Effects of various defects on the electronic properties of single-walled carbon nanotubes: A first principle study

The geometries,formationenergies and electronic band structures of （8, 0） and （14, 0） singlewailed carbon nanotubes （SWCNTs） with various defects, inehlding vaeaney, Stone-Wales defect, and octagon pentagon pair defect, have been investigated within the framework of the density- huictional theory （DFT）, and the influence of the concentration within the same style of deflect on the physical and chenfical properties of SWCNTs is also studied. The results suggest that the existeilcc of vacancy and octagon-pentagon pair deflect both reduce the band gap, whereas the SW- defect induces a band gap opening in CNTs. More int, erestingly, the band gaps of （8, 0） and （14, 0） SWCNTs eonfigurations with two octagon pentagon pair defect presents 0.517 eV and 0.163/eV, which arc a little smaller than the perfectt CNTs. Furthermore, with the concentration of defects increasing, there is a decreasing of band ga.p making the two types of SWCNTs change from a semiconductor to a metallic conductor.     

单壁碳纳米管拉伸变形的原子尺度模拟

采用分子动力学方法对单壁碳纳米管的拉伸变形行为进行了模拟,结果表明,碳纳米管具有较高的断裂应变.在结构产生缺陷之前,碳纳米管表现出弹性变形的特征.通过对能量变化的分析可以看出,能量分布的不均匀是导致结构失稳产生缺陷的主要因素.通过对含初始结构缺陷的碳纳米管在拉伸变形过程中的构型变化进行分析,发现在缺陷附近原来相邻的两个六边形蜂窝结构,随着拉伸变形的发展转变成5 7结构(Stone Wales转变),能量产生突变,应变能的释放使系统能量降低.分析也表明,较少数目的初始缺陷对碳纳米管的力学性质并不会有太大影响.     

Theoretical Studies on Interaction Between Methanol and Functionalized Single-Walled Carbon Nanotubes

We study the adsorption of a methanol molecule on single-walled carbon nanotubes (SWCNTs) with various diameters and chiral angles by using the density functional theory based calculations. We find that methanol prefers to be adsorbed physically on the exterior surface of chiral nanotubes in comparison to the armchair and zigzag tubes with binding energy of about-2.76 kcal/mol, which is consistent with recent experimental andtheoretical investigation results. We further consider the adsorption of methanol on the exterior surface and edge site of functionalized SWCNTs. The obtained results indicate that the binding energy of methanol is significantly increased for adsorption on the sidewall of functionalized nanotubes. It is also found that the adsorption of methanol at the edge site of both functionalizedand pristine SWCNT is remarkably different (chemisoption process) incomparison to the exterior sidewall of the tubes. Furthermore, the electronic structures and Mulliken charge population of the considered complexes at their ground state are discussed within the context.     

Hallmark of perfect graphene

Using first-principles calculations we show that the adsorption of atomic hydrogen on graphene opens a substantial gap in the electronic density of states in which lies a spin-polarized gap state. This spin is quenched by the presence of a rotated C-C bond (a Stone-Wales defect) adjacent to or distant from the H atom. We explain these findings and discuss the implications for nanotubes and magnetic nanographene. Furthermore, we demonstrate that the combined effect of high curvature and a Stone-Wales defect makes H2 chemisorption close to being thermodynamically favorable.     

Computational analysis of effect of modification on the interfacial characteristics of a carbon nanotube-polyethylene composite system

In this study, the non-covalent association of single-walled nanotube (SWNT) with polyethylene (PE) molecule and the influence of sidewall modification on the interfacial bonding between the SWNTs and polymer were investigated using molecular mechanics (MM) and molecular dynamics (MD) simulations. The model of interaction between the initially separated PE and SWNT fragments, which can be either wrapping or filling, was computed. The possible extension of polymers wrapping or filling SWNTs can be used to structurally bridge the SWNTs and polymers to significantly improve the load transfer between them when SWNTs are used to produce nanocomposites. The interfacial bonding characteristics between the single-walled nanotubes, on which -COOH, -CONH₂, -C₆H₁₁, or -C₆H₅ groups have been chemically attached, and the polymer matrix were also investigated by performing pullout simulations. The results show that appropriate functionalization of nanotubes at low densities of functionalized carbon atoms drastically increase their interfacial bonding and shear stress between the nanotubes and the polymer matrix, where chemisorption with -C₆H₅ groups to as little as 5.0% of the nanotube carbon atoms increases the shear stress by about 1700%. Furthermore, this suggests the possibility to use functionalized nanotubes to effectively reinforce other kinds of polymer-based materials as well.     

First principles study on magnetic and electronic properties with rare-earth atoms doped SWCNTs

The adsorptions of rare-earth (RE) atoms on (6, 0) and (8, 0) single-walled carbon nanotubes (SWCNTs) have been investigated by using the first-principles pseudopotential plane wave method within density functional theory (DFT). The binding energy, Mulliken charge, magnetic properties, band structure and DOS were calculated and analyzed. Most of RE atoms including Nd, Sm and Eu have a magnetic ground state with a significant magnetic moment. Some electrons transfer between RE-5d, 6s and C-2p orbitals. Owing to the curvature effect, the values of binding energy for RE atoms doped (6, 0) SWCNT are lower than those of the same atoms on (8, 0) SWCNT. The pictures of DOS show that hybridizations between RE-5d, 6s states and C-2p orbitals and between RE-4f and C-2p orbitals appear near the Fermi level. Results indicate that the properties of SWCNTs can be modified by the adsorptions of RE atoms.     

Effects of doping, Stone Wales and vacancy defects on thermal conductivity of single-wall carbon nanotubes

The thermal conductivity of carbon nanotubes with certain defects (doping, Stone-Wales, and vacancy) is investigated by using the non-equilibrium molecular dynamics method. The defective carbon nanotubes (CNTs) are compared with perfect tubes. The influences of type and concentration of the defect, length, diameter, and chirality of the tube, and the ambient temperature are taken into consideration. It is demonstrated that defects result in a dramatic reduction of thermal conductivity. Doping and Stone-Wales (SW) defects have greater effect on armchair tubes, while vacancy affects the zigzag ones more. Thermal conductivity of the nanotubes increases, reaches a peak, and then decreases with increasing temperature. The temperature at which the thermal conductivity peak occurs is dependent on the defect type. Different from SW or vacancy tubes, doped tubes are similar to the perfect ones with a sharp peak at the same temperature. Thermal conductivity goes up when the tube length grows or diameter declines. It seems that the length of thermal conductivity convergence for SW tubes is much shorter than perfect or vacancy ones. The SW or vacancy tubes are less sensitive to the diameter change, compared with perfect ones.     

Exploring the simultaneous existence of Stone-Wales and carbon ad-dimer defects in the zigzag single-walled carbon nanotubes

We have applied density functional calculations to investigate simultaneous existence of Stone–Wales (SW) and carbon ad-dimer (CD) defects in the zigzag (n, 0) n=5, 6, 7, 8, 9, and 10 SWCNTs, with an extensive search by considering two different orientations of defects. According to our results, the adsorption of a carbon dimer on a hexagonal ring of SWCNTs is easier than the rotation of a C–C bond trough the SW rearrangement. Moreover, the formation of a carbon dimer on the exterior sidewalls of an SW defective SWCNT or the rotation of a C–C bond of a CD defective SWCNT is more favorable than those on the perfect ones. Defect formation energy shows a strong dependence on the both SWCNT radius and defect orientation. The reactivity of SW–CD defective SWCNTs through chemisorption of hydrogen atoms on the central bonds of defect sites shows the thermodynamically lower preference of additions for the CD defective sites in comparison to SW defective sites. Histograms of the ¹³C NMR chemical shifts of SW–CD defective SWCNTs exhibit individual signals for defect sites, which can be attributed to azupyrene- and pentalelene-like structures for SW and CD defect sites, respectively.     

Selective growth, characterization, and field emission performance of single-walled and few-walled carbon nanotubes by plasma enhanced chemical vapor deposition

Single-walled carbon nanotubes (SWCNTs) and few-walled carbon nanotubes (FWCNTs) have been selectively synthesized by plasma enhanced chemical vapor deposition at a relative low temperature (550 °C) by tuning the thickness of iron catalyst. The parametric study and the optimization of the nanotube growth were undertaken by varying inductive power, temperature, catalyst thickness, and plasma to substrate distance. When an iron film of 3-5 nm represented the catalyst thickness for growing FWCNT arrays, SWCNTs were synthesized by decreasing the catalyst thickness to 1 nm. The nanotubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Electron field emission properties of the nanotubes indicate that the SWCNTs exhibit lower turn-on field compared to the FWCNTs, implying better field emission performance.     

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     

Quantum Chemical Study on the adsorption of metformin drug on the surface of pristine,Si- and Al-doped (5, 5) SWCNTs

Adsorption properties of metformin (MF) drug onto pristine, Si- and Al-doped (5, 5) armchair single-wall carbon nanotubes (SWCNTs) were studied using density functional theory (DFT) calculations at the B3LYP and ωB97XD methods with the standard 6–311 G** basis set. The most stable geometries of the MF drug molecule onto pristine, Si- and Al-doped (5, 5) CNTs were selected and evaluated in the gaseous and aqueous environments. We calculated the natural bond orbitals (NBO), Frontier molecular orbital (FMO), density of states (DOS) and molecular electrostatic potential (MEP) of systems upon adsorption of MF drug. It was found that the reaction of MF drug with pure SWCNT is physisorption in nature, while high chemisorption can be achieved by using Al- and Si-doped SWCNTs. Despite Al-doped SWCNT provides stronger adsorption, however the change in the energy gap of Si-doped SWCNT is more pronounced. It is predicted that MF drug incorporating Si-doped SWCNT can be extended as drug delivery system.     

碳纳米管负载矾的第一性原理研究

本文基于密度泛函第一性原理研究了原始和带有缺陷的(Stone-Wales缺陷和单空位缺陷)碳纳米管负载金属V的稳定构型.对于V吸附在原始碳纳米管(CNT)上时,V在内表面的吸附比外表面的吸附有更强的相互作用力,且六元环内表面结构最稳定.当V与Stone-Wales缺陷碳纳米管相互作用时,V原子易吸附在管外七元环C-C键的外表面和内表面处,这说明缺陷位置的有效结合使之局域化加强.而以单空位缺陷碳纳米管为载体时V最易吸附在外缺陷处,相当于碳纳米管的一个C被金属V原子取代,形成了3个V-C_(sur)键,这进一步表明SV管外吸附比管内吸附更容易.我们从上述三种构型载体中发现,金属V吸附在缺陷碳纳米管时的稳定性要优于原始碳纳米管,且SV缺陷对金属V的固定效果最好.     

直立在金膜表面的单壁碳纳米管的研究

用水溶胶体将单壁碳纳米管（ＳＷＣＮＴｓ）组装在晶态金膜表面,用扫描隧道显微镜（ＳＴＭ）研究了表面单壁碳纳米管直立于金膜表面,单根碳管的长度约在１０－１５ｎｍ之间。     

Differences in the catalyst removal from single- and double-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) and double-walled carbon nanotubes (DWCNTs) synthesized by a catalytic chemical vapor deposition method showed partially incorporated metal catalysts inside the graphene walls. In order to remove the metal catalysts, acid and thermal treatments were successively carried out. The methods for effective catalyst removal in SWCNTs and DWCNTs were examined by means of thermogravimetric analysis, electron microscopy, and electron paramagnetic resonance. The DWCNTs showed distinctly different metal catalyst removal behavior from that of SWCNTs due to the double-wall structure. The acid treatment is less efficient for catalyst removal from DWCNTs, while catalysts in SWCNTs are effectively removed by acid treatment. Additional thermal treatment is quite effective to remove metal catalysts from DWCNTs.     

Effect of heat-pretreatment of the graphite rod on the quality of SWCNTs by arc discharge

Single-walled carbon nanotubes (SWCNTs) have been synthesized in high yield by the dc arc discharge technique under heat-pretreatment of the graphite rod conditions. Before executing arc discharge, the graphite rods containing the catalysts were heat treated at 600, 700, 800 and 900 °C for 1–3 h, respectively. Effects of heat-pretreatment of the graphite rod on the quality of SWCNTs by arc discharge were investigated. The heat-treatment temperature and time were found to be crucial for a high yield of high-purity SWCNTs. Optimum parameter was found to be at the heat-treatment temperature of 800 °C for 2 h. The SWCNTs synthesized under the optimum condition have better field-emission characteristics. The turn-on field needed to produce a current density of 10 μA/cm² is found to be 1.9 V/μm and the threshold field where current density reaches 10 mA/cm² is 3.9 V/μm.     

Molecular dynamics of reactions between (4,0) zigzag carbon nanotube and hydrogen peroxide under extreme conditions

ABSTRACT

Single-wall carbon nanotubes (CNTs) have been suggested as potential materials for use in next-generation gas sensors. The sidewall functionalisation of CNTs facilitates gas molecule adsorption. In this study, density functional theory (DFT)-based ab initio molecular dynamics simulations are performed for a periodic zigzag single-wall (4,0) CNT surrounded by a monolayer of hydrogen peroxide molecules in an attempt to find conditions that favour sidewall functionalisation. The dependency of dynamics on charge states of the system is examined. It is found negative charges favour reactions that result in the functionalisation of the CNT. First principles molecular dynamics of defect formation yields chemically reasonable structure of stable defects, which can be reproduced in CNTs of any diameter and chirality. The explored hydroxyl and hydroperoxyl defects increase conductivity in a large diameter (10,0) CNT, while decrease conductivities in a small diameter (4,0) CNT.     

Adsorption of hydrogen on normal and pentaheptite single wall carbon nanotubes

Density functional calculations of the physisorption of molecular hydrogen and the dissociative atomic chemisorption on the external surface of hexagonal and pentaheptite carbon nanotubes, have been carried out. Physisorption binding energies are near 100 meV/molecule and are similar on metallic and semiconducting nanotubes. Full coverage of the nanotube with one molecule per graphitic hexagon decreases the binding energy per molecule. Chemisorption binding energies per H atom are larger on pentaheptites than on hexagonal carbon nanotubes. The molecular physisorption and dissociative chemisorption states on pentaheptites have very similar total energies (some chemisorbed states are even slightly more stable than the physisorbed states), while on hexagonal carbon nanotubes molecular physisorption is more stable than dissociative chemisorption. However, a substantial energy barrier has to be overcome to go from physisorption to dissociative chemisorption in both types of nanotubes.     

拓扑缺陷对单壁碳纳米管电子结构及其光学光谱的影响

应用密度泛函理论计算了半导体型单壁碳纳米管(7,0)和(8,0)以及其发生镜像对称和非镜像对称Stone-Wales形变、形成异质结(7,0)—(8,0)情况下的能带结构、吸收光谱、反射光谱,并对计算结果进行了比较。研究发现： 引入拓扑缺陷态后,碳纳米管的能带结构发生了明显的变化,费米能级在不同缺陷情况下移动方向不一致;碳管的吸收和反射明显减弱且吸收峰和反射峰在低能区发生红移现象;在光子能量约为E=13 eV处各碳管的吸收谱和反射谱中均出现一特征峰,并且在引入缺陷以后该特征峰向高能区移动。文章对计算结果进行了分析和探讨,可望利用这种拓扑缺陷的引入而产生的光电特性来设计碳管光电器件。     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule：ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes (SWCNTs) is investigated by density functional theory calculations. Adsorption energies and equilibrium distances are evaluated, and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared. We also investigated the role of the structural defects on the adsorption capability of the SWCNTs. We could observe larger adsorption energies for the larger diameters semiconducting CNTs, while the story is paradoxical for the metallic CNTs. The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles. Finally, the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon, hexagon, and heptagon sites in the tube surface. We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs. The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption. Consequently, one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule: ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes(SWCNTs)is investigated by density functional theory calculations.Adsorption energies and equilibrium distances are evaluated,and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared.We also investigated the role of the structural defects on the adsorption capability of the SWCNTs.We could observe larger adsorption energies for the larger diameters semiconducting CNTs,while the story is paradoxical for the metallic CNTs.The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles.Finally,the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon,hexagon,and heptagon sites in the tube surface.We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs.The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption.Consequently,one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.