Synthesis and characterization of SWNT-heavy alkali metal intercalation compounds,effect of host SWNTs materials

Singlewall carbon nanotubes (SWNTs) produced by electric-arc and laser ablation methods were characterized by X-ray diffraction before and after the reaction with alkali metals (M=K, Rb, and Cs). Reaction with annealed SWNTs gave MC₈ composition at saturation. The alkali metal lattice showed short range order incommensurate with graphene cylinders of SWNTs. X-ray diffractogram simulations have enabled the study of the influence of SWNTs structure on that of intercalation compounds. Chemically-purified bundles, constituted of open SWNTs, can be intercalated inside and between the tubes forming disordered structures. Annealed or pristine bundles were intercalated only between the tubes leading to short or long range ordered structure depending on host crystallinity and alkali metal (K, Rb or Cs). The expansion of the 2D SWNTs lattice after intercalation is comparable to graphite intercalation compounds. Some 2D arrangements of SWNTs and K atoms are proposed and discussed to reproduce XRD results. ¹³C NMR and ESR studies of annealed doped SWNTs emphasize the fact that the intercalation compounds of SWNTs are metallic.     

TEM纳米云纹法测量纳米碳管变形

提出了透射电子显微镜(TEM)纳米云纹法的新技术,首次将该方法用于单根单壁碳纳米管的残余变形测量。纳米云纹由计算机显示器扫描线与碳纳米管束TEM图像干涉而成。该方法具有纳米级空间分辨率,可直接测量碳纳米管的力学性能。对TEM纳米云纹法的原理进行了详细的阐述,并利用不同管径的单壁碳管束产生了云纹。对直径为7.5nm的弯曲碳管束的残余变形进行测量,直接得到了其中一根直径为1.0nm的单壁碳管的残余变形场。实验结果证明了该方法的可行性。该方法为纳米尺度的碳管力学性能测量提供了新途径。     

Molecular dynamics simulations of hydrogen adsorption/desorption by palladium decorated single-walled carbon nanotube bundle

Utilising molecular dynamics simulations, the hydrogen molecules adsorption isotherms of the (8,?0) palladium decorated single-walled carbon nanotube (SWNT) were obtained. The hydrogen adsorption was studied on the external, interstial and internal surfaces of the SWNT bundle at several temperatures ranging from 77 to 400?K. The results were compared with the bare single-walled carbon nanotube bundle under the same conditions. The decorated carbon nanotube bundle hydrogen adsorption was significantly higher than that of the bare one. The hydrogen desorption and readsorption were studied using temperature as the readsorption/desorption variable. The rate constants were calculated for the hydrogen desorption at different temperatures. The calculated decorated SWNT bundle hydrogen desorption activation energy was higher than that for the bare SWNT bundle. The calculated activation energies for the hydrogen desorption in both nanotube bundles specified the temperature dependency of hydrogen desorption.     

Gases Do not adsorb on the interstitial channels of closed-ended single-walled carbon nanotube bundles

We have experimentally determined the binding energies of Xe, CH4, and Ne on samples of closed-ended single-wall nanotube (SWNT) bundles. We find values for these quantities which are larger by approximately 75% on the SWNT samples than the values found for the same adsorbates on planar graphite. We have also determined the monolayer capacity of a SWNT sample using Xe and Ne adsorption. A comparison of all of our results leads us to conclude that none of the gases studied adsorb on the interstitial channels in the SWNT bundles.     

Evidence of 1D behavior of He4 confined within carbon-nanotube bundles

We present the first low-temperature thermodynamic investigation of the controlled physisorption of He4 gas in carbon single-wall nanotube (SWNT) samples. The vibrational specific heat measured between 100 mK and 6 K demonstrates an extreme sensitivity to outgassing conditions. For bundles with a few number of nanotubes the extra contribution to the specific heat, C(ads), originating from adsorbed He4 at very low density displays 1D behavior, typical for He atoms localized within linear channels as grooves and interstitials, for the first time evidenced. For larger bundles, C(ads) recovers the 2D behavior akin to the case of He4 films on planar substrates (grafoil).     

Formation mechanism of carbon nanotubes in the gas-phase synthesis from colloidal solutions of nanoparticles

Single- and multi-wall carbon nanotubes have been synthesized by the gas-phase catalytic reaction of colloidal solutions of metal nanoparticles using a vertical flow reactor. The reverse micelle solution of the Co–Mo nanoparticles with the mean diameter of 11 nm dissolved in toluene was injected directly into the reactor maintained at 1200 °C. The nanoparticles and the solvent act as the catalyst and carbon source, respectively. When the concentration of the thiophene additive is low (1 wt.%), the formation of SWNT bundles preferentially occurred. The SWNT bundles were present together with the relatively small metal nanoparticles with the diameter of 0.5–5.5 nm. It is likely that the original nanoparticles with the diameter of 11 nm break into smaller ones, 1–2 nm diameters, which is suitable for the SWNT growth. The synactic effect of Co and Mo was also observed.     

Phonon density of states of single-wall carbon nanotubes

The vibrational density of states of single-wall carbon nanotubes (SWNT) was obtained from inelastic neutron scattering data from 0 to 225 meV. The spectrum is similar to that of graphite above 40 meV, while intratube features are clearly observed at 22 and 36 meV. An unusual energy dependence below 10 meV is assigned to contributions from intertube modes in the 2D triangular lattice of SWNT bundles, and from intertube coupling to intratube excitations. Good agreement between experiment and a calculated density of states for the SWNT lattice is found over the entire energy range.     

Diffraction by finite-size crystalline bundles of single wall nanotubes

We calculate the diffraction spectrum of finite-size crystalline bundles of single wall carbon nanotubes (SWNT). The general profile of the spectrum as well as the width and position of the (1 0) diffraction peaks of the 2-D lattice of bundles depend on the tubes symmetry, distribution of tubes diameters and diameter of the bundles. Consequently, any attempt to derive the mean-diameter of the tubes from a diffraction spectrum requires to consider the diameters distribution of the tubes and the size of the bundles. Experimental diffraction profiles of various single wall nanotubes samples are well fitted by the calculated spectra. Received 16 December 1998     

Visible and near-infrared excited-state dynamics of single-walled carbon nanotubes

Excited-state lifetimes of isolated single-walled semiconducting carbon nanotubes (SWNTs) have been measured for the first time; these excited states, observed over the 400- to 1800-nm spectral domain, possess lifetimes that range from several ps to more than 100 ps. Sub-ps to ps decay components are assigned to relaxation in SWNT bundles. Interrogation of the samples with different SWNT mean diameters further confirms the dependence of the excited-state lifetime on roll-up vector. The ratio of fast and slow decaying component contributions in the first van Hove band can be viewed as a measure of the bundle content. PACS 78.67.Ch; 78.47.+p; 61.46.+w; 73.22.-f     

Collapse of single-wall carbon nanotubes is diameter dependent

We present classical molecular dynamics simulations demonstrating that single-wall carbon nanotube (SWNT) bundles collapse under hydrostatic pressure. The collapse pressures obtained as a function of nanotube diameter are in excellent quantitative agreement with new data presented here for small diameter (d approximately 0.8 nm) SWNTs, and the majority of previously published results, although there remain some unreconciled contradictions in the literature. The collapse pressure is found to be independent of the nanotube chirality, and a lower limit on the largest SWNT that remains inflated at atmospheric pressure is established (d>4.16 nm).     

First principle study of Li-intercalated (5, 5) ZnO nanotube bundles

We have investigated the geometric and electronic structure of Li-intercalated (5, 5) zinc oxide nanotube (ZnONT) bundles via density functional theory as implemented in the code WIEN2k. Our results show that the geometrical structures are changed because of intercalation of lithium. The effect of Li intercalation on the density of state and electronic band structure is a shift of the Fermi energy due to the charge transfer from lithium to the ZnONTs. Although, the bundle of clean (5, 5) ZnONTs is semiconductor, all the Li-intercalated (5, 5) ZnONT bundles are found to be metallic. Both inside of the nanotube and the interstitial spaces are susceptible for intercalation.     

Neutron scattering studies of the structure and dynamics of nanobundles of single-wall carbon nanotubes

Elastic and inelastic neutron scattering are used to study the structure and dynamics of single-wall carbon nanotubes (SWNT) self-assembled into nanobundles (NBSWNT). Suspensions of NBSWNT are characterized by small-angle neutron scattering. Neutron diffraction is used as a useful tool to study the structure of both the SWNT and NBSWNT. Calculations on finite-size bundles are compared to the data in order to estimate the distribution of tube diameters. Finally, we present time of flight inelastic scattering measurements of the phonon density of states and discuss the main features of the spectra in comparison with calculations. Received: 9 June 1999 / Accepted: 3 August 1999 / Published online: 27 October 1999     

Selection of isolated and individual single-walled carbon nanotube from a film and its usage in nanodevices

Individual and isolated single-walled carbon nanotubes (SWNTs) are important for fabricating relevant nanode- vices and studying the properties of the SWNT devices. In this work, we demonstrate that individual and isolated SWNT can be selected and obtained from a film containing a huge number of SWNTs. By using both the polymethyl-methacrylate (PMMA) as a negative resist and the electron beam lithography, the selected SWNT can be fixed on a substrate, while the other SWNTs in the film can lift off. The selected SWNT can be used to fabricate nanodevice and a gas sensor of oxygen is demonstrated in this work.     

The effect of a large SWNT diameter distribution on cesium intercalation

Vapor-phase intercalation of a single-walled carbon nanotube sample with Cs was carried out and monitored in situ by Raman spectroscopy. Results indicate that the endpoint of the intercalation was limited by small interstitial gaps in the nanotube bundles. These small-diameter gaps are present because of the significant number of small-diameter nanotubes (0.9-1.0 nm, as calculated from Raman radial breathing mode frequencies) present in the sample. It is not possible to determine from our Raman spectra whether the early endpoint is the result of diffusion limitation or the equilibrium energetics at the endpoint, although some diffusion limitation is observed near the beginning of the reaction. A simple geometric model for expansion of the nanotube bundles under intercalation is presented; this model reproduces, reasonably well, measured expansions reported by others and explains both diffusion- and equilibrium-limited mechanisms in terms of the larger lattice expansion required for smaller-diameter nanotubes. Staging of the intercalation process, in analogy with the staged intercalation of graphite intercalation compounds, is not observed. Instead, the transverse mode peaks undergo a gradual decrease in intensity and a gradual charge transfer- and electronic coupling-induced downshift.     

单壁碳纳米管:纳米发电机和纳米马达

简要回顾了单壁碳纳米管的发现及研究现状,介绍了一种新颖的悬空单壁碳纳米管的制备方法;在此基础上,通过新的一种四电极方法,用实验证明水分子可以进入两端开口的单壁碳纳米管内,由于水分子偶极子与碳纳米管中载流子的相互产生相互耦合作用,载流子的定向运动(电流)可以使水产生定向运动(纳米马达);同时,水的运动又会使碳纳米管中的载流子产生定向运动而产生一个电动势(纳米发电机).     

单壁碳纳米管低温及常温下储氢行为的模拟计算研究

采用巨正则系综蒙特卡罗方法, 通过含有此方法模块的GULP软件, 系统地研究了扶手椅式单壁碳纳米管在低温和常温下的储氢性能, 给出了5种半径的扶手椅管在液氮温度(77 K)和常温(280 K)下的吸附等温线, 同一管径在不同温度不同压强下氢分子在碳纳米管中的分布构型图等. 对77 K和280 K下不同压强不同管径的碳纳米管储氢能力做了较为全面的对比分析, 最后根据模拟计算的结果, 对碳纳米管储氢能力的强化提出了一些建设性意见.     

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.     

Bucky-corn: van der Waals composite of carbon nanotube coated by fullerenes

ABSTRACT

Can a C₆₀ layer cover a surface of single-wall carbon nanotube (SWCNT) forming an exohedral pure-carbon hybrid with only van der Waals interactions? The aim of the present paper is to address this question and to demonstrate that the fullerene shell layer in such a bucky-corn structure can be stable. Theoretical study of the structure, stability and electronic properties of bucky-corn hybrids is reported for the shell of C₆₀ and C₇₀ molecules on an individual SWCNT, C₆₀ dimers on an individual SWCNT as well as C₆₀ molecules on SWNT bundles. The geometry and total energies of the bucky-corn hybrids were calculated by the molecular dynamics method, while the density functional theory method was used to simulate the electronic band structures.     

Hydrogen adsorption in microporous alkali-doped carbons (activated carbon and single wall nanotubes)

Adsorption of hydrogen gas was tested in microporous doped carbons: activated carbon (1600 m²/g) and single wall carbon nanotubes (SWNTs). The isotherms of adsorption of LiC₁₈ and KC₂₄ doped microporous activated carbons were determined in the range [0–30 bar] at room temperature and 77 K. The chemisorption ratio observed at room temperature increases with increasing the alkali/carbon rate. The isotherm profiles of doped activated carbon at 77 K show no clear enhancement of the sorption ratio compared to the raw activated carbon.The adsorption sites of potassium doped SWNTs with closed end were determined by neutron diffraction experiment using deuterium gas. The K-doped SWNTs were found only slightly intercalated by K ions so that empty cavities are preserved in between the tubes. At room temperature, the chemisorption of deuterium was not observed in doped SWNTs bundles, but only in the KC₈ graphite intercalation compound impurities. At low temperature, the isotherms analysis and neutron diffraction experiments have shown that D₂ molecules are physisorbed in the free interstitial voids in between the tubes within the bundles.     

Controllable growth and characterization of isolated single-walled carbon nanotubes catalyzed by Co particles

Discrete Co catalytic nanoparticles with small diameters are obtained by pulsed vacuum arc evaporation on Si/SiO₂ substrates, which are used for the growth of isolated single-walled carbon nanotubes (SWNTs) by an ethanol chemical vapor deposition approach (CVD). The distributions of catalytic nanoparticles change with the number of arc pulses, which allows control of the nanotubes formation. We find that an increase of ethanol pressure during CVD growth can change SWNTs from isolated ones into bundles. A new growth mechanism which combines a tip and base model for SWNT growth has been tentatively proposed. It is suggested that the small size catalytic particles prepared by pulsed arc evaporation have a potential advantage for small diameter SWNT growth. PACS 78.67.Ch; 78.67.Bf; 78.67.-n; 81.07.De; 61.46.-w