Spectral properties of single-walled carbon nanotubes encapsulating fullerenes

Single-walled carbon nanotubes (SWCNTs) with diameter ranged from 1.22 to 1.6 nm filled with C₆₀, C₇₀ and C₆₀H₂₈ molecules (peapods), as well as double-walled carbon nanotubes (DWCNTs) derived from peapods, were studied by HRTEM, UV-vis-NIR and Raman spectroscopy. Suspensions with accurate concentration were used for spectroscopic studies to enable quantitative comparison of different substances. Filling of the SWCNTs with C₇₀ molecules resulted in a reduced van der Waals interaction between the tubes in a bundle. The DWCNTs have lower intensity of the van Hove bands and weaker photoluminescence. Raman spectra at 633 and 1064 nm excitation wavelengths reveal that RBM frequencies of C₆₀ and C₇₀ peapods are equally downshifted compared to empty tubes. It was found that filling of the nanotubes with C₆₀ and C₇₀ caused spectral shifts of absorption bands: thin tubes display red shifts, while thick ones show blue shifts. DWCNTs and C₆₀H₂₈@SWCNTs do not show any shifts. All the results suggest that the filling of nanotubes with fullerenes alters the average diameter of the electron cloud around SWCNT framework; namely, it increases for thin SWCNTs, and decreases for thick ones. Our attempts to structurally assign thick nanotubes using reported extrapolations from data for thin tubes were unsuccessful.     

Cellular structures of carbon nanotubes in a polymer matrix improve properties relative to composites with dispersed nanotubes

A new processing method has been developed to combine a polymer and single wall carbon nanotubes (SWCNTs) to form electrically conductive composites with desirable rheological and mechanical properties. The process involves coating polystyrene (PS) pellets with SWCNTs and then hot pressing to make a contiguous, cellular SWCNT structure. By this method, the electrical percolation threshold decreases and the electrical conductivity increases significantly as compared to composites with well-dispersed SWCNTs. For example, a SWCNT/PS composite with 0.5 wt% nanotubes made by this coated particle process (CPP) has an electrical conductivity of ∼3 × 10⁻⁴ S/cm, while a well-dispersed composite made by a coagulation method with the same SWCNT amount has an electrical conductivity of only ∼10⁻⁸ S/cm. The rheological properties of the composite with a macroscopic cellular SWCNT structure are comparable to PS, while the well-dispersed composite exhibits a solid-like behavior, indicating that the composites made by this new CPP are more processable. In addition, the mechanical properties of the CPP-made composite decrease only slightly, as compared with PS. Relative to the common approach of seeking better dispersion, this new fabrication method provides an important alternative means to higher electrical conductivity in SWCNT/polymer composites. Our straightforward particle coating and pressing method avoids organic solvents and is suitable for large-scale, inexpensive processing using a wide variety of polymers and nanoparticles.     

Electrochemistry of double-wall carbon nanotubes encapsulating C60 and their spectral characterization

Electrochemistry of double-wall carbon nanotubes (DWCNTs) encapsulating C₆₀ (C₆₀@DWCNT) have been studied by preparing a C₆₀@DWCNT modified electrode, and three pairs of reversible electro-reduction waves corresponding to electron transfer reactions of C₆₀ inside DWCNTs have been obtained in a mixed solvent of toluene and acetonitrile (4:1, v:v) containing tetrabutylammonium cation as supporting electrolyte, which indicates that DWCNTs act as molecular wires to allow electrical communication between the underlying electrode and the redox-active guest C₆₀. The influencing factors on the electrochemistry of C₆₀@DWCNT modified electrodes have been investigated. The results suggest that the voltammetric behavior of C₆₀@DWCNT is dependent on the nature of the supporting electrolyte and the solvent system. In addition, spectral characterization of the C₆₀@DWCNT modified electrodes before and after electrochemical scanning reveals interaction between C₆₀ and DWCNT and verifies the reduction of C₆₀ encapsulated in DWCNTs. C₆₀ molecules inside DWCNTs retains their redox activity, and can also act as an electron-transfer mediator to electrocatalyze the reduction of halohydrocarbon.     

Temperature and pressure dependence of molecular adsorption on single wall carbon nanotubes and the existence of an “adsorption/desorption pressure gap”

The interaction of acetone with single wall carbon nanotubes (SWCNTs) was studied by temperature programmed desorption with mass spectrometry (TPD-MS), after reflux, sonication, or exposure to 7.6 Torr of acetone vapors at room temperature. Acetone molecules adsorb strongly on SWCNTs desorbing at ∼400-900 K, corresponding to desorption energies of ∼100-225 kJ/mol, as intact molecules. Exchange of intact adsorbed molecules with gas phase species was observed in successive dosing of hydrogenated and deuterated acetone molecules. The desorption energies reported here are in stark contrast to the desorption energies (∼75 kJ/mol) reported earlier for SWCNTs interacting with acetone under high vacuum at cryogenic temperatures. This result suggests activated adsorption/desorption, and is also observed for adsorption of ethanol, methane, n-butane and 1,3-butadiene on SWCNTs and on carbon black. Quantum chemical calculations suggest that adsorption in interstitial channels of bundles formed of large-diameter SWCNTs is possible and can account for high desorption barriers, a result of strong dispersion interactions between neighboring SWCNTs.     

Catalytic activity of cobalt and iron phthalocyanines or porphyrins supported on different carbon nanotubes towards oxygen reduction reaction

Non-noble metal catalysts for O₂ reduction were prepared by dispersing iron(II) phthalocyanine, cobalt(II) tetra-tert-butylphthalocyanine, cobalt(II) 2,3,7,8,12,13,17,18-octaethyl-porphine, and cobalt(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrine on carbon nanotubes (CNTs) used as high surface area support. Different types of CNTs (SWCNTs, DWCNTs and MWCNTs) were investigated as an effective substitute for commonly used carbon black in carbon-supported phthalocyanines and porphyrins. The oxygen reduction reaction (ORR) activity of those CNT-supported catalysts in alkaline and acidic solutions was studied. The results show that: (i) all catalytic systems including MWCNTs are more efficient for O₂ reduction than those with SWCNTs and DWCNTs, (ii) the oxidative chemical treatment of the CNTs increases the electrocatalytic performance of the corresponding CNT-supported catalysts, (iii) similarly to Vulcan-supported catalysts, iron(II) phthalocyanine gives the best electroactivity among the investigated CNT-supported materials and (iv) finally, the MWCNT-supported iron(II) phthalocyanine catalyst chemically treated in oxidative conditions shows an ORR catalytic activity comparable to a commonly used Pt/C catalyst with similar current densities and a very low overpotential (60 mV).     

Enhanced figure of merit of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) and SWCNT thermoelectric composites by doping with FeCl3

Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole (F8BT) generally has a large Seebeck coefficient, and single-walled carbon nanotubes (SWCNTs) have high electrical conductivity. In this work, we prepared F8BT/SWCNT composites to combine the good Seebeck coefficient of the polymer and the excellent electrical conductivity of SWCNTs to achieve enhanced thermoelectric properties. For the composite materials, the maximum power factor of 1 μW mK⁻² was achieved when the SWCNT content was 60%, with the maximum ZT value of 4.6 × 10⁻⁴. After ferric chloride was employed as the oxidative dopant for the composites, the electrical conductivity of the composites improved significantly. The maximum value of power factor (1.7 μW mK⁻²) was achieved when the SWCNT content was 60%, and the ZT value of 7.1 × 10⁻⁴ was about 1.5 times as high as that of the composites with undoped F8BT. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47011.     

Preparation of transparent and conductive thin films of carbon nanotubes using a spreading/coating technique

This study demonstrates large-scale purification of single-walled carbon nanotubes (SWCNTs) and preparation of transparent and conductive thin films of carbon nanotubes using a spreading/coating technique. Wire-bar, which wraps a stainless steel wire around a shaft, is useful equipment to spread inks on flexible materials. Coating of purified SWCNT film thickness was tunable depending not only on the wire-bar thickness but also on the SWCNT concentration in dispersion. The SWCNT concentration in the dispersion increased concomitantly with the increase of the C₆₀(OH)_n concentration. These two factors, wire-bar thickness and SWCNT concentration in dispersion, control the film’s conductivity and transparency.     

Effect of strain rate on the buckling behavior of single- and double-walled carbon nanotubes

Molecular dynamics simulations are performed on single- (SWCNTs) and double-walled carbon nanotubes (DWCNTs) to investigate the effects of strain rate on their buckling behavior. The Brenner’s second-generation reactive empirical bond order and Lennard-Jones 12-6 potentials are used to describe the short range bonding and long range van der Waals atomic (vdW) interaction within the carbon nanotubes, respectively. The sensitivity of the buckling behavior with respect to the strain rate is investigated by prescribing different axial velocities to the ends of the SWCNTs and DWCNTs in the compression simulations. In addition, the effects of vdW interaction between the walls of the DWCNTs on their buckling behavior are also examined. The simulation results show that higher strain rates lead to higher buckling loads and buckling strains for both SWCNTs and DWCNTs. A distinguishing characteristic between SWCNTs and DWCNTs is that the former experiences an abrupt drop in axial load whereas the axial load in latter decreases over a finite, albeit small, range of strain after buckling initiates. The buckling capability of DWCNT is enhanced in the presence of vdW interaction. DWCNTs can sustain a higher strain before buckling than SWCNTs of similar diameter under otherwise identical conditions.     

Controllable synthesis of single- and double-walled carbon nanotubes from petroleum coke and their application to solar cells

Single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) have been controllably synthesized by an arc discharge in different atmosphere using petroleum coke as carbon source. The morphology and properties of two kinds of carbon nanotubes (CNTs) synthesized with Fe as catalyst were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, UV–visible spectroscopy, inductively coupled plasma optical emission spectrometer, thermogravimetric analysis and infrared spectroscopy. In the He gas atmosphere only SWCNTs were found to be synthesized by arc discharge in contrast to the case in Ar gas atmosphere in which only DWCNTs were formed, In addition, properties of solar cells based on both kinds of CNTs and n-type Si are examined under illumination of light emission diode (LED). It is found that the performance of solar cells depends significantly on the type of CNTs, i.e., SWCNTs-based solar cells show better performance under LED illumination with wavelengths in the range of 400–940 nm than the case of DWCNTs which exhibit high performance under illumination of the 1310 nm infrared light.     

Single-walled carbon nanotubes as a dopant in p-type cuprous oxide films

p-type cuprous oxide (Cu₂O) films doped with single-walled carbon nanotubes (SWCNTs) were synthesized using the two-step process of electrochemical co-deposition and subsequent thermal oxidation. SWCNTs are known to act as a conducting pathway in various SWCNT-based composite materials because of their low electrical resistivity in the longitudinal direction. However, they act as an electron acceptor dopant rather than a carrier pathway in p-type Cu₂O. Results show that the doping of SWCNTs in Cu₂O films increases the hole concentration and decreases the carrier mobility with increasing dopant concentration. As a result, the electrical resistivity decreased from 290 to 0.8 Ω cm as the amount of dopant increased. The electronic energy band structure, as determined by X-ray and ultraviolet photoelectron spectroscopy, revealed that the doping of SWCNTs moved the Fermi levels of Cu₂O films toward the valence band maximum by 0.24 eV. This confirms that the SWCNTs act as an electron acceptor and increase the hole concentration and electrical conductivity of the Cu₂O films, despite the lower mobility.     

Increasing the thermoelectric power factor of polymer composites using a semiconducting stabilizer for carbon nanotubes

Poly(vinyl acetate) (PVAc) copolymer latex-based composites were prepared with multi-walled carbon nanotubes (MWCNT), stabilized with sodium deoxycholate (DOC) or meso-tetra(4-carboxyphenyl) porphine (TCPP). SEM images show that a segregated MWCNT network developed during drying, which resulted in relatively low percolation thresholds (1.62 and 2.17 wt.% MWCNT for DOC and TCPP, respectively). The electrical conductivity (σ) of TCPP-stabilized composites is very similar to that of DOC-stabilized, while the thermopower (or Seebeck coefficient (S)) is five times as large. This enhanced thermopower suggests the MWCNT:TCPP/PVAc composite will have an order of magnitude greater power factor (S²σ), which is an important measure of efficiency for thermoelectric materials (i.e., materials capable of converting a thermal gradient to a voltage). The thermal conductivity of these composites remains comparable to typical polymeric materials due to numerous tube–tube connections that act as phonon scattering centers. The universality of this approach was confirmed using much more electrically conductive double-walled carbon nanotube-filled composites that showed similar improvement with TCPP stabilization. It is possible that other porphyrin derivatives, or semiconducting molecules capable of stabilizing nanotubes in water, could be used to further enhance the Seebeck coefficient and improve the ability of these composites to convert waste heat into electricity.     

Energy generation using thermopower waves: Experimental and analytical progress

Thermopower waves convert chemical energy into electrical power using nanostructured thermal conduits like carbon nanotubes (CNTs) by taking advantage of their high thermal conductivity to propagate the heat released by an exothermic reaction of a fuel layer coated around the conduit. Electron–phonon coupling in the CNTs then leads to an electrical output. Previous work using cyclotrimethylene‐trinitramine coated around multiwalled CNTs has shown electrical output as high as 7 kW kg^?1. This phenomenon has potential to aid the manufacture of nanoscale power sources capable of releasing large power pulses for specific applications. Researchers have studied the effects of other system properties, including the conduit thermal conductivity, the chemical properties of the fuel, and the coupling of the reactions to inorganic thermoelectric materials. An analytical solution for the governing heat and mass balance equations has also been derived. Here, we review the progress made in the field of thermopower waves. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3333–3341, 2013     

Enhancement of Thermoelectric Performance in Hierarchical Mesoscopic Oxide Composites of Ca3Co4O9 and La0.8Sr0.2CoO3

The natural contradiction in enhancing electrical conductivity and thermopower in thermoelectric oxides makes it hard to improve the performance of a single thermoelectric oxide material. We report a facile method to construct a unique architecture of thermoelectric oxides that is promising to realize a simultaneous improvement of overall electrical conductivity and thermopower. Here, a series of two‐phase nanocomposites comprising of Ca₃Co₄O₉ (CCO) and La_0.8Sr_0.2CoO₃ (LSCO) has been synthesized through ball milling followed by spark plasma sintering (SPS) method. The electron microscope images reveal that the two constituents form the unique composites while retaining their individual crystalline and morphological identities. Owing to the hierarchical mesoscopic structure with nanoscale particles and submicrometer scale grain boundaries, an external strain is induced into the CCO grains by the LSCO nanoparticles to enhance the thermopower. The mesoscopic structure is also favorable for improving the electrical conductivity. Moreover, the long‐wavelength phonons can be scattered effectively from LSCO nanoparticles and the thermal conductivity is further suppressed. With compromises between power factor and thermal conductivity, the largest ZT achieved is up to 0.41 at 1000 K for the composites with 25 wt% of LSCO.     

Differential scanning calorimetry analysis of an enhanced LiNi0.8Co0.2O2 cathode with single wall carbon nanotube conductive additives

The replacement of traditional conductive carbon additives with single wall carbon nanotubes (SWCNTs) in lithium metal oxide cathode composites has been shown to enhance thermal stability as well as power capability and electrode energy density. The dispersion of 1 wt% high purity laser-produced SWCNTs in a LiNi_0.8Co_0.2O₂ electrode created an improved percolation network over an equivalent composite electrode using 4 wt% Super C65 carbon black; evidenced by additive connectivity in SEM images and an order of magnitude increase in electrode electrical conductivity. The cathode with 1 wt% SWCNT additives showed comparable active material capacity (185–188 mAh g⁻¹), at a low rate, and Coulombic efficiency to the cathode composite with 4 wt% Super C65. At increased cycling rates, the cathode with SWCNT additives had higher capacity retention with more than three times the capacity at 10C (16.4 mA cm⁻²). The thermal stability of the electrodes was evaluated by differential scanning calorimetry after charging to 4.3 V and float charging for 12 h. A 40% reduction of the cathode exothermic energy released was measured when using 1 wt% SWCNTs as the additive. Thus, the results demonstrate that replacing traditional conductive carbon additives with a lower weight loading of SWCNTs is a simple way to improve the thermal transport, safety, power, and energy characteristics of cathode composites for lithium ion batteries.     

Growth of double-walled carbon nanotubes from silicon oxide nanoparticles

Double-walled carbon nanotubes (DWCNTs) were synthesized by a metal-catalyst-free chemical vapor deposition method using silicon oxide nanoparticles as a catalyst. The diameters and lengths of the DWCNTs are in the ranges of 3–5 nm and 1–5 μm, respectively. The amount of DWCNTs produced is about 70%, while the remainder is single-walled carbon nanotubes. A heat treatment of the SiO₂/Si substrate used was found to be crucial for controlling the size of the catalyst nanoparticles, and hence for the growth of the DWCNTs. Flat or cone-shaped caps were observed for the DWCNTs, indicating that the growth of the DWCNTs from the non-metal catalyst follows a vapor–solid–solid mechanism. Energy dispersive spectroscopy and X-ray photoelectron spectroscopy characterizations confirmed that no metal impurity exists in the obtained DWCNT samples.     

One-pot purification and functionalization of single-walled carbon nanotubes in less-corrosive poly(phosphoric acid)

As-received commercial single-walled carbon nanotubes (SWCNTs) were treated in mild, inorganic polyacid, viz. polyphosphoric acid (PPA) with or without additional phosphorous pentoxide (P₂O₅) at 130, 160, and 190 °C. Unlike the treatment in strong acids such as nitric acid/sulfuric acid mixtures, nitric acid and hydrochloric acid, PPA with or without additional P₂O₅ could selectively remove the tenacious carbonaceous and metallic impurities with little or no damage to the basic frameworks of SWCNTs and crystalline carbon materials. Since the medium PPA/P₂O₅ is known for an efficient “direct” Friedel-Crafts acylation using a carboxylic acid instead of a carboxylic acid chloride, it provides the advantage of combining both purification and functionalization steps into a one-pot process in manufacturing of functionalized SWCNTs.     

Synthesis of single-walled carbon nanotube/metal nanoparticle hybrid materials from potassium-filled nanotubes

The reducing property of potassium-filled single-walled carbon nanotubes (SWCNTs) was used to synthesize single-walled carbon nanotube/metal nanoparticle hybrid materials. Electron transfer from potassium to SWCNTs gives rise to a substantial enhancement of the reducing ability of the carbon nanotubes. Metal ions with redox potentials lower than that of pristine SWCNTs can be reduced by potassium-filled SWCNTs. SWCNTs decorated with copper and zinc nanoparticles were synthesized through redox reactions between potassium-filled SWCNTs and metal ions. These redox reactions cannot take place if the potassium-filled SWCNTs have been exposed to air, because of oxidation of the carbon nanotubes which is shown by a shift of the G band frequency in Raman spectra.     

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.     

Hydrogen sulfide sensing properties of multi walled carbon nanotubes

This paper investigates the effect of functional groups on the hydrogen sulfide sensing properties of multi-walled carbon nanotubes using carboxyl and amide groups and Mo and Pt nanoparticles as decorated precursors in gaseous state at working temperature. Carbon nanotubes were synthesized by the CVD process and decorated with the nano particles; provide higher sensitivity for H₂S gas detection. The MWCNTs were characterized by scanning electron microscopy combined with energy dispersive X-ray (SEM/EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), ATR-IR absorption and Fourier transforms infrared (FT-IR) analyses. The MWCNTs were deposited as a thin film layer between prefabricated gold electrodes on alumina surfaces. The sensitivity of carbon nanotubes was measured for different H₂S gas concentrations and at working temperature. The results showed that the measured electrical conductance of the modified carbon nanotubes with functional groups is modulated by charge transfer with P-type semiconducting characteristics and metal decorated carbon nanotubes exhibit better performances compared to functional groups of carboxyl and amide for H₂S gas monitoring at room temperature.     

Grafting of an aminated poly(phenylene sulphide) derivative to functionalized single-walled carbon nanotubes

An aminated poly(phenylene sulphide) derivative (PPS-NH₂) has been covalently anchored to the surface of epoxy and acid-functionalized single-walled carbon nanotubes (SWCNTs). The characterisation through Fourier transform infrared spectroscopy, nuclear magnetic resonance, thermogravimetric analysis and Kaiser test corroborated the success of the grafting reactions, and allowed the identification and quantification of the covalent moieties. Scanning and transmission electron microscopy indicated an increase in the bundle diameter of the SWCNTs upon anchoring of the polymer chains. The results showed that the storage modulus, glass transition temperature and electrical conductivity of the polymer were exceptionally enhanced by the attachment to the SWCNTs. In contrast, the crystallization and melting temperature, degree of crystallinity and crystal size considerably decreased, as revealed by differential scanning calorimetry and X-ray diffraction experiments, due to the inactive nucleating role of these SWCNTs and the intense restrictions on chain mobility imposed by the SWCNT–polymer interactions. Acid-functionalized SWCNTs were more effective for reinforcing PPS-NH₂ than epoxy-functionalized SWCNTs, attributed to the formation of a larger number of covalent bonds, albeit led to a smaller increase in the electrical conductivity of the polymer. The results herein offer useful insights into the development of multifunctional CNT-reinforced thermoplastic composites for a wide variety of applications.