Regular chemisorption of hydrogen on achiral single-walled carbon nanotubes

Regular chemisorption of hydrogen on achiral single-walled carbon nanotubes has been investigated with the use of AM1 quantum-chemical semiempirical method. It has been found that regular hydrogen chemisorption deforms nanotubes, in some cases leading to stable prismatic modifications. The dependence of the adsorption energy on the density of hydrogen coverage has been found. A procedure for determining the adsorption energy by the spectra of thermally stimulated desorption has been proposed.     

Quasi-one-dimensional liquid hydrogen confined in single-walled carbon nanotubes

H₂ molecules confined in single-walled carbon nanotubes were studied using molecular dynamics simulations and ab initio calculations. It was found that at zero-temperature, H₂ molecules with low density tended to condense. Increasing the linear density of the H₂ molecules confined in the tube, various quasi-one-dimensional solid lattices were observed at low temperature. Heating the lattices above room temperature, molecular H₂ liquids with varying densities were observed. The quenching behavior of the H₂ fluids was examined. PACS 61.46.+w; 78.67.Bf     

卷曲效应对单壁碳纳米管电子结构的影响

利用计入卷曲效应的单壁碳纳米管(SWCNT)的能量色散关系,计算最低导带的电子速度及有效质量,并与不计入卷曲效应的结果进行了比较.计算结果表明:卷曲效应对电子速度及有效质量的影响与SWCNT的类型密切相关,金属锯齿型SWCNT对卷曲效应最为敏感,其次是扶手椅型SWCNT,最不敏感的是半导体锯齿型SWCNT.由此可以推断,卷曲效应对金属锯齿型SWCNT电子结构及低偏压输运特性影响最大,其次是扶手椅型SWCNT,影响最不明显的是半导体锯齿型SWCNT.这些结果与实验测量及密度泛函理论计算结果完全一致. 关键词： 单壁碳纳米管 卷曲效应 电子速度 电子有效质量     

Density and thermodynamics of hydrogen adsorbed on the surface of single-walled carbon nanotubes

A method is proposed for calculating the adsorption of hydrogen in single-walled carbon nanotubes. This method involves solving the Schrödinger equation for a particle (hydrogen molecule) moving in a potential generated by the surrounding hydrogen molecules and atoms forming the wall of the carbon nanotube. The interaction potential for hydrogen molecules is taken in the form of the Silvera-Goldman empirical potential, which adequately describes the experimental data on the interaction between H₂ molecules (including the van der Waals interaction). The interaction of hydrogen molecules with carbon atoms is included in the calculation through the Lennard-Jones potential. The free energy at a nonzero temperature is calculated with allowance made for the phonon contribution, which, in turn, makes it possible to take into account the correlations in the mutual arrangement of the neighboring molecules. The dependences of the total energy, the free energy, and the Gibbs thermodynamic potential on the applied pressure P and temperature T are calculated for adsorbed hydrogen molecules. These dependences are obtained for the first time with due regard for the quantum effects. The pressure and temperature dependences of the hydrogen density m(P, T) are also constructed for the first time.     

单壁BN纳米管和碳纳米管物理吸附储氢性能的理论对比研究

采用巨正则蒙特卡罗方法(GCMC)研究了单壁氮化硼纳米管(SWBNNTs)和单壁碳纳米管(SWCNTs)的物理吸附储氢性能,主要对比研究了纳米管的管径、温度和手性对二者物理吸附储氢量的影响. 研究结果表明：在低温下,SWBNNTs的物理吸附储氢性能优于相应的SWCNTs;但是随着温度的升高,二者的物理吸附储氢性能差别越来越小,在常温下,SWBNNTs不具备有比SWCNTs更强的物理吸附储氢性能,而是和相同条件下的SWCNTs相差不大,只是在高压下的物理吸附储氢量稍稍大于SWCNTs,并给出了合理的理论解释 关键词： 巨正则蒙特卡罗方法(GCMC) 单壁氮化硼纳米管(SWBNNTs) 单壁碳纳米管(SWCNTs) 储氢     

Conductivity of single-walled carbon nanotubes

In a system of N interacting single-level quantum dots (QDs), we study the relaxation dynamics and the current–voltage characteristics determined by symmetry properties of the QD arrangement. Different numbers of dots, initial charge configurations, and various coupling regimes to reservoirs are considered. We reveal that effective charge trapping occurs for particular regimes of coupling to the reservoir when more than two dots form a ring structure with the C_N spatial symmetry. We reveal that the effective charge trapping caused by the C_N spatial symmetry of N coupled QDs depends on the number of dots and the way of coupling to the reservoirs. We demonstrate that the charge trapping effect is directly connected with the formation of dark states, which are not coupled to reservoirs due to the system spatial symmetry C_N. We also reveal the symmetry blockade of the tunneling current caused by the presence of dark states.     

The geometrical and electronic structures of open-end fully functionalized single-walled carbon nanotubes

We have investigated the geometrical and electronic structures of open-end single-walled carbon nanotubes (SWNTs) having chemically modified tips, using semi-empirical AM1 and density functional theory methods. The hydroxyl (–OH), carboxyl (–COOH) and amide (–CONH₂) functional groups were used to saturate the open-ends of nanotubes. The effects of functional groups were studied by comparison with the pristine tubes, of which the tubular lengths vary from two to ten unit-cells (40 Å). The results show that the C–C bond lengths of all model tubes are only slightly different, and the behavior of converging bond lengths in COOH– and CONH₂-SWNTs is very similar to the pristine tube. Tip functionalization alters the frontier orbitals of the pristine tube, but these effects seem to rapidly decrease as the tubule becomes longer. In general, it can be concluded that the geometrical and electronic structures of pristine tubes after tube-end “full” functionalization will be preserved, hence supporting that more real-world “partially” functionalized SWNTs can be used in the same way as the pristine version in most application areas.     

Nucleation of single-walled carbon nanotubes

The nucleation pathway for single-wall carbon nanotubes on a metal surface is demonstrated by a series of total energy calculations using density functional theory. Incorporation of pentagons at an early stage of nucleation is energetically favorable as they reduce the number of dangling bonds and facilitate curvature of the structure and bonding to the metal. In the presence of the metal surface, nucleation of a closed cap or a capped single-wall carbon nanotube is overwhelmingly favored compared to any structure with dangling bonds or to a fullerene.     

Hydrogenation of single-walled carbon nanotubes

Towards the development of a useful mechanism for hydrogen storage, we have studied the hydrogenation of single-walled carbon nanotubes with atomic hydrogen using core-level photoelectron spectroscopy and x-ray absorption spectroscopy. We find that atomic hydrogen creates C-H bonds with the carbon atoms in the nanotube walls, and such C-H bonds can be completely broken by heating to 600 degrees C. We demonstrate approximately 65 +/- 15 at % hydrogenation of carbon atoms in the single-walled carbon nanotubes, which is equivalent to 5.1 +/- 1.2 wt % hydrogen capacity. We also show that the hydrogenation is a reversible process.     

Modeling double-helix carbon chains inside single-walled carbon nanotubes: Stable structures and XRD analysis

Atomic models are applied to investigate quasi-one-dimensional composites. The study presents the theoretical prediction of stable double-helix carbon chains growing inside single-walled carbon nanotubes as a function of tube radius. Meanwhile, our analysis shows that metastable structures may co-existence with the stable one, for small tubes. The classical molecular dynamics simulation shows that the regular and distorted double-helix C-chains are obtained with the tube's diameter smaller and larger than 13.32 Å, respectively. The temperature plays a minor role in the stable carbon chain structure unit it increases to 2500 K. The geometry optimization and the electronic structural analysis of the obtained optimal structure by the DFT calculation further justify our classical force field analysis. The electronic structure of SWCNTs can be significantly modified by the inserted carbon chain. The orbital hybridization between the host-guest molecules plays a key role in stabilizing the encapsulated double-helix carbon chain. Finally, X-ray powder diffraction (XRD) patterns of stable helical structures inside armchair tubes are presented for guidance of future experimental analyses.     

Ester-functionalized soluble single-walled carbon nanotubes

We report the preparation of soluble ester- functionalized single-wall carbon nanotubes (sSWNT-COO(CH₂)₁₇CH₃). By use of solution phase IR spectroscopy we are able to compare the ratio of the carbon atoms in the SWNT backbone to the carbon atoms in the ester and amide functionalities of s-SWNTs. Received: 16 July 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

NMR spectroscopy of hydrogen adsorption on single-walled carbon nanotubes after exposure to high pressure

Hydrogen storage properties of single-walled carbon nanotubes (CNTs) after exposure to a pressure of 14.3 MPa are studied by (1)H nuclear magnetic resonance spectroscopy. The nanotubes were carefully pre-characterized using inductively coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy (TEM), and Raman spectroscopy. We have shown previously that at ambient temperature in the pressure range from 0 to 1.5 MPa, hydrogen adsorption is fast and reversible and must be described as physisorption. However, exposure to a much higher pressure (14.3 MPa) of hydrogen leads to slower desorption kinetics where longer exposure causes greater hydrogen uptake. Our data suggest that interstitial sites and the tube interior may be identified as these strong adsorption sites.     

Amino acid adsorption on single-walled carbon nanotubes

We investigate and discuss the adsorption of a few amino acids on (3,3) carbon nanotubes and on graphite sheets through calculations within density functional theory. Results show weak binding of the biomolecules on both substrates, but through generally favourable adsorption pathways. Zwitterion adsorption through the charged amine and carboxylate groups are bound stronger to the nanotube surface in comparison to their nonionic counterparts, as well as on histidine, phenylalanine, and cysteine side chain groups fixed in specific orientations. Binding strengths on graphite suggest dissimilar trends for amino acid interactions with increasing nanotube diameter.     

Electrical transport measurements on single-walled carbon nanotubes

We review transport measurements on single-walled carbon nanotubes contacted by metal electrodes. At room temperature some devices show transistor action similar to that of p-channel field effect transistors, while others behave as gate-voltage independent wires. At low temperatures transport is usually dominated by Coulomb blockade. In this regime the quantum eigenstates of the finite-length tubes can be studied. At higher temperatures power law behaviour is observed for the temperature and bias dependence of the conductance. This is consistent with tunneling into a one-dimensional Luttinger liquid in a nanotube. We also discuss recent developments in contacting nanotubes which should soon allow study of their intrinsic transport properties. Received: 17 May 1999 / Accepted 18 May 1999 / Published online: 4 August 1999     

Photophysics of polymer-wrapped single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) are successfully dispersed in two conjugated polymer poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) and poly[2-methoxy-5- (2’-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEHPPV) solutions. Steady-state and time-resolved photoluminescence spectroscopy in the near-infrared and visible spectral regions are used to study the interaction of the dispersed carbon nanotube and the wrapped polymer in the nano-hybrids. The SWNTs infrared emission is the signatures of the separation of single semiconducting tubes, the lifetime of the photoluminescence of these tubes is bi-exponential with the first component varying from 6 ps (in MEHPPV wrapped SWNTs) to 14 ps (in PFO wrapped SWNTs), while the second component of the decay for all samples is in the range of 30-40 ps, revealing the intrinsic lifetime of the SWNTs. The study of the photoluminescence of the nano-hybrids in the visible spectral range shows, in the case of the PFO, a relatively strong quenching, the photoluminescence lifetime for the hybrid is more than 100 ps shorter than the one of the pristine polyfluorene solution. For the MEHPPV-SWNT hybrid an opposite behavior is revealed with the photoluminescence lifetime surprisingly longer than the polymer solution. The possible mechanism for the interaction of the two conjugated polymers and the SWNTs is discussed in terms of their electronic band structure.     

单壁纳米碳管的声子谱研究

通过五步旋转操作方便地得到了不同位置原子间的力常数矩阵，从而可以使对各种不同类型管的声子谱的计算变得简便. 计算表明，非螺旋的扶手椅型（n, n）管与锯齿型(n, 0)管的非简并和二重简并模式数分别为12和6(n-1)，这与从群论等方法所得结果相符. 关键词： 纳米碳管 声子谱 振动模式密度 动力学矩阵     

Flame synthesis of single-walled carbon nanotubes

Flames offer potential for synthesis of carbon nanotubes in large quantities at considerably lower costs than that of other methods currently available. This study aims to examine conditions for carbon nanotube formation in premixed flames and to characterize the morphology of solid carbon deposits and their primary formation mechanisms in the combustion environment. Single-walled nanotubes have been observed in the post-flame region of a premixed acetylene/oxygen/15 mol% argon flame operated at 6.7 kPa with Fe(CO)₅ vapor used as a source of metallic catalyst necessary for nanotube growth. Thermophoretic sampling and transmission electron microscopy were used to characterize the solid material present in the flame at various heights above burner (HAB), giving a resolution of formation dynamics within the flame system. Catalyst particle formation and growth is observed to dominate the immediate post-flame region (10–40 mm HAB). Nanotubes were observed to be present after 40 mm HAB with nanotube inception occurring as early as 30 mm HAB. Between 40 and 70 mm HAB, nanotubes are observed to coalesce into clusters. A nanotube formation ‘window’ is evident with formation limited to fuel equivalence ratios between 1.5 and 1.9. A continuum of morphologies ranging from relatively clean clusters of nanotubes to amorphous material is observed between these lower and upper limits. High-resolution TEM and Raman spectroscopy revealed nanotube bundles with each nanotube being single-walled with diameters between 0.9 and 1.5 nm.     

Purification and fractionation of single-walled carbon nanotubes

This study presents the approach to the purification and subsequent metallic/semiconductive (M/S) fractionation of single-walled carbon nanotubes (SWCNTs) with diameter from 1.04 to 1.60 nm produced via laser ablation. SWCNTs were purified through 3-fold refluxing processes in nitric acid followed by the multiple washings with sodium hydroxide and hydrochloric acid. The purified-annealed SWCNTs sample was divided into seven batches. One batch was dispersed in acetone as a reference sample. Each of the remaining batches were dispersed in one of the following surface agents: sodium dodecyl sulfate, sodium cholate acid (SCA), sodium deoxycholate, cetrimonium bromide, cetylpyridinium chloride, and benzalkonium chloride (BKC). SWCNT suspensions were fractionated via free solution electrophoresis technique. The recovered fractions from electrode and control areas were analyzed via optical absorption spectroscopy in UV–Vis–NIR range to evaluate the efficiency of the separation process. Raman spectroscopy was applied to analyze the purity of the samples. The catalyst content was estimated by atomic absorption spectroscopy. The morphology of the investigated samples was observed via high-resolution transmission electron microscopy. This contribution clearly shows that among the investigated surfactants there are two promising candidates (SCA and BKC) which can efficiently enrich the bulk sample in one electronic type of carbon nanotubes when FSE is applied.     

Bactericidal action of single-walled carbon nanotubes

The action of single-walled carbon nanotubes (SWCNTs) on cells of the genetically engineered K12 TG1 strain of Escherichia coli, which have a luminescent phenotype generated by the cloning of the lux operon of the native luminescent marine bacterium Photobacterium leiognathi into the strain, is studied in this work. The survival rate of the bacterial cells and their morphological changes are studied by means of atomic force microscopy as a function of their exposure to SWCNTs.     

Growth of single-walled carbon nanotubes on silicon nanowires

Single-walled carbon nanotubes (SWNTs) have been grown on silicon nanowires (SiNWs) by ethanol chemical vapor deposition (CVD) with Co catalysts. We have found that a surface SiO_x layer of SiNWs is necessary for the formation of active Co catalysts. In fact, the yield of the SWNT/SiNW heterojunctions gradually decreases as the thickness of the surface SiO_x layer decreases. Since thin SiNWs are transparent to an electron beam, the Co nanoparticles on SiNWs can be easily observed as well as SWNTs by TEM. Therefore, the relationship between the diameters of each SWNT and its catalyst nanoparticle has been investigated. The diameters of SWNTs are equal to or slightly smaller than those of the catalyst nanoparticles.