst particle size on the purity, yield, and purification efficiency of single wall carbon nanotubes (SWCNTs) synthesized via pulsed laser vaporization were investigated. The purity of as-produced SWCNT material synthesized using Ni and Co nanometal (∼13 nm diameter) catalyst particles was compared to material synthesized using conventional micronmetal (2–3 μm diameter) particles. The SWCNT material from nanometal catalysts demonstrated a 50% increase in SWCNT purity as assessed by optical absorption spectroscopy and thermogravimetric analysis (TGA). A change in the thermal oxidation properties was also observed with the nanometal-SWCNTs exhibiting a suppression of the exothermic oxidation of post-synthesis catalyst. Statistical analysis of the TGA residue yielded mean post-synthesis catalyst particle diameters of 18 ± 6 nm and 3 ± 1 nm for the micronmetal and nanometal produced material, respectively. When a thermal oxidation profile was performed, the micronmetal-produced material showed the typical decrease in SWCNT purity with increasing oxidation temperature while the nanometal-produced material showed increasing SWCNT purity with increasing temperature. Overall, the use of nanometal catalysts significantly increases synthesis yield and offers novel thermal oxidation procedures to thermally remove carbonaceous impurities without the aid of acid treatments for the development of potential large-scale purification processing.