Adatom complexes and self-healing mechanisms on graphene and single-wall carbon nanotubes

Point defects play a role in the functionalization, chemical activation, carrier transport, and nano-engineering of graphitic systems. Here, we use first-principles calculations to describe several processes that alter the properties of graphene and single-wall carbon nanotubes (SWCNTs) in the presence of self-interstitials (SI’s). We find that, while two or four SI’s are stabilized in hillock-like structures that stay idle unless the system is heated to very high temperatures, clustering of three C adatoms leads to the formation of mobile protrusions on graphene and large enough SWCNTs. For different SI concentrations and SWCNT size, the interplay between mobile and immobile species may favor one of the two competing processes, self-healing or formation of adatom superstructures.     

Iron(III) protoporphyrin IX—single-wall carbon nanotubes modified electrodes for hydrogen peroxide and nitrite detection

Iron(III) protoporphyrin IX (Fe(III)P), adsorbed either on single-walled carbon nanotubes (SWCNT) or on hydroxyl-functionalized SWCNT (SWCNT-OH), was incorporated within a Nafion matrix immobilized on the surface of a graphite electrode. From cyclic voltammetric measurements, performed under different experimental conditions (pH and potential scan rate), it was established that the Fe(III)P/Fe(II)P redox couple involves 1e⁻/1H⁺. The heterogeneous electron transfer process occurred faster when Fe(III)P was adsorbed on SWCNT-OH (11 s⁻¹) than on SWCNT (4.9 s⁻¹). Both the SWCNT-Fe(III)P- and SWCNT-OH-Fe(III)P-modified graphite electrodes exhibit electrocatalytic activity for H₂O₂ and nitrite reduction. The modified electrodes sensitivities were found varying in the following sequences: S_{SWCNT-OH-Fe(III)P} = 2.45 mA/M ≈ S_{SWCNT-Fe(III)P} = 2.95 mA/M > S_Fe(III)P = 1.34 mA/M for H₂O₂, and S_{SWCNT-Fe(III)P} = 3.54 mA/M > S_Fe(III)P = 1.44 mA/M > S_{SWCNT-OH-Fe(III)P} = 0.81 mA/M for NO₂⁻.     

Ion-exchange adsorption of copper(II) ions on functionalized single-wall carbon nanotubes immobilized on a glassy carbon electrode

The cation-exchange property of oxidatively treated carbon nanotubes (CNTs) is newly reported. Single-wall carbon nanotubes (SWNTs), which were oxidatively treated, were immobilized on a glassy carbon surface and, on this CNT-modified electrode, Cu(II) ions were spontaneously adsorbed and their redox waves electrochemically measured. It is suggested that the adsorption of the cationic Cu(II) ions occurs by their electrostatic interaction with the negatively charged carboxylic anions on the CNTs after the ion-exchange with protons. The surface coverage of the adsorbed Cu(II) ions depending on the dipping time, the amount of immobilized CNTs, and the Cu(II) concentration was estimated from the electrochemical chronocoulometric measurements. The effect of the ionic strength on the adsorption of the Cu(II) ions was investigated and the adsorption strengths of various alkali metal cations and protons were compared. It is hoped that this new cation-exchange property of CNT-modified electrodes may extend their range of electrochemical applications.     

Electrochemical behavior of metallic and semiconducting single-wall carbon nanotubes for electric double-layer capacitor

Electrochemical behavior of metallic and semiconducting single-wall carbon nanotubes (SWCNTs) separated by agarose gel chromatography was analyzed as electrodes of electric double-layer capacitor (EDLC). Due to the doping of ions to semiconducting SWCNTs, the cyclic voltammogram of semiconducting SWCNTs showed amphoteric behavior, which is analogous to that of dopable conducting polymers. As the potential was increased or decreased from the flat band potential, the capacitance of semiconducting SWCNTs was increased, but that of metallic SWCNTs was slightly increased. The high capacitance of semiconducting SWCNTs at the high potential is beneficial for EDLC due to the possible limitation of capacitance.     

Improvement single-wall carbon nanotubes (SWCNTs) based on functionalizing with monomers 2-hydroxyethylmethacryate (HEMA) and N-vinylpyrrolidone (NVP) for pharmaceutical applications as cancer therapy

The functionalized carbon nanotubes play significant roles in the fields such as preparation of composite materials and biological technologies. This paper explains the covalent functionalization of single-wall carbon nanotubes (SWCNTs) with biomedical important monomers, 2-hydroxyethylmethacryate (HEMA) and N-vinylpyrrolidone (NVP) by chemical grafting of HEMA and PVP monomers via free radical polymerization. To get carboxylic acid functionalized SWCNTs, first the nanotubes were oxidized with a mixture of nitric acid and sulfuric acid (1:3). Then, the binding of HEMA and NVP onto the surface of SWCNTs was performed by chemical functionalization of HEMA, NVP with acid chloride-bound carbon nanotube by esterification reaction. These results were confirmed by FT-IR and SEM. The cell culture experiments conducted for pharmaceutical applications were used as cancer therapy.     

Growth of large-diameter (∼4 nm) single-wall carbon nanotubes in the nanospace of mesoporous material SBA-15

Single-wall carbon nanotubes (SWCNTs) have been synthesized by supported-catalyst chemical vapor deposition (CCVD) using one-dimensional (1D) channels of mesoporous silica (SBA-15; mean channel diameter, 6.0 nm) functionalized with carboxyl groups where Co and Fe complexes are encapsulated. The synthesized SWCNTs have much larger diameters than the SWCNTs synthesized by conventional CCVD. Transmission electron microscope observations reveal that large-diameter SWCNTs (<4.2 nm) are grown in 1D channels of SBA-15. Large metal particles formed in the channels should play an important role in the growth of the SWCNTs with larger diameters.     

Surface modifications for the effective dispersion of carbon nanotubes in solvents and polymers

The preparation of effective dispersions of carbon nanotubes (CNTs) presents a major impediment to the extension and utilization of CNTs. CNTs intrinsically tend to bundle and/or aggregate. The prevention of such behavior has been explored by testing various surface modification techniques to improve the dispersibility of CNTs in a variety of solvents and polymer matrices. General guidelines for the design of end-use tailor-fit surface modifications to achieve a particular CNT dispersibility have not thus far been articulated. This review aims to identify such guidelines by providing a perspective of the state of the art in surface modifications and the resultant dispersibility of CNTs. Surface modifications and dispersion properties must first be defined by agreeing upon a few new terms, such as the degree of surface modification, degree of substitution, and degree of dispersion, to determine the possible relationship(s) that may exist between surface characteristics and the dispersibility of CNTs. Furthermore, several critical issues that require concerted in-depth studies are discussed with particular emphasis on the quantitative characterization of CNT surface modifications and dispersions. This discussion describes the Flory–Huggins interaction parameter based on the solubility parameter for CNTs, which is correlated with the dispersibility in the surrounding media.     

The morphology, electrical conductivity and vapour sensing ability of inkjet-printed thin films of single-wall carbon nanotubes

Thin films containing single-wall carbon nanotubes (SWCNTs) have been prepared using the inkjet printing (IJP) technique. Atomic force microscopy (AFM) has been used to investigate the morphology of these layers. The inkjet printed films consisted of small, randomly-oriented islands of nanotubes, the topography of which was dependent on the nature of the substrate surface. The in-plane electrical characteristics of the films were measured at room temperature. The current versus voltage data exhibited non-linear behaviour, which could be fitted to the theoretical model for Poole-Frenkel conductivity. Preliminary measurements are also reported on the use of the thin layers to detect alcohol vapour.     

Effect of multiwalled carbon nanotubes on crystallization behavior of poly(vinylidene fluoride) in different solvents

In this study, the poly(vinylidene fluoride) (PVDF)—multiwalled carbon nanotubes (MWNTs) composites have been prepared by solution casting in two different solvents: dimethyl sulfoxide (DMSO) and dimethylacetamide (DMAc). Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimeter (DSC) results showed that the crystal phases of PVDF are quite different in the two solvents. When DMSO is used as the solvent, the PVDF crystalline phases could be greatly alternated from α‐form to β‐form by the incorporation of MWNTs. While the crystalline structure of PVDF hardly change in the case of DMAc. The DSC and polarized optical microphotographs implied that MWNTs not only act as nucleating agents for PVDF but also confine the crystallization of PVDF. Besides, it was found that the storage modulus (E′) of the composites were significantly enhanced with an appropriate content of MWNTs. And when using DMSO as the solvent, one relaxation process emerges in the loss tan δ (loss factor) curves of the neat PVDF and PVDF/MWNTs composites, while it was not observed in the DMAc system. The obtained results revealed that varing solvents have different effects on the crystallization behavior of PVDF with the addition of MWNTs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Origin of the 2450 cm Raman bands in HOPG, single-wall and double-wall carbon nanotubes

The second order Raman signals around the G′-band region of graphite and carbon nanotubes have been investigated at more than 15 excitation laser lines. Two distinct Raman bands have been observed around 2700 cm⁻¹; a prominent one is due to the so-called G′-band and the other is a weak band around 2450 cm⁻¹. Both two bands can be from the double resonance process involving two phonons around the K-point in the phonon dispersion of a two-dimensional graphite. The 2450 cm⁻¹-band has exhibited little power dependence, whereas the intensity of G′-band has shown large photon energy dependence as already reported. The 2450 cm⁻¹-band and the G′-band correspond to non-dispersive q = 0 and fully-dispersive q = 2k, respectively. From the phonon dispersion and the corresponding phonon frequency, the 2450 cm⁻¹-band can be assigned as an overtone mode of LO phonon (i.e. 2LO). This is revealed by calculated Raman spectra of graphite with proper electron-phonon matrix elements. The present study is the first report on the origin and assignment of the 2450 cm⁻¹-band, which is based on the double resonance Raman scattering.     

Exfoliated graphite and ozonated single-wall carbon nanotubes for encapsulation of the single-molecule magnet Mn12

We outline experiments on single-wall carbon nanotubes (SWNT) and exfoliated graphite (EG), as templates for producing nanostructures of the nanomagnetic manganese acetate cluster (Mn₁₂[(CH₃COO)₁₆(H₂O)₄O₁₂] · 2CH₃COOH · 4H₂O),Mn₁₂. Mn₁₂ grown in EG and SWNT exhibit downward shifts in its blocking temperature, ac susceptibility response and magnetic hysteresis loops. Temperature dependence of the magnetization reversal dynamics shows that encapsulation in EG or ozonated SWNT shortens the Arrhenius relaxation time for magnetization reversal, τ_o, from 7.8 × 10⁻⁸ to 1.4 × 10⁻⁸s, with a marginal lowering of the activation barrier from 68 ± 5 to 60 ± 5 K. The role of Mn-O modes in the magnetization dynamics together with these data indicate the potential for controlling Mn₁₂ properties via encapsulation.     

In situ inelastic neutron scattering studies of the rotational and translational dynamics of molecular hydrogen adsorbed in single-wall carbon nanotubes (SWNTs)

Inelastic neutron scattering (INS) spectra were measured in situ from progressively increased amounts of para-hydrogen physisorbed in bundles of single-walled carbon nanotubes at temperatures in the vicinity of 20 K. INS from the bound H₂ molecules consists of two distinct parts carrying complementary information. In the low energy and momentum transfer region, at about 14.5 meV we observe a sharp line corresponding to rotational transitions between the ground para-J = 0 state and the ground ortho-J = 1 state without change of the translational state of the molecular centre of mass (CoM). This we call the “bound” spectrum. At higher energy transfers, a series of broad peaks are observed, corresponding to rotational transitions between the para-J = 0 state and different ortho-states (J = 1, 3, 5, … ,) shifted out in energy transfer by an amount equal to the CoM recoil energy. This we call the “recoil” spectrum. Both parts of each spectrum are analysed using the Young and Koppel model. From the “bound” spectrum we estimate the mean height of the barrier to rotation and the mean square displacements of the molecules accommodated at different adsorption sites. The “recoil” spectrum allows us to derive the mean translational kinetic energy of the adsorbed hydrogen as a function of the surface concentration.     

Raman spectroscopy and nitrogen vapour adsorption for the study of structural changes during purification of single-wall carbon nanotubes

Raman spectroscopy and nitrogen adsorption measurements were combined to study the surface features of semi-conducting and metallic single-wall nanotubes (SWNTs). The nanotubes were treated chemically and with heat under moderate conditions that more than doubled the mesopore volume of the tested samples, which consistently led to a significant rise in the total surface area of up to 1550 m²/g. The large increase in the number of micropores of less than 1 nm in diameter was associated with the loosening of nanotube bundles as well as the creation of structural flaws on the surface of individual SWNTs due to chemical treatment. Micropores in the 1.0-1.8 nm range were associated with the holes created on the surface of individual tubes. Heating at 1000 °C was shown to restore nanotube diameter to their initial pre-chemical treatment levels with the change in the chirality of SWNTs and diminish the porosity by closing small holes. It was assumed that the intermediate frequency range (500-1100 cm⁻¹) was associated with the degree of imperfection of HiPco SWNTs crystalline structures, and therefore provided information about the degree of tube surface damage due to the presence of functional groups. A hypothesis explaining the transformation of SWNT porous structure during heat treatment is proposed.     

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.     

Enzymatic synthesis of phosphatidylcholine with fatty acids,isooctane, carbon dioxide,and propane as solvents

Phosphatidylcholine (PC) was synthesized from lyso-PC and long polyunsaturated fatty acids (PUFA) with phospholipase A₂. In previous investigations, performed in small glass tubes, the enzymatic synthesis reaction was optimized. This paper presents results from experiments performed in a high-pressure reactor filled with an immobilized enzyme (Im.E.). Fatty acids were used as the main solvent while isooctane, CO₂, or propane was used as an additional solvent. The water content was carefully controlled over wide ranges. The temperature was kept constant at 45°C for up to 50 h. The highest initial reaction rate was attained with pure fatty acids under relatively humid conditions (water=35% of dry Im.E.). The reaction rates were more than three times as high in the high-pressure reactor than in previous experiments in glass tubes. In all solvent systems, the best yield was attained after long times under dry conditions (water <15% of dry Im.E.). Addition of CO₂ to the PUFA reduced the yield, while addition of isooctane or propane increased the yield. After 20 h at 45°C, the best yield (25%) was attained at a solvent composition of 91% PUFA and 9% propane.     

Optimized process for the inclusion of carbon nanotubes in elastomers with improved thermal and mechanical properties

The effects of addition of reinforcing carbon nanotubes (CNTs) into hydrogenated nitrile–butadiene rubber (HNBR) matrix on the mechanical, dynamic viscoelastic, and permeability properties were studied in this investigation. Different techniques of incorporating nanotubes in HNBR were investigated in this research. The techniques considered were more suitable for industrial preparation of rubber composites. The nanotubes were modified with different surfactants and dispersion agents to improve the compatibility and adhesion of nanotubes on the HNBR matrix. The effects of the surface modification of the nanotubes on various properties were examined in detail. The amount of CNTs was varied from 2.5 to 10 phr in different formulations prepared to identify the optimum CNT levels. A detailed analysis was made to investigate the morphological structure and mechanical behavior at room temperature. The viscoelastic behavior of the nanotube filler elastomer was studied by dynamic mechanical thermal analysis (DMTA). Morphological analysis indicated a very good dispersion of the CNTs for a low nanotube loading of 3.5 phr. A significant improvement in the mechanical properties was observed with the addition of nanotubes. DMTA studies revealed an increase in the storage modulus and a reduction in the glass‐transition temperature after the incorporation of the nanotubes. Further, the HNBR/CNT nanocomposites were subjected to permeability studies. The studies showed a significant reduction in the permeability of nitrogen gas. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Materials science of carbon nanotubes: fabrication,integration, and properties of macroscopic structures of carbon nanotubes

In this Account, we summarize some of our recent studies on the materials properties of the carbon nanotubes (CNTs). The focus is on single-wall carbon nanotubes (SWNTs). We describe experiments on synthesis of SWNTs with controlled molecular structures and assembly of functional macroscopic structures. In addition, we present results on the electron field emission properties of macroscopic CNT cathodes.