High-purity Single-walled Carbon Nanotubes Research Articles

Cytometry in the Short-Wave Infrared.

Cytometry plays a crucial role in characterizing cell properties, but its restricted optical window (400-850 nm) limits the number of stained fluorophores that can be detected simultaneously and hampers the study and utilization of short-wave infrared (SWIR; 900-1700 nm) fluorophores in cells. Here we introduce two SWIR-based methods to address these limitations: SWIR flow cytometry and SWIR image cytometry. We develop a quantification protocol for deducing cellular fluorophore mass. Both systems achieve a limit of detection of ∼0.1 fg cell-1 within a 30 min experimental time frame, using individualized, high-purity (6,5) single-wall carbon nanotubes as a model fluorophore and macrophage-like RAW264.7 as a model cell line. This high-sensitivity feature reveals that low-dose (6,5) serves as an antioxidant, and cell morphology and oxidative stress dose-dependently correlate with (6,5) uptake. Our SWIR cytometry holds immediate applicability for existing SWIR fluorophores and offers a solution to the issue of spectral overlapping in conventional cytometry.

Single-Walled Carbon Nanotube-Reinforced PEDOT: PSS Hybrid Electrodes for High-Performance Ionic Electroactive Polymer Actuator

Ionic electroactive polymer (iEAP) actuators are recognized as exceptional candidates for artificial muscle development, with significant potential applications in bionic robotics, space exploration, and biomedical fields. Here, we developed a new iEAP actuator utilizing high-purity single-walled carbon nanotubes (SWCNTs)-reinforced poly(3, 4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT: PSS, PP) hybrid electrodes and a Nafion/EMIBF4 ion-exchange membrane via a straightforward and efficient spray printing technique. The SWCNT/PP actuator exhibits significantly enhanced electric conductivity (262.9 S/cm) and specific capacitance (22.5 mF/cm2), benefitting from the synergistic effect between SWCNTs and PP. These improvements far surpass those observed in activated carbon aerogel bucky-gel-electrode-based actuators. Furthermore, we evaluated the electroactive behaviors of the SWCNT/PP actuator under alternating square-wave voltages (1–3 V) and frequencies (0.01–100 Hz). The results reveal a substantial bending displacement of 6.44 mm and a high bending strain of 0.61% (at 3 V, 0.1 Hz), along with a long operating stability of up to 10,000 cycles (at 2 V, 1 Hz). This study introduces a straightforward and efficient spray printing technique for the successful preparation of iEAP actuators with superior electrochemical and electromechanical properties as intended, which hold promise as artificial muscles in the field of bionic robotics.

High-crystallinity single-walled carbon nanotube aerogel growth: Understanding the real-time catalytic decomposition reaction through floating catalyst chemical vapor deposition

In this study, high-purity single-walled carbon nanotubes (SWCNTs) are synthesized with additional carrier gas through floating catalyst chemical vapor deposition. The presence of Ar during the SWCNT aerogel formation affects to the precursor decomposition and to the formation of different reactive hydrocarbons. Furthermore, the concentration of produced various carbon species is sensitive to the carrier gas compositions. The in-situ sampling methods prove the thermodynamic pathway for the hydrocarbon cracking during carbon nanotube (CNT) aerogel formation process. The addition of Ar promoted the formation of reactive hydrocarbon species, such as CH3, CH4, and C2H4/CO, to improve CNT morphology and graphitization. Ar has improved purity of CNTs compared to when only H2 is used. The synthesized CNTs were narrow in size, and the diameter decreased from 1.8 to 1.2 nm with the carrier gas composition (Rx) according to Ar addition. The IG/ID ratio of the CNTs changed from 78 to 3 at R0.1 and R0.57, respectively. Furthermore, the purity also increased to approximately 10% from 78% to 91% depending on Rx.

Supercapacitor with electrodes based on high-purity single-walled carbon nanotubes

We studied a supercapacitor with high purity carbon paper electrodes [1] with a specific gravity of 20 g/m2. The specific capacitance of the electrode during assembly in a coin cell housing with an aqueous 6M KOH electrolyte, at a scan rate of 1 mV/s, is 52 F/g. The specific power is 195.42 W/kg and the specific energy is 0.19 W⋅h/kg at a scan rate of 100 mV/s, which is included in the region of supercapacitors in the Ragone plot.

From Bio to Nano: A Review of Sustainable Methods of Synthesis of Carbon Nanotubes

This review summarizes the up-to-date techniques devised to synthesize carbon nanotubes (CNTs) from liquid or solid precursors of sustainable nature. The possibility to replace petroleum-based feeds for renewable resources such as essential oils or plant shoots is critically examined. The analysis shows that the complex nature of such resources requires the optimization of the reaction conditions to obtain products of desired microstructure and chemical composition. However, appropriate tuning of the process parameters enables the synthesis of even high-purity single-walled CNTs with a spectrum of demonstrated high-performance applications at low cost. The sheer number of successful studies completed on this front so far and described herein validate that the development of techniques for the manufacture of such products of high-added value from common precursors is not only possible but, most importantly, promising.

Directly crosslinked dextran gels for SWCNT separation

The gel column chromatography method allows high-throughput and high-purity single-wall carbon nanotube (SWCNT) separation. However, the role of the gel in this system has not been fully understood. In this study, five gels with different dextran concentrations were synthesized by directly crosslinking dextran with epichlorohydrin. The low dextran concentration gels work for metal/semiconductor separation and diameter sorting of semiconducting SWCNTs. This is evidence that the chemical structure in the gel that is responsible for the selective adsorption of semiconducting SWCNTs is dextran. However, high dextran concentration gels did not adsorb SWCNTs, although the adsorption site was dextran. Micro-Raman measurements on gel slices revealed that the high dextran concentration gel has a pore size too small to allow deep diffusion of SWCNTs. Not only the chemical structure but also the physical structure is important for designing high-performance gels for SWCNT separation in the near future.

Rotational dynamics and dynamical transition of water inside hydrophobic pores of carbon nanotubes

Water in a nanoconfined geometry has attracted great interest from the viewpoint of not only basic science but also nanofluidic applications. Here, the rotational dynamics of water inside single-walled carbon nanotubes (SWCNTs) with mean diameters larger than ca. 1.4 nm were investigated systematically using 2H nuclear magnetic resonance spectroscopy with high-purity SWCNTs and molecular dynamics calculations. The results were compared with those for hydrophilic pores. It was found that faster water dynamics could be achieved by increasing the hydrophobicity of the pore walls and decreasing the pore diameters. These results suggest a strategy that paves the way for emerging high-performance filtration/separation devices. Upon cooling below 220 K, it was found that water undergoes a transition from fast to slow dynamics states. These results strongly suggest that the observed transition is linked to a liquid-liquid crossover or transition proposed in a two-liquid states scenario for bulk water.

(Invited) Plasma-Based Technology for Mass Production of Graphene and Other 2D Layered Materials

Arc discharge plasma is as one of the most practical and efficient methods to synthesize various carbon nanostructures such as single-walled carbon nanotubes (SWCNT) and graphene with minimal defects and large yield. This is achieved due to the relatively high synthesis temperature and eco-friendly growth mechanism. Moreover, by introducing a magnetic field during synthesis process, large-scale graphene and high-purity SWCNT can be obtained in one step. In addition, the yield of graphene can be controlled by external parameters, such as the type and pressure of buffer gas, the temperature of substrate, and plasma density and temperature. Bulk graphene (graphene platelets, flakes) is usually characterized by several layer (2-20 nm) graphene pieces having characteristics sizes of about microns to ten microns. Currently, the main method for synthesis of bulk graphene is chemical exfoliation, where chemicals are utilized to separate the graphene sheets from the piece of graphite. Current production capability are quite limited and estimated to be around several tens of tons of material annually worldwide. This work is focused on development of novel highly efficient and low cost plasma-based method for graphene production in industrial quantities characterized by exceptional product properties. The synthesis is based on utilization of arc discharge supported by ablation of anode material at atmospheric pressures. Pure carbon anode (several millimeters in diameter) and arc current in the range 50-100A were utilized for the synthesis. The graphene was synthesized on the metal substrate and was mechanically remove using metallic brush immediately after the synthesis. The synthesized samples were characterized using SEM, TEM and Raman spectroscopy. Typical size of the graphene platelets was found to be about several microns. The graphene platelets down to ~2 layers were obtained. We present state-of-the-art experimental data on various attempts to employ the arc plasma technique for the graphene synthesis and consider growth mechanisms including precipitation, surface-catalyzed processes and a substrate-independent approach. The potential of arc synthesis for the growth of other types of 2D materials and future prospects are discussed.

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.

Elucidating the effect of heating induced structural change on electrical and thermal property improvement of single wall carbon nanotube

We have clarified that the electrical and thermal properties of single-walled carbon nanotubes (SWCNTs) are improved by multiple structural changes (wall number, diameter, and crystallinity) induced by high temperature treatment. Focusing on the relationship between structural change and electrical and thermal properties, high-purity SWCNTs were fabricated using the water-assisted CVD method and treated at high temperatures (1500–2000°C) in an argon atmosphere. We showed that the electrical and thermal properties of the SWCNTs were improved by ∼2.9 and 3.0, respectively, which required lower treatment temperatures than for multi-walled CNTs (MWCNTs). In addition to the crystallinity improvement, the wall number and diameter increased with treatment temperature. When compared to as-grown SWCNTs of similar wall number and diameter, the heat treated SWCNTs exhibited higher electrical and thermal properties, which suggested that the property improvements could be attributed to not only to the wall number and diameter but also to the improvement in crystallinity.

Spatially Selective Au Nanoparticle Deposition and Raman Analysis of Ion-Irradiated Single-Wall Carbon Nanotubes

Electroless deposition of gold nanoparticles (Au-NPs) onto ion-irradiated single-wall carbon nanotubes (SWCNTs) represents a selective method to spatially profile defects by scanning electron microscopy (SEM). High purity SWCNT papers were irradiated with 150 keV 11B+ and subsequently exposed to 0.01 M KAuBr4(aq) to nucleate Au-NPs. Based on statistical image analysis, a 30 s KAuBr4(aq) exposure is sufficient to indicate the presence of defects by Au-NP nucleation, resulting in particle radii of ∼14 nm and minimal coalescence. A decrease in interparticle distance along individual SWCNT bundles and an increase in Au-NP areal density from 3 to 58 Au-NPs/μm2 are measured over the fluence range of 1 × 1013–1 × 1015/cm2, respectively. Raman analysis shows that the G′-band peak position progressively downshifts for the SWCNTs due to ion irradiation, whereas purified SWCNTs exhibit an upshift from charge transfer with KAuBr4(aq). A strong correlation between the Au-NP areal density from SEM and the relative ratios for the Raman D and G′ peaks confirms the method is directly monitoring ion irradiation-induced structural damage. Overall, the procedure provides a rapid assessment of SWCNT defect density based on microscopy analysis and shows that SWCNTs can be used as a fluence-based dosimeter or adequate support for controlled NP deposition.

Paper-based ultracapacitors with carbon nanotubes-graphene composites

In this paper, a paper-based ultracapacitors were fabricated by the rod-rolling method with the ink of carbon nanomaterials, which were synthesized by arc discharge under various magnetic conditions. Composites of carbon nanostructures, including high-purity single-walled carbon nanotubes (SWCNTs) and graphene flakes were synthesized simultaneously in a magnetically enhanced arc. These two nanostructures have promising electrical properties and synergistic effects in the application of ultracapacitors. Scanning electron microscope, transmission electron microscope, and Raman spectroscopy were employed to characterize the properties of carbon nanostructures and their thin films. The sheet resistance of the SWCNT and composite thin films was also evaluated by four-point probe from room temperature to the cryogenic temperature as low as 90 K. In addition, measurements of cyclic voltammetery and galvanostatic charging/discharging showed the ultracapacitor based on composites possessed a superior specific capacitance of up to 100 F/g, which is around three times higher than the ultracapacitor entirely fabricated with SWCNT.

Influence of the purification process on the semiconducting content of single-walled carbon nanotubes synthesized by arc discharge

Single-walled carbon nanotubes (SWCNTs) were synthesized by arc discharge and then purified by a two-step process including thermal and acid treatments. As-synthesized, thermal-treated, and fully purified (thermal- and acid-treated) samples were characterized using thermogravimetric analysis, continuous resonant Raman scattering, and ultraviolet–visible–near infrared (UV–Vis–NIR) absorption spectroscopy. Thermal and acid treatments eliminate carbonaceous particles and metal catalyst particles, respectively, resulting in high-purity SWCNTs. Continuous resonant Raman scattering and UV–Vis–NIR absorption spectroscopy demonstrated that the metallic content of the arc-synthesized SWCNTs varied according to the purification process; as-synthesized (∼15%), thermal-treated (∼30%), and thermal/acid-treated (∼25%). Transparent conducting films were prepared using three different purity grades and their properties were analyzed. Thermal-treated nanotubes displayed superior performance compared with the other samples owing to its higher metallic content and smaller bundle diameters.

Purification and Dispersion of Single-walled Carbon Nanotubes for Transparent Conducting Films

In our study, air oxidation together with three different procedures for purifying single-walled carbon nanotubes (SWCNTs) was investigated. High purity SWCNTs were obtained. The purified SWCNTs were dispersed into four different types of dispersants and different ratio of SWCNTs to dispersant was evaluated in order to find the optimal condition. Transparent conducting films were fabricated by the purified and well dispersed SWCNT solution. Nitric acid concentration was optimized to enhance the film conductivity. SWCNT films with low sheet resistance and high transmittance were obtained by nitric acid treatment.

Emission spectra analysis of arc plasma for synthesis of carbon nanostructures in various magnetic conditions

Arc discharge supported by the erosion of anode materials is one of the most practical and efficient methods to synthesize various high-quality carbon nanostructures. By introducing a non-uniform magnetic field in arc plasmas, high-purity single-walled carbon nanotubes (SWCNT) and large-scale graphene flakes can be obtained in a single step. In this paper, ultraviolet-visible emission spectra of arc in different spots under various magnetic conditions are analyzed to provide an in situ investigation for transformation processes of evaporated species and growth of carbon nanostructures in arc. Based on the arc spectra of carbon diatomic Swan bands, vibrational temperature in arc is determined. The vibrational temperature in arc center was measured around 6950 K, which is in good agreement with our simulation results. Experimental and simulation results suggest that SWCNT are formed in the arc periphery region. Transmission electronic microscope and Raman spectroscope are also employed to characterize the properties of carbon nanostructures.

Simultaneous Synthesis of Single-walled Carbon Nanotubes and Graphene in a Magnetically-enhanced Arc Plasma

Carbon nanostructures such as single-walled carbon nanotubes (SWCNT) and graphene attract a deluge of interest of scholars nowadays due to their very promising application for molecular sensors, field effect transistor and super thin and flexible electronic devices(1-4). Anodic arc discharge supported by the erosion of the anode material is one of the most practical and efficient methods, which can provide specific non-equilibrium processes and a high influx of carbon material to the developing structures at relatively higher temperature, and consequently the as-synthesized products have few structural defects and better crystallinity. To further improve the controllability and flexibility of the synthesis of carbon nanostructures in arc discharge, magnetic fields can be applied during the synthesis process according to the strong magnetic responses of arc plasmas. It was demonstrated that the magnetically-enhanced arc discharge can increase the average length of SWCNT (5), narrow the diameter distribution of metallic catalyst particles and carbon nanotubes (6), and change the ratio of metallic and semiconducting carbon nanotubes (7), as well as lead to graphene synthesis (8). Furthermore, it is worthwhile to remark that when we introduce a non-uniform magnetic field with the component normal to the current in arc, the Lorentz force along the J×B direction can generate the plasmas jet and make effective delivery of carbon ion particles and heat flux to samples. As a result, large-scale graphene flakes and high-purity single-walled carbon nanotubes were simultaneously generated by such new magnetically-enhanced anodic arc method. Arc imaging, scanning electron microscope (SEM), transmission electron microscope (TEM) and Raman spectroscopy were employed to analyze the characterization of carbon nanostructures. These findings indicate a wide spectrum of opportunities to manipulate with the properties of nanostructures produced in plasmas by means of controlling the arc conditions.

High NIR-purity index single-walled carbon nanotubes for electrochemical sensing in microfluidic chips

Single-walled carbon nanotubes (SWCNTs) should constitute an important natural step towards the improvement of the analytical performance of microfluidic electrochemical sensing. SWCNTs inherently offer lower detection potentials, higher surfaces and better stability than the existing carbon electrodes. However, pristine SWCNTs contain some carbonaceous and metallic impurities that influence their electrochemical performance. Thus, an appropriate processing method is important for obtaining high purity SWCNTs for analytical applications. In this work, a set of 0.1 mg mL(-1) SWCNT dispersions with different degrees of purity and different dispersants (SDBS; pluronic F68 and DMF) was carefully characterized by near infrared (NIR) spectroscopy giving a Purity Index (NIR-PI) ranging from 0.039 to 0.310. The highest purity was obtained when air oxidized SWCNTs were dispersed in SDBS, followed by centrifugation. The SWCNT dispersions were utilized to modify microfluidic chip electrodes for the electrochemical sensing of dopamine and catechol. In comparison with non-SWCNT-based electrodes, the sample with the highest NIR-PI (0.310) exhibited the best analytical performance in terms of improved sensitivity (3-folds higher), very good signal-to-noise ratio, high resistance-to-fouling in terms of relative standard deviation (RSD 7%; n = 15), and enhanced resolution (2-folds higher). In addition, very well-defined concentration dependence was also obtained with excellent correlation coefficients (r ≥ 0.990). Likewise, a good analytical sensitivity, suitable detection limits (LODs) and a very good precision with independence of the concentration assayed (RSDs ≤ 5%) was achieved. These valuable features indicate the suitability of this material for quantitative analysis. NIR-PI and further TEM and XRD characterization demonstrated that the analytical response was driven and controlled by the high NIR-PI of the SWCNTs used. The significance of this work is the demonstration for the first time of the sensitivity-purity relationship in SWCNT microfluidic chips. A novel and valuable analytical tool for electrochemical sensing has been developed: SWCNTs with high purity and a rich surface chemistry with functional groups, both essential for analytical purposes. Also, this work helps to better understand the analytical potency of SWCNTs coupled to microfluidic chips and it opens new gates for using these unique dispersions in real-world applications.

Sharper and Faster “Nano Darts” Kill More Bacteria: A Study of Antibacterial Activity of Individually Dispersed Pristine Single-Walled Carbon Nanotube

To further our understanding on the antibacterial activity of single-walled carbon nanotubes (SWCNTs), high purity SWCNTs with average diameter of 0.83 nm and (7,5) chirality as dominate (n,m) structure were dispersed in a biocompatible surfactant solution. Ultraviolet-visible-near-infrared radiation absorption spectroscopy was employed to monitor the aggregation of SWCNTs. The results demonstrated that individually dispersed SWCNTs were more toxic than SWCNT aggregates toward bacteria (gram-negative Escherichia coli, Pseudomonas aeruginosa, and gram-positive Staphylococcus aureus, Bacillus subtilis). Individually dispersed SWCNTs can be visualized as numerous moving "nano darts" in the solution, constantly attacking the bacteria; thereby, degrading the bacterial cell integrity and causing the cell death. Controlled experimental results suggested that inhibiting cell growth and oxidative stress were not the major causes responsible for the death of cells. Furthermore, the detrimental effects of Co metal residues (up to 1 mug/mL) on SWCNT samples can be ruled out. Atomic force microscope study conducted in suspension proved that the death rates of bacteria were strongly correlated with their mechanical properties; soft cells were more vulnerable to SWCNT piercing. The antibacterial activity of SWCNTs can be remarkably improved by enhancing the SWCNT physical puncture on bacteria in the following ways: (1) dispersing SWCNTs individually to sharpen the nano darts; (2) increasing SWCNT concentration to raise the population density of nano darts; and (3) elevating the shaking speed of incubation to speed up the nano darts. This study elucidated several factors controlling the antibacterial activity of pristine SWCNTs and it provided an insight in developing strategies that can maximize the SWCNT application potentials while minimizing the health and environment risks.

Variation of single wall carbon nanotube dispersion properties with alkyl amide and halogenated aromatic solvents

Organic solvents from the alkyl amide and halogenated aromatic classes have been analyzed as dispersion agents for high purity single wall carbon nanotubes (SWCNTs). The resulting dispersions from two novel SWCNT solvents, N,N,N′,N′-tetramethylmalonamide (TMMA) and 1-chloronaphthalene (1-CLN), have been compared to the well-established solvents, N,N-dimethylacetamide (DMA) and 1,2-dichlorobenzene (DCB). Optical absorption spectroscopy on a series of high purity SWCNT concentrations was used to obtain solvent-dependent dispersion limits, extinction coefficients, and dispersion stability. The variation in SWCNT optoelectronic properties was measured for each solvent dispersion as a function of ultrasonication time and the results demonstrate that under conventional ultrasonication times the halogenated aromatic solvents (DCB and 1-CLN) can significantly affect the SWCNT optical absorption. A post-dispersion analysis was performed on samples, after removal of the solvents, by Raman spectroscopy to monitor structural changes in the SWCNTs. The spectroscopy results for the halogenated aromatic solvents are consistent with formation of a sonopolymer and subsequent interaction with the SWCNTs. In comparison, the alkyl amide solvents (DMA and TMMA) show similar dispersion limits with no significant change in absorbance as a function of ultrasonication, and can easily be removed without affecting the SWCNTs.

Ferromagnetic properties of single-walled carbon nanotubes synthesized by Fe catalyst arc discharge

Abstract Single-walled carbon nanotubes (SWCNTs) were directly synthesized by a hydrogen arc discharge method using only Fe catalyst. The synthesized carbon materials indicated high-purity SWCNTs with Fe catalyst encapsulated with several graphite layers. The diameter of Fe catalysts encapsulated with graphene layers is 1.5–2.0 nm. From the ferromagnetic resonance measurements, the as-synthesized SWCNTs show the ferromagnetic properties at room temperature. The ferromagnetic properties of SWCNTs would be attributed to Fe catalysts encapsulated by graphite layers.