Open-ended Nanotubes Research Articles

Fabrication of open-ended high aspect-ratio anodic TiO2 nanotube films for photocatalytic and photoelectrocatalytic applications

A facile process is introduced to flake high aspect-ratio anodic TiO(2) nanotube (TiNT) arrays off Ti substrates and then chemically remove the bottom caps to obtain open-ended TiNT films that exhibit high activity to photocatalytic degradation of methylene blue and efficient hydrogen production from photoelectrocatalytic water splitting.

The evolution of morphology of ordered porous TiO2 films fabricated from sol-gel method assisted ZnO nanorod template

Ordered porous TiO2 films, including TiO2 nanotube arrays, are fabricated by a sol-gel dip-coating approach via ZnO nanorod templates obtained from aqueous solution approach. The results indicate that the morphologies of ordered porous TiO2 films have been great affected by the sol-gel dip-coating cycle number. Open-ended TiO2 nanotube arrays can be obtained in optimum dip-coating cycle numbers. The TiO2 nanotubes with the inner diameter matching well with the diameters of ZnO nanorods, are well assembled and separate each other. When the cycle number is less than this optimum value, no intact porous TiO2 film can be obtained. As the cycle number is larger than this optimum value, an ordered porous TiO2 film with many throughout holes is formed. The evolutive mechanism of ordered porous TiO2 films is proposed.

Practical Modeling of Heterogeneous Bundles of Single-Walled Carbon Nanotubes for Adsorption Applications: Estimating the Fraction of Open-Ended Nanotubes in Samples

A practical approach for adsorption modeling of heterogeneity of single-walled carbon nanotube (SWNT) bundles has been developed. The method integrates experimental analysis with grand canonical Monte Carlo (GCMC) simulation of a small probe molecule, such as nitrogen at 77 K. Using this method, it is possible for one to separately estimate adsorption inside the nanotubes, adsorption on the external surface of the bundles, and adsorptive contributions from the impurities present in samples. By introducing a scaling parameter for adsorption in the internal porous volume of the bundles, the predicted adsorption isotherm results in a near replication of the experimental N2 adsorption isotherm. We refer to this parameter as the volume fraction of open-ended nanotubes. Our GCMC-assisted experimental characterization method has been applied successfully to several commercial samples obtained from different suppliers, such as MER Corp., Carbon Nanotechnologies Inc., Carbon Solutions Inc., Carbolex Inc., and Buck...

Controlled filling and external cleaning of multi-wall carbon nanotubes using a wet chemical method

A controlled, material-independent and adaptable cold wet chemical procedure is described. It allows organic and inorganic compounds to be confined inside multi-wall carbon nanotubes. The procedure mainly consists of a lyophilization process to fill multi-wall carbon nanotubes (MWCNTs), and a washing method to clean their outer surface without removing the encapsulated material. The technique was tested by synthesizing CdS crystals inside the nanotubes. Morphological and structural studies of the CdS crystals demonstrated a complete control of the synthesis process, and the possibility of maximizing the crystal size and the filling efficiency that approached 70% of open-ended nanotubes.

Effects of synthetic conditions on the structure and morphology of open-ended vanadium oxide nanotubes and study of their growth mechanism

Vanadium oxide nanotubes (VOx-NTs) have been synthesized by using n-butylamine as structure-directing template and V2O5 as precursor under hydrothermal conditions. XRD, FTIR, SEM, TEM, BET and TG-DTA characterizations have been performed to both optimize the synthetic conditions and understand the growth mechanism of VOx-NTs. The results showed that open-ended VOx-NTs were obtained under the optimized conditions (hydrothermal temperature: 150–160°C, hydrothermal time: 5–7 d, the molar ratio of V2O5 to n-butylamine is 1:1) with diameters ranging from about 30 to 100 nm and several micrometers in length. The BET surface area and the desorption cumulative pore volume of pores of the as-synthesized sample were about 27.4609 m2/g and 0.191087 cm3/g, respectively. The result presents that the synthesis of VOx-NTs is controlled by the “rolling” mechanism and temperature is primary driving force for rolling.

Structure and electronic properties of armchair boron nitride nanotubes

The structure and electronic properties of armchair boron nitride nanotubes have been investigated as a function of tube diameter using density functional theory. The length of each nanotube is kept constant. The structural parameters of the open end nanotube are studied. The variation in structural parameters is analyzed based on atomic charges of Mulliken and natural population analyses schemes. A topological analysis for charge density ( ρ), and its second derivative (∇ 2 ρ) for bonds have been performed using atoms in molecules (AIM) theory. Finally, the analysis of the charge distribution and charge transfer processes have been studied using the NBO partitioning scheme, which helps us to understand the interactions inside the boron nitride nanotubes which are responsible for the stabilization of the armchair boron nitride nanotubes.

Nonequilibrium molecular dynamics simulation to describe the rotation of rigid, low aspect ratio carbon nanotubes in simple shear flow

In this paper, the rotation of short carbon nanotubes in simple shear liquid argon flow was investigated by nonequilibrium molecular dynamics (MD) simulation. In their simulations, nanotubes were described as rigid cylinders of carbon atoms. Lennard-Jones potential was employed to represent both argon-argon and argon-carbon interactions. Results show that time period of a nanotube as calculated from MD simulations is longer than what would be calculated from Jeffery's equation based on the aspect ratio of the cylinder. The difference is much higher at low shear rates and for small aspect ratios. Results also reveal that adding caps to an open-ended nanotube speeds up its rotation.

Adsorption site analysis of impurity embedded single-walled carbon nanotube bundles

Bundle morphology and adsorptive contributions from nanotubes and impurities are studied both experimentally and by simulation using a computer-aided methodology, which employs a small physisorbed probe molecule to explore the porosity of nanotube samples. Grand canonical Monte Carlo simulation of nitrogen adsorption on localized sites of a bundle is carried out to predict adsorption in its accessible internal pore volume and on its external surface as a function of tube diameter. External adsorption is split into the contributions from the clean surface of the outermost nanotubes of the bundle and from the surface of the impurities. The site-specific isotherms are then combined into a global isotherm for a given sample using knowledge of its tube-diameter distribution obtained by Raman spectroscopy. The structural parameters of the sample, such as the fraction of open-ended nanotubes and the contributions from impurities and nanotube bundles to total external surface area, are determined by fitting the experimental nitrogen adsorption data to the simulated isotherm. The degree of closure between experimental and calculated adsorption isotherms for samples manufactured by two different methods, to provide different nanotube morphology and contamination level, further strengthens the validity and resulting interpretations based on the proposed approach. The average number of nanotubes per bundle and average bundle size, within a sample, are also quantified. The proposed method allows for extrapolation of adsorption properties to conditions where the purification process is 100% effective at removing all impurities and opening access to all intrabundle adsorption sites.

Theoretical and Experimental Investigation of Morphology and Temperature Effects on Adsorption of Organic Vapors in Single-Walled Carbon Nanotubes

Hexane adsorption on single-walled carbon nanotube (SWNT) bundles is studied by both simulation and experimentally using a previously developed computer-aided methodology, which employed a smaller physisorbed probe molecule, nitrogen, to explore the porosity of nanotube samples. Configurational-bias grand canonical Monte Carlo simulation of hexane adsorption on localized sites of the bundles is carried out to predict adsorption on their external surface and in their internal sites. These localized isotherms are then combined into a global isotherm for a given sample by using knowledge of its tube-diameter distribution and structural parameters, such as the fraction of open-ended nanotubes and the external surface area of bundles in samples, which have been independently determined from the standard nitrogen adsorption isotherm. The near-perfect replication of experimental isotherms demonstrates the validity of our method for structural characterization of SWNT samples. The effect of temperature on adsorption is also studied and the simulation results are extrapolated to predict the limiting hexane adsorption capacity of the samples. The similarity between the hexane adsorption isotherms and those of other organic molecules demonstrates that the adsorption mechanisms explored here are not specific to hexane, and that the proposed methodology can be potentially applicable to other sorbates with equal success.

Structural Preferences of Single‐Walled Silica Nanostructures: Nanospheres and Chemically Stable Nanotubes

Structural preferences of single-walled and coordinatively saturated spherical and tubular nanostructures of silica have been determined by ab initio calculations. Two families of spherical (SiO2)n clusters derived from Platonic solids and Archimedean polyhedra are depicted, with n ranging from 4-120. The analogue of a truncated icosidodecahedron, Ih-symmetric Si120O240, is favored in energy, closely followed by the Ih-symmetric Si60O120-truncated icosahedron. The silica nanotubes derived from spherical clusters are capped by Si2O2 rings, whereas the tubular section consists of single oxygen bridges. Periodic studies performed with open-ended silica nanotubes and the alpha-quartz polymorph of silica, along with a comparisons to fullerenes and carbon nanotubes, suggest that tubes with diameters of approximately 1 nm should be chemically stable.

Template‐Synthesized LiCoO2, LiMn2O4, and LiNi0.8Co0.2O2 Nanotubes as the Cathode Materials of Lithium Ion Batteries.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Aligned Arrays of Nanotubes and Segmented Nanotubes on Substrates Fabricated by Electrodeposition onto Nanorods

We describe an electrochemical-based approach to create vertically aligned nanotube arrays on substrates. Initially, nanoporous anodic alumina films are used as templates to electrodeposit nanorods, and then the alumina templates are removed and nanotube arrays are electrodeposited using the nanorod arrays as templates. We have used this approach to fabricate gold nanotube arrays using nickel nanorods as templates. By anodizing the ends of the nickel nanorods before gold electrodeposition, no deposition occurs at the ends of the rods, resulting in open-ended nanotubes. In addition, we have used layered nickel-gold nanorods as templates to create gold nanostructure arrays with alternating segments of filled and empty nanotubes. This approach is versatile and may be used to electrodeposit a wide range of nanotube materials with good control over the nanotube dimensions.

Electrochemical insertion of magnesium in open-ended vanadium oxide nanotubes

Vanadium oxide nanotubes were obtained as the main product in a sol–gel reaction followed by hydrothermal treatment from V 2O 5 precursors and octadecylamine. The tubes consist of concentric shells of highly crystalline vanadium oxide separated by alternation organic amine layers. The vanadium oxide nanotubes are redox-active and can electrochemically insert magnesium reversibly. The electrochemical insertion magnesium properties of vanadium oxide nanotubes were studied by electrochemical impedance (EIS) and cyclic voltammogram.

Self-consistent tight binding model adapted for hydrocarbon systems

A self-consistent environment-dependent tight binding method is presented that was developed to simulate eigenvalue spectra, electron densities and Coulomb potential distributions for hydrocarbon systems. The method builds on a non-self-consistent environment-dependent tight binding model for carbon [Tang et al., Phys. Rev. B 53, 979 (1996)] with parameters added to describe hydrocarbon bonds and to account for self-consistent charge transfer. A detailed description of the parameterization procedure is given. Case studies that examine electron emission-related properties of carbon nanotubes demonstrate the utility of the method. The results of these calculations indicate that field enhancement in the vicinity of a nanotube tip is higher for open-ended than for capped nanotubes. At the same time open-ended nanotubes exhibit a higher potential barrier in the tip region. This barrier deteriorates the coupling between conducting states in the nanotube and free electron states in vacuum, and may increase the field emission threshold.

Template-Synthesized LiCoO2, LiMn2O4, and LiNi0.8Co0.2O2 Nanotubes as the Cathode Materials of Lithium Ion Batteries

The first point of this work is to synthesize LiCoO2, LiNi0.8 Co0.2 O2, and LiMn2O4 nanotubes with the template of porous anodic aluminum oxide by thermal decomposition of sol-gel precursors. The as-synthesized materials were open-ended nanotubes with uniform shape and size based on the analysis of scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. An "in situ reaction from nanoparticle to nanotube" mechanism was discussed for the formation process of the nanotubes. The second point of this paper is to investigate the electrochemical properties of the as-synthesized nanotubes for the cathode materials of lithium ion batteries. It was found that the nanotube electrodes exhibited better reversibility and higher discharge capacities than that of their nanocrystalline counterparts. The reason for the improved electrochemical performance of the nanotube electrodes was also interpreted.

Argon adsorption in open-ended single-wall carbon nanotubes

Thermodynamic and neutron-diffraction measurements combined with molecular dynamics simulation are used to determine the adsorption energies and the structure of argon condensed in the various adsorption sites of purified open-ended single-wall nanotube bundles. On the basis of these experiments and the simulation results, a consistent adsorption scenario has been derived. The adsorption proceeds first by the population of the walls inside the open nanotubes and the formation of one-dimensional Ar chains in the grooves at the outer surface of the bundles, followed by the filling of the remaining axial sites inside the nanotubes and the completion of a quasihexagonal monolayer on the outer surface of the bundle. The measurements also provide an estimate of the relative abundance of the various adsorption sites revealing that a major part of the adsorbed Ar is stored inside the open-ended nanotubes. Nanotube bundles generally show a certain degree of heterogeneity and some interstitial sites should be populated over a range of Ar chemical potential. However, for the sample used here, diffraction data and simulations suggest that heterogeneity is not a key feature of the bundles and there is little direct evidence of interstitial sites being populated.

Mg intercalation properties into open-ended vanadium oxide nanotubes

Vanadium oxide nanotubes (VO x -NTs) were obtained as the main product in a sol–gel reaction followed by hydrothermal treatment from V 2O 5 precursors and primary amines. The material has a considerable large distance between the layers (ca. 3.5 nm), a wide inner (15–40 nm) and outer diameter (60–100 nm), and the open tube ends which are favorable for the magnesium ion insertion. VO x -NTs are a new kind of material with a unique nanostructured morphology, which can electrochemically insert/deinsert magnesium ions reversibly from the cyclic voltammogram. AC impedance (EIS) demonstrated that Mg 2+ diffusion into the nanotubes is faster than polycrystalline V 2O 5 during intercalation Mg 2+ into the cathodes. X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) results gave the mechanism of Mg 2+ insertion into the nanotubes, however, the specific capacity of the rechargeable magnesium is lower than that of lithium.

Structural Characterization of Single-Walled Carbon Nanotube Bundles by Experiment and Molecular Simulation

A procedure, combining molecular simulation, Raman spectroscopy, and standard nitrogen adsorption, is developed for structural characterization of single-walled carbon nanotube (SWNT) samples. Grand canonical Monte Carlo simulations of nitrogen adsorption are performed on the external and internal adsorption sites of homogeneous arrays of SWNTs of diameters previously determined by Raman spectroscopy of the sample. The results show the importance of the peripheral grooves of a nanotube bundle at low relative pressure and the insensitivity of nanotube diameter toward adsorption on the external surface of the bundle at higher pressures. Simulations also reveal that samples containing thin nanotubes have less internal adsorption capacity that saturates at lower pressure than those comprising large diameter nanotubes. The fraction of open-ended nanotubes in a sample can be estimated by scaling the simulated internal adsorption inside nanotubes to obtain a near perfect fit between simulated and experimental isotherms. This procedure allows extrapolation of adsorption properties to conditions in which all nanotubes in the sample are open-ended.

Electroless deposition of open-end Cu nanotube arrays

Cu nanotube arrays were fabricated by electroless deposition using porous anodic aluminium oxide membranes as templates. This was accomplished by a four-step procedure, i.e. pore-wall modification, polishing treatment, sensitization–activation and electroless deposition. The as-synthesized Cu nanotubes possess controllable inner diameter and open ends.

Energetics of finite, clean and hydrogenated silicon nanotubes

Abstract The energetics and relative stability of infinite and finite, clean and hydrogenated open-ended Si nanotubes is investigated using the extended Brenner potential. The calculations show that the excess strain energy of infinite clean Si tubes is reduced when the tubes are hydrogenated on both sides of the tubular shell. For finite Si tubes the total energy exhibits a minimum which reflects a balance between the strain energy of the shell and the chemical energy of the open ends. If hydrogen atoms are chemisorbed on the outer surface of finite Si nanotubes, the tubes show a tendency to close their open ends. For very short, large-diameter tubes, topologically different structures are formed––hydrogenated silicon tori.