Calculation of the energy of binding of titanium and scandium complexes to the surface of carbon nanotubes

Complexes of zigzag-type carbon nanotubes (CNTs) with transition metal atoms, scandium and titanium, were studied. It was demonstrated that the energy of binding of both atoms with a carbon surface decreases whereas the rate of diffusion along the surface increases with increasing nanotube diameter. The rate constant of migration of scandium atoms over a CNT surface are several orders of magnitude higher than that for titanium atoms, because the CNT surface—Sc atom binding energy is substantially lower.     

Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.     

Sidewall fluorination and hydrogenation of single-walled carbon nanotubes: a density functional theory study

The fluorination and hydrogenation reactions on (6, 6) and (10, 0) single-walled carbon nanotubes (SWCNTs) have been examined via computing the reaction energy for the chemisorption. The examined nanotubes have comparable lengths and diameters, with or without Stone-Wales defects on the sidewall. The two fluorine or hydrogen atoms are anchored to the external walls of the SWCNTs. The computed chemisorption energies of these virtual reactions reveal that the fluorination and hydrogenation of the nanotubes are moderately sensitive to the nanotube chirality and the sidewall topology, and the (10, 0) SWCNT with Stone-Wales defect can be easily fluorinated and hydrogenated.      

Experimental investigation and ab initio calculation of the properties of Sc-, in-doped bismuth titanates with the pyrochlore type structure

Using ab initio calculations, the data have been obtained on the structural, electronic, and optical properties of bismuth titanates with the pyrochlore type structure and compounds with the substitution of scandium or indium atoms for bismuth and titanium atoms. The results of the theoretical calculations agree with the experimentally obtained structural and optical characteristics of the synthesized compounds doped with scandium or indium. It has been shown that the substitution of scandium or indium atoms for bismuth atoms in the pyrochlore structure is energetically favorable. The energies corresponding to the direct and indirect electronic transitions in scandium- and indium-doped bismuth titanates have been determined based on the optical spectroscopy data obtained for the studied samples. These energies are in agreement with the theoretically calculated values.     

Oxidation of carbon nanotubes by singlet O2

Chemisorption of singlet (1)Delta(g) O2 on single-walled carbon nanotubes is reexamined by first principles calculations, and the reaction barrier is substantially lower than previously reported when the spin on O2 is correctly treated. The process is initiated by the cycloaddition of a singlet O2 on top of a C-C bond and ended with an epoxy structure with each of the two oxygen atoms occupying a bridge position. The overall process is exothermic, with an activation barrier as low as 0.61 eV for the (8, 0) tube. Our results raise the possibility that carbon nanotubes with small diameters could be degraded after exposure to air and sunlight, similar to the degradation of natural rubber and synthetic plastics.     

Optimization of the calculations of the electronic structure of carbon nanotubes

A method is proposed for calculating the electronic structure and physical properties (in particular, Young’s modulus) of nanotubes, including single-walled carbon nanotubes. This method explicitly accounts for the periodic boundary conditions for the geometric structure of nanotubes and makes it possible to decrease considerably (by a factor of 10–10³) the time needed to calculate the electronic structure with minimum error. In essence, the proposed method consists in changing the geometry of the structure by partitioning nanotubes into sectors with the introduction of the appropriate boundary conditions. As a result, it becomes possible to reduce substantially the size of the unit cell of the nanotube in two dimensions, so that the number of atoms in a new unit cell of the modified nanotube is smaller than the number of atoms in the initial unit cell by a factor equal to an integral number. A decrease in the unit cell size and the corresponding decrease in the number of atoms provide a means for drastically reducing the computational time, which, in turn, substantially decreases with an increase in the degree of partition, especially for nanotubes with large diameters. The results of the calculations performed for carbon and non-carbon (boron nitride) nanotubes demonstrate that the electronic structures, densities of states, and Young’s moduli determined within the proposed approach differ insignificantly from those obtained by conventional computational methods.     

Fabrication and photochromic study of titanate nanotubes loaded with silver nanoparticles

Pure anatase-TiO₂ and/or titanate nanotubes, photochromic Ag loaded titanium dioxide nanotubes (TNTs) and AgCl loaded titanate nanotubes were synthesized by hydrothermal method. The pH value during the neutralization process plays a crucial role in controlling the morphology and composition of the nanotubes. All these nanotubes were confirmed by XRD, TEM, EDS and XPS analysis. Most of them have open ends with inner/outer diameters of 7/10 nm and several hundred nanometers in length. For photochromic behavior in the case of AgCl-titanate nanotubes, the red color can be clearly observed after irradiation by red light, while the yellow, green, blue ones displayed pale black after the corresponding irradiation. On the other hand, Ag loaded TNT sample exhibited multicolor photochromism corresponding to that of incident light. The photoreduction of silver halide to Ag particle in the case of loaded AgCl particles and a particle-plasmon-assisted electron transfer from Ag nanoparticles to TiO₂ in the case of loaded Ag particles are considered to be responsible for this different behavior.     

Characterization and field emission characteristics of carbon nanotubes modified by titanium carbide

Carbon nanotubes (CNTs) were modified by depositing a thin layer of titanium film on the surface using magnetron sputtering method, followed by vacuum annealing at 900 °C for 2 h. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed that the as-deposited thin titanium film reacted with carbon atoms to form titanium carbide after annealing. The experiment results show that the thickness of sputter-deposited titanium film has significant effect on the field emission J-E characteristic of modified CNTs film. The titanium carbide-modified CNTs film obtained by controlling the titanium sputtering time to 2 min showed an improved field emission characteristics with a significant reduction in the turn-on electric field and an obvious increase in the emission current density as well as an improvement in emission stability. The improvement of field emission characteristics achieved is attributed to the low work function and good resistance to ion bombardment of titanium carbide.     

扶手椅型碳化硅纳米管电子结构和光学性质的研究

本文基于密度泛函理论研究了扶手椅型碳化硅纳米管(SiCNT)的电子结构、成键机制以及其光学性质。研究结果表明:当碳和硅的原子比为1∶1时,SiCNT的结构最为稳定,并且表现出诸多的优良性质。通过分析计算结果我们发现,SiCNT是间接带隙材料,并且管子的带隙随着直径的增加而增加。从SiCNT的轨道图谱中我们看到碳和硅原子之间属于sp2杂化,同时硅原子周围的电子密度明显要低于碳原子周围的电子密度。对能态密度的计算我们得知碳原子和硅原子分别主导价带和导带。与其它纳米管(BN)有所不同,SiCNT的光学性质更接近于各向同性材料。     

Functionalization of (<Emphasis Type="Italic">n</Emphasis>, 0) CNTs (<Emphasis Type="Italic">n</Emphasis> = 3–16) by uracil: DFT studies

Density functional theory (DFT) calculations were performed to investigate stabilities and properties for uracil (U)-functionalized carbon nanotubes (CNTs). To this aim, the optimized molecular properties were evaluated for (n, 0) models of CNTs (n = 3–16) in the original and U-functionalized forms. The results indicated that the dipole moments and energy gaps were independent of tubular diameters whereas the binding energies showed that the U-functionalization could be better achieved for n = 8–11 curvatures of (n, 0) CNTs. Further studies based on the evaluated atomic-scale properties, including quadrupole coupling constants (C _Q ), indicated that the electronic properties of atoms could detect the effects of diameters variations of (n, 0) CNTs, in which the effects were very much significant for the atoms around the U-functionalization regions. Finally, the achieved results of singular U, original CNTs, and CNT-U hybrids were compared to each other to demonstrate the stabilities and properties for the U-functionalized (n, 0) CNTs.     

Adsorption on the carbon nanotubes

Adsorption on single walled carbon nanotubes (SWCNTs) is a subject of growing experimental and theoretical interest. The possible adsorbed patterns of atoms and molecules on the single-walled carbon nanotubes vary with the diameters and chirality of the tubes due to the confinement. The curvature of the carbon nanotube surface enlarges the distance of the adsorbate atoms and thus enhances the stability of high coverage structures of adsorbate. There exist two novel high-coverage stable structures of potassium adsorbed on SWCNTs, which are not stable on graphite. The electronic properties of SWCNTs can be modified by adsorbate atoms and metal-semiconductor and semiconductor-semi-conductor transitions can be achieved by the doping of alkali atoms.     

The effect of anodising time on the electrochemical behaviour of the Ti/TiO<Subscript>2</Subscript> NTs/IrO<Subscript>2</Subscript>-RuO<Subscript>2</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> anode

Nowadays, mixed metal oxide (MMO) anodes are a superior alternative to lead alloys in electrowinning processes. Passivation of titanium substrate is the most common mechanism of deactivation in these anodes. In this research, titanium oxide nanotubes have been utilised as an interlayer between the substrate and a mixed metal oxide coating in order to improve the anode electrochemical behaviour and life via retardation of titanium passivation. Anodising of the substrate was done in 0.5 wt% hydrofluoric acid for 30, 60 and 240 min. The samples were subsequently coated with a coating composed of IrO₂-RuO₂-Ta₂O₅. The microstructure of different samples was observed by scanning with an electron microscope, and the electrochemical behaviour of the samples was studied by accelerated life test, cyclic voltammetry and electrochemical impedance spectroscopy. The studies showed that formation of titanium oxide nanotubes with anodising times of 60 and 240 min increases the life of the anode through the provision of a compact coating. The life of the anode which was anodised for 240 min lasted about 20% longer than the sample which had a substrate without any anodised layer.     

用微米级LaNi5为催化剂生长的碳管的ESR谱研究

用微米级LaNi₅合金粉末为催化剂, 以乙炔为原料, 采用化学气相沉积(CVD)法合成了多壁碳纳米管. 在100~290 K温度下测量了41 μm≤d≤150 μm粒径催化剂制备的不同直径分布的碳纳米管的电子自旋共振（ESR）谱,研究了测量温度、微米级催化剂粒径及制备过程的氢气氛对生成的碳纳米管的ESR谱线型、g因子、线宽的影响. 发现碳纳米管的g因子随其直径的增大而增大,分别为2.040 0（催化剂粒径41 μm≤d≤50 μm, 碳纳米管的直径分布为10 nm到20 nm）和2.089 8（催化剂粒径100 μm≤d≤150 μm,碳纳米管的直径分布为70 nm到120 nm）. 发现小管径纳米管的ESR谱图有一个峰, 而大管径纳米管的ESR谱图有两个峰A和B, 且随测量温度的升高, 峰B强度增大.     

Effects of catalysts on the internal structures of carbon nanotubes and corresponding electron field-emission properties

Using a chemical vapor deposition (CVD) method, multi-walled carbon nanotubes with uniform diameters of approximately 10 nm were synthesized on silicon substrates by the decomposition of acetylene using Fe, Co and Ni as the catalysts. Catalyst effects on the internal structures of the carbon nanotubes were evident in the Fe, Co and Ni catalyzed nanotubes. Although these nanotubes demonstrated similar morphologies, due to the variety of internal structures, the nanotubes synthesized from different catalysts demonstrated various electron field-emission characteristics including turn-on field, threshold field and field enhancement factor. Compared with carbon nanotubes from Ni catalyst, nanotubes from Fe and Co with the same diameters have better field-emission properties. Graphite layers in nanotubes from Fe and Co are much straighter and more parallel to the tube axis with fewer defects. For instance, the turn-on field and threshold field for nanotubes from Ni are 5 V/m and 9 V/m, respectively. These electric fields are much higher than those for nanotubes from Fe, which are 0.35 V/m and 2.8 V/m, respectively. This could be due to the effect of catalysts on the work function of nanotubes, since the catalyst particle usually terminates the free end of the nanotube, and the influence of internal structure on electron transportation along the nanotube axis. Therefore, this study suggests that besides a small diameter, good graphitization (crystallization) is an important prerequisite for a good carbon nanotube emitter. PACS 79.70.+q; 68.37.Lp; 81.07.De     

Formation of titanium carbide coating with micro-porous structure

Micro-porous titanium carbide coating was successfully synthesized in a vacuum gas carburizing furnace by using a sequential diffusion technology. The composition and structure of the as-synthesized TiC were examined by X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and glow discharge mass spectrometry (GDMS), and scanning electron microscopy (SEM). All of the XRD, XPS and GDMS analysis results indicate that carbon atoms effectively diffused into the titanium alloys and formed a uniform acicular TiC coating with micro-porous structure.     

Imaging as-grown single-walled carbon nanotubes originated from isolated catalytic nanoparticles

Discrete catalytic nanoparticles with diameters in the range of 1–3 nm are obtained by placing controllable numbers of metal atoms into the cores of apoferritin. With nanoparticles placed on transmission electron microscope (TEM) grids coated with ultra-thin alumina membranes, isolated single-walled carbon nanotubes are grown by chemical vapor deposition and directly examined by TEM. The characterizations, carried out at single-tube and single-particle level, obtain clear evidence that the diameters of the nanotubes are determined by the diameters of catalytic nanoparticles. For the first time, both ends of an as-grown single-walled nanotube are imaged by TEM, leading to a microscopic picture of the nanotube-growth mechanism. Received: 19 September 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

First-principles study of nanotubes within the tetragonal,hexagonal and dodecagonal cycle structures

A systematic study has been done on the structural and electronic properties of carbon, boron nitride and aluminum nitride nanotubes with structure consisting of periodically distributed tetragonal (T ≡A₂X₂), hexagonal (H ≡A₃X₃) and dodecagonal (D ≡A₆X₆) (AX=C₂, BN, AlN) cycles. The method has been performed using first-principles calculations based on density functional theory (DFT). The optimized lattice parameters, density of state (DOS) curves and band structure of THD-NTs are obtained for (3, 0) and (0, 2) types. Our calculation results indicate that carbon nanotubes of these types (THD-CNTs) behave as a metallic, but the boron nitride nanotubes (THD-BNNTs) (with a band gap of around 4 eV) as well as aluminum nitride nanotubes (THD-AlNNTs) (with a band gap of around 2.6 eV) behave as an semiconductor. The inequality in number of atoms in different directions is affected on structures and diameters of nanotubes and their walls curvature.     

Effect of carbon addition on synthesis of BN nanolayers encapsulating Fe fine particles and BN nanotubes

Boron nitride (BN) nanolayers encapsulating iron (Fe) fine particles and BN nanotubes were synthesized by annealing mixture powders of hematite, boron and carbon (C) at 1473 K for 2 h in a nitrogen atmosphere. The particles exhibited good soft magnetic properties. The thickness of BN nanolayers increased in the range of 10-100 nm with increasing C content in the mixture powders, which results in providing improvement of oxidation resistance of the particles. In the BN layers, no C was detected. BN nanotubes with diameters of ∼100 nm were also synthesized, and they had cup-stacked and bamboo-like structures.     

Hot filament CVD of Fe-Cr catalyst for thermal CVD carbon nanotube growth from liquid petroleum gas

A hot filament chemical vapor deposition (HFCVD) method was used to prepare Fe-Cr thin film on Si substrate. The produced layers were used as catalysts for growing carbon nanotubes (CNTs) from liquid petroleum gas (LPG) at 825 °C by thermal CVD (TCVD) method. To characterize the obtained catalysts or CNTs, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Raman spectroscopy were used. CNTs were grown on HFCVD derived Fe-Cr catalyst with the LPG as carbon source successfully. It was found that an annealing process on catalysts enhances the surface concentration of Cr atoms and reduces the sizes of catalyst particles. The grown CNTs on annealed sample were morphologically denser with smaller diameters compared to the as deposited one. In addition, the effect of filament temperature on CNTs was investigated. By increasing the filament temperature from 850 to 1050 °C the surface density and diameters of CNTs were improved.     

与富勒烯C_(36)直径(0.5nm)相等的碳纳米管及其制备

在电弧放电方法制备碳纳米管中 ,通过用碳纳米管填充阳极进行放电实验 ,成功地得到了小直径单层碳纳米管 .同时在多层管的最内层得到了直径 0 5nm的碳纳米管 .这个结果表明直径小于C60 (直径 0 7nm)的碳纳米管是存在的 .