A multi-step strategy for cutting and purification of single-walled carbon nanotubes

A multi-step procedure has been developed to cut and purify single-walled carbon nanotubes (SWCNTs) from the pristine soot synthesized by catalytic chemical vapor decomposition, which contains significant amount of multiwalled carbon nanotube (MWCNT) impurities. The procedure involves refluxing in dilute HNO₃ solution followed by (NH₄)₂S₂O₈/H₂SO₄ ultrasonication and a novel ammonia heat treatment step. The metal impurities are removed in the HNO₃ refluxing step. In the (NH₄)₂S₂O₈/H₂SO₄ treatment step, the SWCNTs are cut uniformly into micrometer long, while the MWCNTs are selectively cut into very short curled pieces. These short MWCNT pieces and the amorphous carbon impurities are partly removed in the (NH₄)₂S₂O₈/H₂SO₄ treatment step, and most of them are finally removed by the final ammonia heat treatment. The ammonia heat treatment step also recovers the structures of SWCNTs by healing defects on the sidewall. The final SWCNT products have purity higher than 95%, a length distribution between 1 and 2 μm, and very few defects.     

Parametric study of synthesis conditions in plasma-enhanced CVD of high-quality single-walled carbon nanotubes

High-quality single-walled carbon nanotubes (SWCNTs) have been synthesized from H₂-CH₄ mixtures on a MgO-supported bimetallic Mo/Co catalyst using microwave plasma-enhanced chemical vapor deposition (PECVD). Reaction parameters including temperature, H₂:CH₄ ratio, plasma power, and synthesis time have been examined to assess their influence on SWCNT synthesis. Raman spectroscopy and high-resolution field emission scanning electron microscopy reveal that the quality, selectivity, density and predominant diameter of SWCNTs depend on the varied synthesis parameters. Results of this study can be used to optimize SWCNT synthesis conditions and products and to improve understanding of the growth of SWCNTs by PECVD.     

Evidence for large hydrogen capacity in single-walled carbon nanotubes encapsulated by thin Pd layers onto a Pd substrate

We report a study of hydrogen storage and its mechanism in a novel material, representing single-walled carbon nanotubes (SWCNTs) encapsulated by thin Pd layers onto a Pd substrate. A synergetic effect resulting in combination of the Pd and the SWCNT properties with regard to hydrogen has been achieved. We showed that adding SWCNTs increases the H₂-capacity of the Pd–SWCNT composite under electrochemical loading only by up to 25% relative to the Pd metal alone. At the same time, with regard to the added SWCNTs, such synergetic approach (providing high H₂ pressure from highly H-loaded massive Pd substrate into a small fraction of deposited SWCNT) allowed us to achieve a net capacity of 8–12 wt.%. H₂, thus, bringing a unique chance to study hydrogen storage mechanism in highly H-loaded SWCNT. Using ESR technique it was established that the Pd–C_x π-complexes forming at the openings of SWCNTs could be considered as hydrogen adsorption sites, providing both high gravimetric capacity (H/C > 1) and low hydrogen binding energy in the Pd encapsulated SWCNT.     

Fluidized-bed synthesis of sub-millimeter-long single walled carbon nanotube arrays

The rapid growth method for vertically aligned, single walled carbon nanotube (SWCNT) arrays on flat substrates was applied to a fluidized-bed, using ceramic beads as catalyst supports as a means to mass produce sub-millimeter-long SWCNT arrays. Fe/Al₂O_x catalysts were deposited on the surface of Al₂O₃ beads by sputtering and SWCNTs were grown on the beads by chemical vapor deposition (CVD) using C₂H₂ as a feedstock. Scanning electron microscopy and transmission electron microscopy showed that SWCNTs of 2–4 nm in diameter grew and formed vertically aligned arrays of 0.5 mm in height. Thermogravimetric analysis showed that the SWCNTs had a catalyst impurity level below 1 wt.%. Furthermore, they were synthesized at a carbon yield as high as 65 at.% with a gas residence time as short as <0.2 s. Our fluidized-bed CVD, which efficiently utilizes the three-dimensional space of the reactor volume while retaining the characteristics of SWCNTs on substrates, is a promising option for mass-production of high-purity, sub-millimeter-long SWCNT arrays.     

Polyaniline/single-wall carbon nanotube (PANI/SWCNT) composites for high performance supercapacitors

PANI/SWCNT composites were prepared by electrochemical polymerisation of polyaniline onto SWCNTs and their capacitive performance was evaluated by means of cyclic voltammetry and charge-discharge cycling in 1 M H₂SO₄ electrolyte. The PANI/SWCNT composites single electrode showed much higher specific capacitance, specific energy and specific power than pure PANI and SWCNTs. The highest specific capacitance, specific power and specific energy values of 485 F/g, 228 W h/kg and 2250 W/kg were observed for 73 wt.% PANI deposited onto SWCNTs. PANI/SWCNT composites also showed long cyclic stability. Based upon the variations in the surface morphologies and specific capacitance of the composite, a mechanism is proposed to explain enhancement in the capacitive characteristics. The PANI/SWCNT composites have demonstrated the potential as excellent electrode materials for application in high performance supercapacitors.     

The growth of single-walled carbon nanotubes on a silica substrate without using a metal catalyst

Single-walled carbon nanotubes (SWCNTs) have been directly grown on a SiO₂ substrate using the chemical vapor deposition (CVD) of ethanol without a catalyst. Care was taken to exclude the possibility that the SWCNT growth was induced by conventional metal catalysts such as Fe, Co and Ni resulting from the contamination. Pretreatment of the SiO₂ at 950 °C or a higher temperature in H₂ before CVD was critical for the synthesis of SWCNTs. After CVD process, nano-scale carbon particles were produced besides SWCNTs. Based on these results, we propose that the annealing of SiO₂ substrates in H₂ at high temperature generates defects on their surfaces, and these defects provide nucleation sites for the formation of carbon nanoparticles and assist the formation of carbon nanocaps, thus leading to the SWCNT growth.     

Preparation of single-walled carbon nanotube/TiO2 hybrid atmospheric gas sensor operated at ambient temperature

Single-walled carbon nanotubes (SWCNTs)/TiO₂ hybrid gas sensors operated at a room temperature were fabricated. SWCNTs were stabilized on a Si substrate with interdigitated Pt-electrodes to prepare a gas sensor. Sensing properties of the gas sensor were measured in various concentrations of NO gas. Resistance of the prepared SWCNT based gas sensor decreased with increase of NO gas concentration due to electron transfer from p-type SWCNTs to NO molecules. The SWCNT gas sensor showed high sensitivity and rapid response to the test gas. The hybrid gas sensor using SWCNTs doped with anatase TiO₂ nano-particles was developed, which could work at room temperature under UV-LED (λ = 377 nm) irradiation. It showed rapid recovery to the initial state and higher sensitivity than the SWCNT gas sensor due to TiO₂ photocatalytic effect.     

Spectroscopic characterization of contaminants and interaction with gases in single-walled carbon nanotubes

Several spectroscopic techniques have been used to investigate the presence of contaminants in a commercial purified single-walled carbon nanotube (SWCNT) bucky paper, to determine their cleaning procedure in ultra-high-vacuum conditions and to study how impurities influence the interaction between SWCNTs and gas phase molecules. Nickel catalyst particles and sodium-containing species, likely a residual of the surfactant bath, were fully removed only after prolonged (>2 h) annealing at 1270 ± 30 K. Other impurity elements (S and Si) remain in the material as localised clusters that do not interact with the SWCNTs and do not interfere with their properties.A dramatic difference was observed when the Na-contaminated or the Na-free nanotubes interacted with molecular oxygen. O₂ adsorption was strongly altered by the Na traces, which simulated an intense sample oxidation causing a modification of the tube electronic properties. On the contrary, for the Na-free sample the lack of adsorbed oxygen and the stability of the C1s core level after large O₂ doses demonstrated the absence of any chemical bond between SWCNTs and O₂. Similarly, exposures to N₂, H₂O and CO do not have influence on the electronic properties of SWCNTs. Instead, a sizeable effect on the electronic spectra was observed for SO₂, NO and NO₂ adsorption. The sensitivity of the SWCNT electronic spectra to ppb quantities of nitrogen oxides and sulfur oxide undoubtedly foresees applications in the field of toxic gas sensing.     

Towards high purity graphene/single-walled carbon nanotube hybrids with improved electrochemical capacitive performance

CoMgAl layered double hydroxides were prepared as catalysts for the in situ synchronous growth of graphene and single-walled carbon nanotubes (SWCNTs) from methane by chemical vapor deposition. The as-calcined CoMgAl layered double oxide (LDO) flakes served as the template for the deposition of graphene, and Co nanoparticles (NPs) embedded on the LDOs catalyzed the growth of SWCNTs. After the removal of CoMgAl LDO flakes, graphene (G)/SWCNT/Co₃O₄ hybrids with SWCNTs directly grown on the surface of graphene and 27.3 wt.% Co₃O₄ NPs encapsulated in graphene layers were available. Further removal of the Co₃O₄ NPs by a CO₂-oxidation assistant purification method induced the formation of G/SWCNT hybrids with a high carbon purity of 98.4 wt.% and a high specific surface area of 807.0 m²/g. The G/SWCNT/Co₃O₄ hybrids exhibited good electrochemical performance for pseudo-capacitors due to their high Co₃O₄ concentration and the high electrical conductivity of SWCNTs and graphene. In another aspect, the G/SWCNT hybrids can be used as excellent electrode materials for double-layer capacitors. A high capacity of 98.5 F/g_electrode was obtained at a scan rate of 10 mV/s, 78.2% of which was retained even when the scan rate increased to 500 mV/s.     

Surfactant-free assembling of functionalized single-walled carbon nanotube buckypapers

The electrical and textural properties of single-walled carbon nanotube buckypapers were tunned through chemical functionalization processes. Single-walled carbon nanotubes (SWCNTs) were covalently functionalized with three different chemical groups: Carboxylic acids (-COOH), benzylamine (-Ph-CH₂-NH₂), and perfluorooctylaniline (-Ph-(CF₂)₇-CF₃). Functionalized SWCNTs were dispersed in water or dimethylformamide (DMF) by sonication treatments without the addition of surfactants or polymers. Carbon nanotube sheets (buckypapers) were prepared by vacuum filtration of the functionalized SWCNT dispersions. The electrical conductivity, textural properties, and processability of the functionalized buckypapers were studied in terms of SWCNT purity, functionalization, and assembling conditions. Carboxylated buckypapers demonstrated very low specific surface areas (< 1 m²/g) and roughness factor (R_a = 14 nm), while aminated and fluorinated buckypapers exhibited roughness factors of around 70 nm and specific surface areas of 160-180 m²/g. Electrical conductivity for carboxylated buckypapers was higher than for as-grown SWCNTs, but for aminated and fluorinated SWCNTs it was lower than for as-grown SWCNTs. This could be interpreted as a chemical inhibition of metallic SWCNTs due to the specificity of the diazonium salts reaction used to prepare the aminated and fluorinated SWCNTs. The utilization of high purity as-grown SWCNTs positively influenced the mechanical characteristics and the electrical conductivity of functionalized buckypapers.     

Thermally induced variation in redox chemical bonding structures of single-walled carbon nanotubes exposed to hydrazine vapor

The effect of hydrazine (N₂H₄) vapor on the properties of single-walled carbon nanotube (SWCNT) networks was investigated by sheet resistance measurement, scanning electron microscopy, Raman spectroscopy, ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy (XPS). Our results show that, even after an auxiliary thermal desorption treatment at 80 °C, the n-doping effect on our SWCNTs caused by N₂H₄ vapor still persistently remained. Further analysis on the XPS data suggests that a reactive chemical species, nitrene (NH), generated during thermal decomposition of N₂H₄, could react with SWCNTs by cycloaddition to form cyclic nitrogen-containing aziridine structures on SWCNTs. Our results also show that the formed nitrogen-containing bonding structures were thermally metastable and could be significantly eliminated upon further annealing at 350 °C. Moreover, it was found that the N₂H₄ vapor treatment could introduce nitroso groups and carbonyl groups, but not carboxyl groups, to our pristine SWCNTs. The mild oxidation could be attributed to the HNO₂ and H₂O₂ produced from the reactions of NH and N₂H₄ with oxygen, respectively, when a N₂H₄ treatment was performed in air.     

Gas sensors based on thick films of semi-conducting single walled carbon nanotubes

A comparative study was made of sorted semi-conducting single walled carbon nanotube (SWCNT) films and unsorted SWCNT films for gas sensing applications. The transmission line method is used to monitor separately the SWCNTs film resistance and the contact resistance between electrodes and the SWCNTs, thus revealing that the sensing mechanism mainly relies on a modification of the tube conductivity during gas exposure. The fabricated sensors demonstrate a detection limit of 20 ppb NO₂ and 600 ppb NH₃ mainly attributed to experimental setup limitations. Moreover, semi-conducting nanotubes happened to be 2.5 times more sensitive to NH₃ than unsorted ones, thus proving that selectivity can be improved by sorting the SWCNTs. The temperature dependence of the sensor sensitivity was studied, and a good agreement was found between experimental results and the Langmuir adsorption model.     

Moderating carbon supply and suppressing Ostwald ripening of catalyst particles to produce 4.5-mm-tall single-walled carbon nanotube forests

Millimeter-tall single-walled carbon nanotube (SWCNT) forests were grown by chemical vapor deposition (CVD) from C₂H₂/H₂O/Ar using Fe/Al–Si–O catalysts. Using combinatorial catalyst libraries coupled with real-time monitoring of SWCNT growth, the catalyst and CVD conditions were systematically studied. The keys for this growth are to maintain the C₂H₂ pressure below its upper limit to prevent the killing of the catalysts and to grow the SWCNTs before the catalyst particles lose their activity because of coarsening through Ostwald ripening. Lower temperatures lead to lower limits for the C₂H₂ pressure which result in lower growth rates but also lead to even lower coarsening rates which result in even longer growth lifetimes. Using these principles, we grew 4.5-mm-tall SWCNT forests in 2.5 h at 750 °C.     

A comparative study of electrochemical and biointerfacial properties of acid- and plasma-treated single-walled carbon-nanotube-film electrode systems for use in biosensors

The electrocatalytic and biointerfacial properties of acid- and O₂-plasma-treated single-walled carbon nanotube (SWCNT) electrodes were investigated. The SWCNT-modified electrodes were characterized using scanning electron microscopy and X-ray photoelectron spectroscopy. The electrochemical performance of these electrodes was analyzed by cyclic voltammetry and chronoamperometry. Glucose oxidase was covalently immobilized on the surface of the treated SWCNTs, and the analytical characteristics of the integrated glucose sensor were investigated using glucose as a target analyte. The plasma-activated SWCNT electrode exhibited a much higher sensitivity to the glucose and a lower detection limit than the acid-treated electrode, indicating that a larger amount of enzyme was immobilized on the plasma-treated SWCNT electrode than on the acid-treated electrode. This is due to the fact that the oxygenated functional groups are mainly located at the ends of the tubes in the acid-treated SWCNTs, while the plasma-treated SWCNTs have an even larger surface area available for enzyme immobilization owing to the functional groups covering the entire surface of the SWCNTs.     

Electrochemical characterization of single-walled carbon nanotubes for electrochemical double layer capacitors using non-aqueous electrolyte

Single-walled carbon nanotubes (SWCNTs) were investigated by cyclic voltammetry and electrochemical impedance spectroscopy in a non-aqueous electrolyte, 1 M Et₄NBF₄ in acetonitrile, suitable for supercapacitors. Further, in situ dilatometry and in situ conductance measurements were performed on single electrodes and the results compared to an activated carbon, YP17. Both materials show capacitive behavior characteristic of high surface area electrodes for supercapacitors, with the maximum full cell gravimetric capacitance being 34 F/g for YP17 and 20 F/g for SWCNTs at 2.5 V with respect to the total active electrode mass. The electronic resistance of SWCNTs and activated carbon decreases significantly during charging, showing similarities of the two materials during electrochemical doping. The SWCNT electrode expands irreversibly during the first electrochemical potential sweep as verified by in situ dilatometry, indicative of at least partial debundling of the SWCNTs. A reversible periodic swelling and shrinking during cycling is observed for both materials, with the magnitude of expansion depending on the type of ions forming the double layer.     

Fabrication of single-walled carbon nanotube Schottky diode with gold contacts modified by asymmetric thiolate molecules

We have fabricated single-walled carbon nanotube (SWCNT) Schottky diodes by asymmetrically modifying the two Au/SWCNT contacts using different thiolate molecules, methanethiol (CH₃SH) and trifluoroethanethiol (CF₃CH₂SH). Characterization has revealed that highly asymmetrical contacts with Schottky barrier heights of ∼190 and ∼40 meV (increased by over 70% and decreased by over 60%, respectively with respect to that of pristine Au/SWCNT contact of ∼110 meV) were achieved for the Au/SWCNT contacts modified by CH₃SH and CF₃CH₂SH, respectively. The performance of our SWCNT Schottky diodes is as follows: the forward and reverse current ratio (I_forward/I_reverse) higher than 10⁴, a forward current as high as ∼5 μA, a reverse leakage current as low as ∼100 pA, and a current ideality factor as low as ∼1.42. This is at least comparable to, if not better than SWCNT Schottky diodes fabricated with asymmetrical metals, where one contact is a metal with a work function lower than that of SWCNTs to yield a Schottky contact, while the other has a work function higher than that of SWCNTs to achieve an ohmic (more near ohmic) contact.     

Synthesis of single-walled carbon nanotubes produced using a three layer Al/Fe/Mo metal catalyst and their field emission properties

Single-walled carbon nanotubes (SWCNTs) were synthesized on SiO₂/Si substrates by thermal chemical vapor deposition using an Al/Fe/Mo triple layer catalyst, methane (CH₄) as the carbon source, and a mixture of Ar/H₂ (10% H₂) as the carrier gas. The effects of volume ratio of CH₄ to Ar/H₂ (10% H₂), pretreatment time, growth temperature, and Al underlayer thickness on SWCNT growth were studied. The pretreatment time in Ar/H₂ and Al underlayer thickness were found to be crucial for a high-yield of high-purity SWCNTs, since they both governed the size of the catalyst nanoparticles. The optimum growth conditions were found to be a pretreatment time of 20 min, growth time of 10 min, growth temperature of 900 °C, and CH₄/Ar/H₂ flow rates of 50/900/100 sccm, with a catalyst composed of Al (2 nm)/Fe (1 nm)/Mo (0.5 nm). The SWCNTs grown under these conditions have excellent field emission characteristics with low turn-on and threshold fields of 2.4 and 4.3 V/μm, respectively, and a current density of 38.5 mA/cm² at 5 V/μm.     

Self-assembled nano-arrays of single-walled carbon nanotube-octa(hydroxyethylthio)phthalocyaninatoiron(II) on gold surfaces: Impacts of SWCNT and solution pH on electron transfer kinetics

The construction by sequential self-assembly process of reproducible, highly stable and pH-responsive redox-active nanostructured arrays of single-walled carbon nanotubes (SWCNTs) integrated with octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc) via ester bonds on a gold surface (Au-Cys-SWCNT-FeOHETPc) is investigated and discussed. The successful construction of this electrode is confirmed using atomic force microscopy and X-ray photoelectron spectroscopy as well as from the distinct cyclic voltammetric and electrochemical impedance spectroscopic profiles. The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes, the surface pK_a is estimated as 7.3. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes (Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc) suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (k_app) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (∼1.7 × 10⁻² cm⁻² s⁻¹) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 × 10⁻³ cm⁻² s⁻¹) is attributed to the possible effect of the central metal on the phthalocyanine core and substituents on the peripheral positions of the phthalocyanine rings. We also prove that aligned SWCNT arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs.     

Variations in the microstructure and electrical resistance of the SWCNT films under consecutive photoflash exposures

A film of unpurified single-walled carbon nanotubes (SWCNTs) synthesized by the floating catalyst method using ferrocene as the catalyst precursor was subjected to different numbers of flashes and the products were studied. In addition to the remaining SWCNTs, Fe₂SiO₄ particles covered with amorphous carbon were found to attach on the SWCNTs, and the size increased with flash numbers. Fe₂SiO₄ arose from the oxidation of Fe₃C, a ferrocene-induced catalyst particle embedded in the SWCNTs, where Si provided by SiO₂ released from the mullite tube at 1200 °C during SWCNT growth. The amorphous carbon coating was attributed to insufficient time of the precipitated carbon to crystallize during rapid cooling after the flash. Variation of the Raman I_D/I_G ratio from an initial value of 0.035 to 0.025 after 100 flashes was due to competition between the removal of carbon from the nanotubes and the formation of amorphous carbon on the Fe₂SiO₄ particle surface. The electrical resistance of the SWCNT film increased with the number of flashes but the change became progressively smaller, with the increment decreasing from 17.5% to 0.2%. Similar experiments using purified SWCNTs were performed, and no such particles were observed.     

Nondestructive purification of single-walled carbon nanotube rope through a battery-induced ignition and chemical solution approach

A two-step method for the purification of single-walled carbon nanotube (SWCNT) rope containing substantial catalyst particles embedded in carbonaceous shells was developed. The first step was the triggering of rope ignition using a 9-V battery, which resulted in pre-oxidization of the carbon shells on the Fe₃C catalyst and oxidation of the exposed Fe₃C to form Fe₂O₃. In addition, SWCNTs with open-end structures due to ignition-induced cutting remained. In the second step, both oxalic acid (H₂C₂O₄) and hydrochloric acid (HCl) were used as the reactants to remove the Fe₂O₃ particles. No damage on the SWCNT walls after H₂C₂O₄ or HCl purification was found. In addition, adsorption of H₂C₂O₄ was also found on the H₂C₂O₄ purified SWCNT rope and it can be effectively removed by heating the rope at 200 °C in vacuum for 40 min. Samples were characterized by SEM, TEM, Raman spectroscopy, TGA, FTIR, XPS, and UV-Vis-NIR.