The Cohesive Energy and Vibration Characteristics of Parallel Single-Walled Carbon Nanotubes

Based on the van der Waals (vdW) interaction between carbon atoms, the interface cohesive energy between parallel single-walled carbon nanotubes was studied using continuous mechanics theory, and the influence of the diameter of carbon nanotubes and the distance between them on the cohesive energy was analyzed. The results show that the size has little effect on the cohesive energy between carbon nanotubes when the length of carbon nanotubes is over 10 nm. At the same time, we analyzed the cohesive energy between parallel carbon nanotubes with the molecular dynamics simulation method. The results of the two methods were compared and found to be very consistent. Based on the vdW interaction between parallel carbon nanotubes, the vibration characteristics of the two parallel carbon nanotube system were analyzed based on the continuous mechanical Euler-beam model. The effects of the vdW force between carbon nanotubes, the diameter and length of carbon nanotubes on the vibration frequency of carbon nanotubes was studied. The obtained results are helpful in improving the understanding of the vibration characteristics of carbon nanotubes and provide an important theoretical basis for their application.     

Analysis of Single-Walled Carbon Nanotubes Using a Chemical Bond Element Model

A three dimensional nano-scale finite element model (FEM), called the chemical bond element model, is proposed for the simulation of mechanical properties of single-walled carbon nanotubes (SWCNTs) based upon molecular mechanics method. Chemical bonds between carbon atoms are modeled by chemical bond elements. The constants of a sub-stiffness matrix are determined by using a linkage between molecular mechanics and continuum mechanics. In order to evaluate the correctness and performance of the proposed model, simulation was done to determine the influence of nanotube wall thickness, radius and length on the elastic modulus (Young's modulus and shear modulus) of SWCNTs. The simulation results show that the choice of wall thickness significantly affects the Young's modulus and shear modulus. The force field constants is also very important, because the elastic modulus is sensitive to force field constants and the elastic properties of SWCNT are related to the radii of the tubes. The contribution of length to elastic modulus is insignificant and can be ignored. In comparison with the Young's modulus and shear modulus reported in the literature, the presented results agree very well with the corresponding theoretical results and many experimental measurements. Furthermore, if the force constants are properly chosen, the present method could be conveniently used to predict the mechanical behavior of other single-walled nanotubes such as boron nitride nanotubes. The results demonstrate the value of the proposed model as a valuable tool in the study of mechanical behaviors of carbon nanotubes and in the analysis of nanotube-based equipments.     

A Modiˉed Molecular Structural Mechanics Method for Analysis of Carbon Nanotubes

A modified molecular structural mechanics method, based on molecular mechanics and similar to the finite element method, was developed. The energy of a system was expressed by the force field functions of the molecular mechanics. Under the small deformation assumption and by the principle of minimum potential energy, the system function was established. The properties of tension and bending of single-walled carbon nanotubes were analyzed. The Young's modulus is about 0.36 TPa nm, which agrees perfectly with the results of previous analysis by other researchers. It is found, for the first time, that the Young's moduli, for Zigzag nanotubes, are different from each other when the system energy was expressed as the sum of two or three individual energy terms in molecular mechanics. Whereas, the Young's moduli were the same for the Armchair nanotubes. It is found, when simulating the bending, that the deflections are closer to the theoretical ones, of the classical elasticity, when the diameter of the carbon nanotube increases.     

Phase transition of nanotube-confined water driven by electric field

The effects of electric field on the phase behaviors of water encapsulated in a thick single-walled carbon nanotube (SWCNT) (diameter = 1.2 nm) have been studied by performing extensive molecular dynamics simulations at atmospheric pressure. We found that liquid water can freeze continuously into either pentagonal or helical solidlike ice nanotube in SWCNT, depending on the strengths of the external electric field applied along the tube axis. Remarkably, the helical one is new ice phase which was not observed previously in the same size of SWCNT in the absence of electric field. Furthermore, a discontinuous solid-solid phase transition is observed between pentagonal and helical ice nanotubes as the strengths of the external electric field changes. The mechanism of electric-field-induced phase transition is discussed. The dependence of ice structures on the chiralities of SWCNTs is also investigated. Finally, we present a phase diagram of confined water in the electric field-temperature plane.     

Optical properties of single-walled 4 A carbon nanotubes

Optical properties of a series of finite sized hydrogenated carbon nanotubes with the smallest diameter of 4 A are studied systematically. Their absorption spectra are calculated with the localized-density-matrix method. The semiempirical MNDO parametric method 3 (PM3) Hamiltonian is employed. The finite optical gaps are predicted for the infinite long single-walled carbon nanotubes. Strong anisotropy characteristics of the dynamic polarizabilities are found for these tubes. The calculated results are in good agreement with the recent experimental findings. Further the compositions of the dipole-induced excitations are examined by projecting the corresponding density matrices onto the Hartree-Fock molecular orbital representation. Unlike the larger diameter carbon nanotubes whose absorption spectra are insensitive to the tube chiralities, the absorption spectra of 4 A single-walled carbon nanotubes depend very much on their chiralities. The chirality of the single-walled 4 A carbon nanotubes synthesized in the channels of the porous zeolites is thus determined to be (5,0) by comparing the calculated and measured absorption spectra.     

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.     

Integrated QMMM and Monte Carlo methods for analysis of adsorptive interactions between goethite cluster,carbon nanotubes,and arsenate

Iron‐immobilized nanoporous carbon is a well‐known adsorbent used in treating arsenic‐contaminated waters. In this contribution, we present findings on the adsorptive interactions and dynamics of arsenate–goethite cluster ([FeO(OH)]₆) with carbon nanotubes (CNTs) using hybridized quantum mechanics/molecular mechanics (QMMM) calculations. The CNTs adsorption mechanism is of interest since a better understanding of the fundamental interactions between arsenate, goethite, and carbon surfaces would translate to advances in CNT‐based adsorbent production and utilization. Novel applications of general amber force field (GAFF) and isobaric‐isothermal Gibbs ensemble Monte Carlo (NpT‐GEMC) methods are described. By the abovementioned methods, we postulate that the [FeO(OH)]₆/CNT‐2.3 (diameter 2.3 nm ‐ mesoporous) system enhances the qualitative (i.e., improved chemisorption) rather than the quantitative adsorptive aspect (i.e., total ions adsorbed) in comparison to the [FeO(OH)]₆/CNT‐1.6 (diameter 1.6 nm ‐ microporous) system.     

Thermal decomposition of ferrocene as a method for production of single-walled carbon nanotubes without additional carbon sources

A new method to grow bulk quantities of single-walled carbon nanotubes (SWCNTs) by a catalytic chemical vapor deposition (CVD) process with the possibility of varying the pressure has been developed and is reported in this paper. Thermal decomposition of ferrocene provides both catalytic particles and carbon sources for SWCNT growth using Ar as a carrier gas. Upon an increase in the pressure, the mean diameter of the SWCNTs decreases. In fact, high abundances of SWCNT with diameters as small as 0.7 nm, which is the limit for stable caps with isolated pentagons, can be obtained. An additional advantage of this method is that as no external carbon sources are required, SWCNT synthesis can be achieved at temperatures as low as 650 degrees C.     

On the applicability of cluster models to study the chemical reactivity of carbon nanotubes

We have performed a comparative study on the reactivity of metallic and semiconducting nanotubes using infinite and finite models. Infinite models were created using periodic boundary conditions while finite ones were constructed by means of hydrogen terminated nanotubes sections. Cluster models systematically underestimate the reactivity of metallic single wall carbon nanotube (SWCNT)s. We have confirmed that metallic nanotubes are more reactive than semiconducting species, in disagreement with previous works. The differences can be attributed to the presence of an instability in the singlet ground state of the wavefunction corresponding to semiconducting nanotubes clusters. When lower electronic states of the pristine cluster are considered, semiconducting nanotubes become less reactive as compared with metallic SWCNTs. Particularly, if an antiferromagnetic solution is considered for the semiconducting (10,0) SWCNT cluster, it becomes less reactive than the (5,5) SWCNT, as observed for infinite models. Because semiconducting nanotubes are less reactive than metallic counterparts, their reaction energies converge faster to the values observed for graphene. For a 1.6-nm diameter semiconducting nanotube, the addition energy is comparable with graphene. Thus, semiconducting nanotubes with diameters larger than 1.6 nm are going to be as reactive as graphene and the effects of curvature will be unimportant.     

Single‐Wall Carbon Nanotubes Covalently Functionalized with Polylysine: Synthesis,Characterization and Analytical Applications for the Development of Electrochemical (Bio)Sensors

This work reports the synthesis of single‐wall carbon nanotubes (SWCNT) covalently functionalized with polylysine (Plys) and the analytical performance of glassy carbon electrodes (GCE) modified with this material (GCE/SWCNT‐Plys). The resulting electrodes showed an important decrease in the overvoltages for the oxidation of ascorbic acid, uric acid and hydrogen peroxide as well as for the reduction of hydrogen peroxide. The favorable interaction of glucose oxidase (GOx) with SWCNT‐Plys allowed the sensitive and selective glucose biosensing at ?0.100 V without any permselective membrane. The proposed sensor was challenged with different real samples without pretreatment showing an excellent correlation with the reported values.     

Unraveling the 13C NMR chemical shifts in single-walled carbon nanotubes: dependence on diameter and electronic structure

The atomic specificity afforded by nuclear magnetic resonance (NMR) spectroscopy could enable detailed mechanistic information about single-walled carbon nanotube (SWCNT) functionalization as well as the noncovalent molecular interactions that dictate ground-state charge transfer and separation by electronic structure and diameter. However, to date, the polydispersity present in as-synthesized SWCNT populations has obscured the dependence of the SWCNT (13)C chemical shift on intrinsic parameters such as diameter and electronic structure, meaning that no information is gleaned for specific SWCNTs with unique chiral indices. In this article, we utilize a combination of (13)C labeling and density gradient ultracentrifugation (DGU) to produce an array of (13)C-labeled SWCNT populations with varying diameter, electronic structure, and chiral angle. We find that the SWCNT isotropic (13)C chemical shift decreases systematically with increasing diameter for semiconducting SWCNTs, in agreement with recent theoretical predictions that have heretofore gone unaddressed. Furthermore, we find that the (13)C chemical shifts for small diameter metallic and semiconducting SWCNTs differ significantly, and that the full-width of the isotropic peak for metallic SWCNTs is much larger than that of semiconducting nanotubes, irrespective of diameter.     

Molecular beam-controlled nucleation and growth of vertically aligned single-wall carbon nanotube arrays

The main obstacle to widespread application of single-wall carbon nanotubes is the lack of reproducible synthesis methods of pure material. We describe a new growth method for single-wall carbon nanotubes that uses molecular beams of precursor gases that impinge on a heated substrate coated with a catalyst thin film. In this growth environment the gas and the substrate temperature are decoupled and carbon nanotube growth occurs by surface reactions without contribution from homogeneous gas-phase reactions. This controlled reaction environment revealed that SWCNT growth is a complex multicomponent reaction in which not just C, but also H, and O play a critical role. These experiments identified acetylene as a prolific direct building block for carbon network formation that is an order of magnitude more efficient than other small-molecule precursors. The molecular jet experiments show that with optimal catalyst particle size the incidence rate of acetylene molecules plays a critical role in the formation of single-wall carbon nanotubes and dense vertically aligned arrays in which they are the dominant component. The threshold for vertically aligned growth, the growth rate, the diameter, and the number of walls of the carbon nanotubes are systematically correlated with the acetylene incidence rate and the substrate temperature.     

Adsorption of polyaromatic hydrocarbons on single wall carbon nanotubes of different functionalities and diameters

Adsorption from toluene solution of phenanthrene and tetracene on single wall carbon nanotubes (SWCNT) is measured. Comparison of adsorbents such as laser ablation and HipCO samples reveals multiple factors influencing the adsorption mechanism. Acid functionalized carbon nanotubes have shown markedly increased adsorbability for the polyaromatic molecules. The linear tetracene molecule's adsorption is more promoted on nanotubes with increasing diameter, but also additionally with presence of the carboxylic groups. The adsorption mechanisms on carboxylic sites and on the bold, non-functionalized large-diameter nanotubes are suggested and supported by detailed characterization of the SWCNTs applied.     

Electrochemical oxidation and nanomolar detection of acetaminophen at a carbon-ceramic electrode modified by carbon nanotubes: a comparison between multi walled and single walled carbon nanotubes

Carbon-ceramic electrodes (CCE) modified with carbon nanotubes were prepared, and the electrochemical behavior towards acetaminophen (ACOP) was investigated using both a bare CCE and electrodes modified with either single walled carbon nanotubes (SWCNT) or multi walled carbon nanotubes (MWCNT) in an effort to understand which of them is the better choice in terms of electrocatalyzing the oxidation of ACOP, and thus for sensing it. The SWCNT are found to be the better material in significantly enhancing the oxidation peak current and improving the reversibility of the oxidation. Under optimal conditions, linearity between the oxidation peak current and the concentration of ACOP is obtained for the concentration range from 40?nM to 85???M, with a detection limit of 25?nM. Finally, ACOP was successfully determined with the SWCNT modified electrode in pharmaceutical samples.

Enthalpy and entropy effects in hydrogen adsorption on carbon nanotubes

Interaction energies and entropies associated with hydrogen adsorption on the inner and outer surfaces of zigzag single-wall carbon nanotubes (SWCNT) of various diameters are analyzed by means of molecular mechanics, density functional theory, and ab initio calculations. For a single molecule the strongest interaction, which is 3.5 greater than that with the planar graphite sheet, is found inside a (8,0) nanotube. Adsorption on the outer surfaces is weaker than that on graphite. Due to the steric considerations, both processes are accompanied by an extremely strong decline in entropy. Absence of specific adsorption sites and weak attractive interaction between hydrogen molecules within carbon nanotubes results in their close packing at low temperatures. Using the calculated geometric and thermodynamic parameters in Langmuir isotherms we predict the adsorption capacity of SWCNTs at room temperature to be smaller than 1 wt % even at 100 bar.     

Immobilized carbon nanotubes as matrix for MALDI-TOF-MS analysis: Applications to neutral small carbohydrates

In this work, we reported on the advantages of immobilized carbon nanotubes as a novel MALDI-matrix. Recently, carbon nanotubes have been reported to be an effective MALDI matrix for small molecules (Anal. Chem.2003, 75, 6191), as it can eliminate the interfering matrix peaks as well as form a web morphology to fully disperse the analyte and allow strong ultraviolet absorption for enhanced pulsed laser desorption and ionization. In our study, to overcome the problem that the carbon nanotube matrix may fly off from the target, a type of polyurethane adhesive, NIPPOLAN-DC-205, is introduced to immobilize carbon nanotubes on the target, which enables widespread application of carbon nanotubes as matrix for MALDI-MS analysis. At the same time, the properties of the carbon nanotubes as an efficient matrix remained after immobilization. The presence of NIPPOLAN-DC-205 increases the time for analysis at a particular desorption spot by minimizing the time-consuming search for "hot spots" and facilitating experiments such as post source decay (PSD) which need longer-lasting signals. Moreover, NIPPOLAN-DC-205 produces no interference peaks and can easily be cleaned with acetone. Fast evaporation technology may be used to enhance signal reproducibility in MALDI analysis using carbon nanotubes as matrix. Consequently, the applicability of the carbon nanotube as matrix for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) analysis of low molecular mass analytes is highly improved. The feasibility of the method employing polyurethane is demonstrated by comparison of the results produced from the carbon nanotube matrix with and without immobilization. In addition, neutral small carbohydrates, which are difficult to be ionized normally, can be cationized with high efficiency by MALDI-TOF-MS using the immobilized carbon nanotube matrix. The method was further applied to analyze peptides and detect urine glucose successfully.     

Carbon nanotubes as adsorbent of solid-phase extraction and matrix for laser desorption/ionization mass spectrometry

A method with carbon nanotubes functioning both as the adsorbent of solid-phase extraction (SPE) and the matrix for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) to analyze small molecules in solution has been developed. In this method, 10 microL suspensions of carbon nanotubes in 50% (vol/vol) methanol were added to the sample solution to extract analytes onto surface of carbon nanotubes because of their dramatic hydrophobicity. Carbon nanotubes in solution are deposited onto the bottom of tube with centrifugation. After removing the supernatant fluid, carbon nanotubes are suspended again with dispersant and pipetted directly onto the sample target of the MALDI-MS to perform a mass spectrometric analysis. It was demonstrated by analysis of a variety of small molecules that the resolution of peaks and the efficiency of desorption/ionization on the carbon nanotubes are better than those on the activated carbon. It is found that with the addition of glycerol and sucrose to the dispersant, the intensity, the ratio of signal to noise (S/N), and the resolution of peaks for analytes by mass spectrometry increased greatly. Compared with the previously reported method by depositing sample solution onto thin layer of carbon nanotubes, it is observed that the detection limit for analytes can be enhanced about 10 to 100 times due to solid-phase extraction of analytes in solution by carbon nanotubes. An acceptable result of simultaneously quantitative analysis of three analytes in solution has been achieved. The application in determining drugs spiked into urine has also been realized.     

Electrostatic current switching and negative differential resistance behavior in a molecular device based on carbon nanotubes

The electronic transport properties of an all-carbon mechanically controlled molecular device based on carbon nanotubes are studied using non-equilibrium Green's function in combination with density functional theory. A segment of (10,0) single-walled carbon nanutube (SWCNT) is placed concentrically outside a (5,0) SWCNT, namely, a (5,0)@(10,0) double-walled carbon nanotube (DWCNT). It is found that the position, orientation and length scaling of the (10,0) SWCNT have crucial effects on the electronic transport properties of the system. When the (10,0) SWCNT is mechanically pushed forward along the axial direction, alternation of on/off switching behavior under low bias and negative differential resistance behavior under high bias are observed. Significant changes in the electronic transport properties arise when rotating the (10,0) SWCNT around the common axis or adding carbon atom layers in the transport direction. Theoretical explanations are proposed for these phenomena.     

异型碳纳米管储氢性能的分子动力学模拟研究

采用分子动力学(MD)方法对三种理想的Y型碳纳米管[记为Y(4,4), Y(6,6), Y(10,0)]和三种L型碳纳米管[记为L(9,0), L(6,6), L(10,0)]之储氢性能进行了模拟研究, 并与相应的直线型碳纳米管的储氢能力进行了比较, 同时考察了温度、碳纳米管的直径和螺旋性以及缺陷的位置和大小对异型碳纳米管储氢性能的影响. 结果表明, 在室温和低温条件下, 异型碳纳米管的储氢量高于直线型碳纳米管的储氢量, 且其储氢量大小随温度的降低和碳管直径的增大而增加, 椅式碳纳米管的储氢性能优于齿式碳纳米管, 而缺陷的位置和大小对异型碳管之储氢性能的影响则因碳管的形貌和直径的大小不同而存在差异.