Mercury telluride crystals encapsulated within single walled carbon nanotubes: A density functional study

The structure and binding energies of mercury telluride crystals encapsulated within single walled carbon nanotubes (SWNTs) have been studied using density functional theory. The energies of three different pseudo one‐dimensional crystals of HgTe with 4:4, 3:3, and 2:2 coordination are compared. The initial structure for the 4:4 crystal was a 2 × 2 cubic motif derived from rock salt bulk structure, the 3:3 crystal corresponds to a novel structure found when HgTe was intercalated within SWNTs, and the 2:2 crystal is a chain motif derived from cinnabar (HgS) bulk structure. The isolated 3:3 crystal was found to be the most thermodynamically stable of the three structures. Calculations were performed on the 3:3 crystal inserted into three different SWNTs, (15, 0), (9, 9), and (17, 0), in order to investigate the perturbations on the molecular and electronic structure of the crystal and the SWNT, and the energy of formation of the HgTe@SWNT composites. The calculated structures are in good agreement with the experimental high resolution transmission electron microscopy images of the HgTe@SWNT composite. The calculated binding energies and density of states show that the interaction between nanotubes and the HgTe crystals is noncovalent. Since the energy difference of the “free” 4:4 and 3:3 structures is small and of the order of magnitude of the binding energies with the nanotubes, we carried out calculations on 4:4 HgTe structure inserted in to two different SWNTs, (15, 0) and (17, 0). The calculated binding energies show that, when the 4:4 structure is inserted into the smallest tube, the resultant composite has an energy comparable to the 3:3 structure, suggesting that this polymporph may also be found experimentally. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Interaction of atomic hydrogen with single-walled carbon nanotubes: a density functional theory study

We have studied the interaction of atomic hydrogen with (5,5) and (10,0) single-walled carbon nanotubes (SWNT) using density functional theory. These calculations use Gaussian orbitals and periodic boundary conditions. We compare results from the local spin density approximation, generalized gradient approximation (GGA), and hybrid density functionals. We have first kept the SWNT geometric structure fixed while a single H atom approaches the tube on top of a carbon atom. In that case, a weakly bound state with binding energies from -0.8 to -0.4 eV was found. Full geometry relaxation leads to a strong SWNT deformation, weakening the nearest C-C bonds and increasing the binding energy by about 1 eV. Full hydrogen coverage of the (5,5) SWNT converts this metallic nanotube into an insulator with a band gap of 3.4 eV for the GGA functional and 4.8 eV for the hybrid functional. Hybrid functionals perform similar to pure density functional theory functionals for the calculation of binding energies while band gaps critically depend on the functional choice.     

Time-resolved red luminescence from europium-catalyzed single walled carbon nanotubes

The photo-physical properties of Eu-SWCNTs indicate that intrinsic excitonic properties of SWCNTs sensitize the lanthanoid element europium (Eu) to emit time-resolved red luminescence.     

Noncovalent interactions of molecules with single walled carbon nanotubes

In this critical review we survey non-covalent interactions of carbon nanotubes with molecular species from a chemical perspective, particularly emphasising the relationship between the structure and dynamics of these structures and their functional properties. We demonstrate the synergistic character of the nanotube-molecule interactions, as molecules that affect nanotube properties are also altered by the presence of the nanotube. The diversity of mechanisms of molecule-nanotube interactions and the range of experimental techniques employed for their characterisation are illustrated by examples from recent reports. Some practical applications for carbon nanotubes involved in non-covalent interactions with molecules are discussed.     

Chemical and biochemical sensing with modified single walled carbon nanotubes

The nano dimensions, graphitic surface chemistry and electronic properties of single walled carbon nanotubes make such a material an ideal candidate for chemical or biochemical sensing. Carbon nanotubes can be nondestructively oxidized along their sidewalls or ends and subsequently covalently functionalized with colloidal particles or polyamine dendrimers via carboxylate chemistry. Proteins adsorb individually, strongly and noncovalently along nanotube lengths. These nanotube-protein conjugates are readily characterized at the molecular level by atomic force microscopy. Several metalloproteins and enzymes have been bound on both the sidewalls and termini of single walled carbon nanotubes. Though coupling can be controlled, to a degree, through variation of tube oxidative pre-activation chemistry, careful control experiments and observations made by atomic force microscopy suggest that immobilization is strong, physical and does not require covalent bonding. Importantly, in terms of possible device applications, protein attachment appears to occur with retention of native biological structure. Nanotube electrodes exhibit useful voltammetric properties with direct electrical communication possible between a redox-active biomolecule and the delocalized pi system of its carbon nanotube support.     

Transport properties of nitrogen in single walled carbon nanotubes

Transport properties including collective and tracer diffusivities of nitrogen, modeled as a diatomic molecule, in single walled carbon nanotubes have been studied by equilibrium molecular dynamics at different temperatures and as a function of pressure. It is shown that while the asymptotic decay of the translational and rotational velocity autocorrelation function is algebraic, the collective velocity decays exponentially with the relaxation time related to the interfacial friction. The tracer diffusivity in the nanochannel, which is comparable in magnitude with diffusivity in the equilibrium bulk phase, depends only weakly on the conditions at the fluid-solid interface, whereas the collective diffusivity is a strong function of the hydrodynamic boundary conditions and is found to be three orders of magnitude higher than self-diffusivity in carbon nanotubes and for the comparatively rough surface of the rare-gas tube it is one order of magnitude greater. A relationship between the collective diffusivity and the Maxwell coefficient describing wall collisions is obtained. The transport coefficients appear to be insensitive to the long-range details of the potential function.     

Effect of chemical potential on the computer simulation of hydrogen storage in single walled carbon nanotubes

Hydrogen is a kind of clean, sustainable and renewable energy carrier. Of the problems to be solved for the utilization of hydrogen energy, how to store and transport hydrogen has been given high priority on the research agenda. Recently, carbon nanotubes (CNTs) were reported to be very promising candidates for hydrogen uptake[1], which may have possibility to satisfy the benchmark set by the US Department of Energy (DOE) Hydrogen Plan for fuel cell powered vehicles: a gravimetric density …     

Electrochemical functionalization of single walled carbon nanotubes with polyaniline in ionic liquids

Single walled carbon nanotubes (SWNTs) are covalently functionalized during the electropolymerization of aniline in ionic liquids. In our experiment, 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIPF₆) containing 1 M trifluoroacetic acid (CF₃COOH) was selected as the ionic liquid media to separate SWNTs and to perform the electropolymerization of aniline within. The morphology of the resulting composite material of SWNT and polyaniline (PANI) was studied by scanning electron microscopy (SEM). Covalent bonding was evidenced by the increase of intensity ratio of the D band vs. G band in the Raman spectrum, whilst SWNTs may also be incorporated as big dopant anions to the PANI backbone. This paper provides a novel method by which large amount of SWNTs (15 mg/ml) can be modified by aniline electrochemically. p-type conducting polymer and n-type SWNTs can be thus copolymerized and applied to organic photovoltaics.     

Interactions in single wall carbon nanotubes/pyrene/porphyrin nanohybrids

This work provides an in-depth look at a range of physicochemical aspects of (i) single wall carbon nanotubes (SWNT), (ii) pyrene derivatives (pyrene(+)), (iii) porphyrin derivatives (ZnP(8)()(-)() and H(2)()P(8)()(-)()), (iv) poly(sodium 4-styrenesulfonate), and (v) their combinations. Implicit in their supramolecular combinations is the hierarchical integration of SWNT (as electron acceptors), together with ZnP(8)()(-)() or H(2)()P(8)()(-)() (as electron donors), in an aqueous environment mediated through pyrene(+). This supramolecular approach yields novel electron donor-acceptor nanohybrids (SWNT/pyrene(+)/ZnP(8)()(-)() or SWNT/pyrene(+)/H(2)()P(8)()(-)()). In particular, we report on electrochemical and photophysical investigations that as a whole suggest sizeable and appreciable interactions between the individual components. The key step to form SWNT/pyrene(+)()/ZnP(8)()(-)() or SWNT/pyrene(+)()/H(2)()P(8)()(-)() hybrids is pi-pi interactions between SWNT and pyrene(+), for which we have developed for the first time a sensitive marker. The marker is the monomeric pyrene fluorescence, which although quenched is (i) only present in SWNT/pyrene(+) and (ii) completely lacking in just pyrene(+). Electrostatic interactions help to immobilize ZnP(8)()(-)() or H(2)()P(8)()(-)() onto SWNT/pyrene(+) to yield the final electron donor-acceptor nanohybrids. A series of photochemical experiments confirm that long-lived radical ion pairs are formed as a product of a rapid excited-state deactivation of ZnP(8)()(-)() or H(2)()P(8)()(-)(). This formation is fully rationalized on the basis of the properties of the individual moieties. Additional modeling shows that the data are likely to be relevant to the SWNTs present in the sample, which possess wider diameters.     

Adsorption of xenon on purified HiPco single walled carbon nanotubes

We have measured adsorption of xenon on purified HiPco single-walled carbon nanotubes (SWNTs) for coverages in the first layer. We compare the results on this substrate to those our group obtained in earlier measurements on lower purity arc-discharge produced nanotubes. To obtain an estimate for the binding energy of Xe, we measured five low-coverage isotherms for temperatures between 220 and 260 K. We determined a value of 256 meV for the binding energy; this value is 9% lower than the value we found for arc discharge nanotubes and is 1.59 times the value found for this quantity on planar graphite. We have measured five full monolayer isotherms between 150 and 175 K. We have used these data to obtain the coverage dependence of the isosteric heat. The experimental values obtained are compared with previously published computer simulation results for this quantity.     

Direct imaging of o-carborane molecules within single walled carbon nanotubes

Ortho-carborane molecules have been inserted into single walled carbon nanotubes (SWNTs) and imaged directly by high resolution transmission electron microscopy (HRTEM); both discrete molecules and 'zig-zag' 1D chains of o-carborane 'petit pois' were observed to pack into the tubule capillaries.     

Studies on the encapsulation of F- in single walled nanotubes of different chiralities using density functional theory calculations and Car-Parrinello molecular dynamics simulations

In this study, the encapsulation of F(-) in different nanotubes (NTs) has been investigated using electronic structure calculations and Car-Parrinello molecular dynamics simulations. The carbon atoms in the single walled carbon nanotube (CNT) are systematically doped with B and N atoms. The effect of the encapsulation of F(-) in the boron nitride nanotube (BNNT) has also been investigated. Electronic structure calculations show that the (7,0) chirality nanotube forms a more stable endohedral complex (with F(-)) than the other nanotubes. Evidence obtained from the band structure of CNT calculations reveals that the band gap of the CNT is marginally affected by the encapsulation. However, the same encapsulation significantly changes the band gap of the BNNT. The density of states (DOS) derived from the calculations shows significant changes near the Fermi level. The snapshots obtained from the CPMD simulation highlight the fluctuation of the anion inside the tube and there is more fluctuation in BNNT than in CNT.     

Evaluating the hydrogen chemisorption and physisorption energies for nitrogen-containing single-walled carbon nanotubes with different chiralities: a density functional theory study

The hydrogen adsorption energies for nitrogen-containing carbon nanotubes (N-CNTs) and for bare carbon nanotubes were calculated using the density functional theory methods at the B3LYP/6–31-G(d) level, including dispersion force corrections. The N-CNTs were finite saturated and non-saturated single-walled carbon nanotubes that contained one or more pyrimidine units, the relative positions of which defined the different configurations of the nanotube. The chemisorption of atomic hydrogen to a full exocyclic monolayer of zigzag, armchair, and chiral N-CNTs was studied as a function of the structural parameters. Zigzag N-CNTs of any configuration, with a larger number of nitrogen atoms, a small diameter and a small length, are more reactive compared to chiral and armchair N-CNTs. The presence of nitrogen in the carbon nanotubes enhances their reactivity to chemisorb atomic hydrogen, showing exothermic energy values. In contrast, the physisorption of molecular hydrogen was endothermic for most of the studied saturated N-CNTs, even when including corrections for van der Waals interactions. The endothermicity was greatest for zigzag nanotubes, then decreased for chiral nanotubes and decreased again for armchair nanotubes. In general, the endothermicity decreased for longer nanotubes, which have larger diameters, and a small number of nitrogen atoms. The results of this study suggest that, with saturated bare carbon nanotubes, saturated, and unsaturated N-CNTs could potentially have a higher capacity as hydrogen-storage media than the corresponding unsaturated carbon nanotubes.     

In-depth study into the interaction of single walled carbon nanotubes with anthracene and p-terphenyl

Solubilization of single walled carbon nanotubes (SWNT) in the presence of polycyclic aromatic hydrocarbons (PAHs) such as p-terphenyl and anthracene has been shown. The suspensions formed are stable for periods greater than 48 months but to date experimental research is scarce regarding the interactions that are taking place. Spectroscopic analysis such as Raman and fluorescence are used to probe the interactions occurring between the PAHs and the SWNT over a wide concentration range. Previous studies show the fluorescence of the PAHs is quenched on interaction with SWNT and in the case of p-terphenyl, the spectrum is red shifted. This result prompted a study of a large range of concentrations to quantify the degree of interaction between the SWNT and PAHs. It was found at high concentrations that both the PAHs and SWNT formed aggregates and at lower concentrations it was found that free PAHs and isolated SWNT were interacting. The radial breathing modes (RBMs) in Raman spectroscopy gave detail as to how diameter selective the PAH samples are when compared to the pristine SWNT modes. An increase in the wavenumber of the RBMs for both composite spectra was observed and it is believed that such a result is due to the debundling of the SWNT on interaction with the PAHs. It was also found that anthracene and p-terphenyl selectively interact with SWNT and the selected SWNT were found to be within a distinct diameter range and possessed unique physical properties.     

Spin probe ESR studies of dynamics of single walled carbon nanotubes

The highly sensitive technique of spin-probe Electron Spin Resonance (ESR) has been used to study dynamics of carbon nanotubes. The ESR signals were recorded for the nitroxide free radical TEMPO in carbon nanotubes from 5 to 300 K. The onset of the fast dynamics of the probe molecule was indicated by appearance of a narrow triplet at 230 K. The ESR measurements were also done on TEMPO in methanol for the comparative studies in the same temperature range, and in the latter observations, no change in spectra was seen around 230 K. The results indicate the occurrence of a change in the dynamics of carbon nanotubes around this temperature.     

Molecular dynamics simulations on the effects of diameter and chirality on hydrogen adsorption in single walled carbon nanotubes

We present systematic molecular dynamics simulation studies of hydrogen storage in single walled carbon nanotubes of various diameters and chiralities using a recently developed curvature-dependent force field. Our main objective is to address the following fundamental issues: 1. For a given H2 loading and nanotube type, what is the H2 distribution in the nanotube bundle? 2. For a given nanotube type, what is the maximal loading (H2 coverage)? 3. What is the diameter range and chirality for which H2 adsorption is most energetically favorable? Our simulation results suggest strong dependence of H2 adsorption energies on the nanotube diameter but less dependence on the chirality. Substantial lattice expansion upon H2 adsorption was found. The average adsorption energy increases with the lowering of nanotube diameter (higher curvature) and decreases with higher H2 loading. The calculated H2 vibrational power spectra and radial distribution functions indicate a strong attractive interaction between H2 and nanotube walls. The calculated diffusion coefficients are much higher than what has been reported for H2 in microporous materials such as zeolites, indicating that diffusivity does not present a problem for hydrogen storage in carbon nanotubes.     

NMR chemical shifts of molecules encapsulated in single walled carbon nanotubes

We present density functional theory calculations of the nuclear magnetic resonance spectroscopy of molecules encapsulated within single walled carbon nanotubes. Ring currents in the nanotube induce shifts in the chemical shift of the nuclei comprising the encapsulated molecule. These changes in the chemical shifts are shown to have characteristic dependence on the chirality of the surrounding nanotubes.     

A density functional theory study of van der Waals interaction in carbon nanotubes

In this article, we investigate the effect of van der Waals force in zigzag carbon nanotubes (CNTs) including single-wall CNT (SWCNT) and double-walled CNT (DWCNT) structures with several interaction configurations. The solid-state density functional theory is employed to calculate the geometric optimization, normal mode frequencies, and IR and Raman spectra with the periodic boundary condition. For SWCNTs, we find that the Raman intensity is not affected by the tube diameter or the electronic structure. The IR absorption, however, increases with the tube diameter. We find that the close metallicity of the electronic structure has a significant impact on the IR simulations. When the van der Waals force is applied outside the CNTs at a distance longer than 3.0, the effect on Raman spectra is minimal but some effects can still be confirmed by IR absorption. When the van der Waals force acts inside the CNTs, the effect on the spectrum can be observed, especially at a distance of 2.8 Å, both IR and Raman can be significantly enhanced in many modes.     

Multiplexed multicolor Raman imaging of live cells with isotopically modified single walled carbon nanotubes

We show that single walled carbon nanotubes (SWNTs) with different isotope compositions exhibit distinct Raman G-band peaks and can be used for multiplexed multicolor Raman imaging of biological systems. Cancer cells with specific receptors are selectively labeled with three differently "colored" SWNTs conjugated with various targeting ligands including Herceptin (anti-Her2), Erbitux (anti-Her1), and RGD peptide, allowing for multicolor Raman imaging of cells in a multiplexed manner. SWNT Raman signals are highly robust against photobleaching, allowing long-term imaging and tracking. With narrow peak features, SWNT Raman signals are easily differentiated from the autofluorescence background. The SWNT Raman excitation and scattering photons are in the near-infrared region, which is the most transparent optical window for biological systems in vitro and in vivo. Thus, SWNTs are novel Raman tags promising for multiplexed biological detection and imaging.     

Two confined phases of argon adsorbed inside open single walled carbon nanotubes

Isothermal adsorption of Ar on single walled carbon nanotubes (SWNTs) has been studied at 77 and 87 K. The SWNTs have been grown by laser vaporization of a graphite pellet containing 0.6% (atomic) Ni/Co catalyst. The nanotubes have been prepared for argon adsorption measurements by prolonged outgassing of as-grown material in a vacuum at room temperature (295 K), at elevated temperatures of up to 475 K, and by oxidization for 2 h in dry air at 470 K. Formation of two condensed phases of Ar in the interior of SWNTs has been observed at 77 K. The low-density phase is formed at 155(5) microTorr, while the high-density phase, at 120(5) microTorr. At 87 K, only a single phase has been observed at 185(5) microTorr. Condensation at both 77 and 87 K appears to be the first-order phase transition. Onset of the quasi-one-dimensional linear (one-channel) phase and the quasi-two-dimensional monolayer (six-channel) phase formation on the external surface of bundles has been observed at 77 K near 0.0017 and 0.8 Torr, respectively, and at 87 K near 0.018 and 5 Torr, respectively. Isosteric heats of adsorption for the one-channel phase, the first external layer, and the second external layer have been determined to be equal to 137, 107, and 70 meV, respectively.