Hydrogen adsorption in defected carbon nanotubes

Recently there has been lot of interest in the development of hydrogen storage in various systems for the large-scale application of fuel cells, mobiles and for automotive uses. Hectic materials research is going on throughout the world with various adsorption mechanisms to increase the storage capacity. It was observed that physisorption proves to be an effective way for this purpose. Some of the materials in this race include graphite, zeolite, carbon fibers and nanotubes. Among all these, the versatile material carbon nanotube (CNT) has a number of favorable points like porous nature, high surface area, hollowness, high stability and light weight, which facilitate the hydrogen adsorption in both outer and inner portions. In this work we have considered armchair (5,5), zig zag (10,0) and chiral tubes (8,2) and (6,4) with and without structural defects to study the physisorption of hydrogen on the surface of carbon nanotubes using DFT calculations. For two different H₂ configurations, adsorption binding energies are estimated both for defect free and defected carbon nanotubes. We could observe larger adsorption energies for the configuration in which the hydrogen molecular axis perpendicular to the hexagonal carbon ring than for parallel to C–C bond configuration corresponding to the defect free nanotubes. For defected tubes the adsorption energies are calculated for various configurations such as molecular axis perpendicular to a defect site octagon and parallel to C–C bond of octagon and another case where the axis perpendicular to hexagon in defected tube. The adsorption binding energy values are compared with defect free case. The results are discussed in detail for hydrogen storage applications.     

Designing carbon nanotube membranes for efficient water desalination

The transport of water and ions through membranes formed from carbon nanotubes ranging in diameter from 6 to 11 A is studied using molecular dynamics simulations under hydrostatic pressure and equilibrium conditions. Membranes incorporating carbon nanotubes are found to be promising candidates for water desalination using reverse osmosis, and the size and uniformity of tubes that is required to achieve a desired salt rejection is determined. By calculating the potential of mean force for ion and water translocation, we show that ions face a large energy barrier and will not pass through the narrower tubes studied ((5,5) and (6,6) "armchair" type tubes) but can pass through the wider (7,7) and (8,8) nanotubes. Water, however, faces no such impediment due to the formation of stable hydrogen bonds and crosses all of the tubes studied at very large rates. By measuring this conduction rate under a hydrostatic pressure difference, we show that membranes incorporating carbon nanotubes can, in principle, achieve a high degree of desalination at flow rates far in excess of existing membranes.     

受限于不同螺旋性的纳米碳管中水的分子动力学模拟

近年来将纳米碱米碳管引入到与生命过程息息相关的离子通道膜的研究逐渐成 为热点，而其中的关键就是要了解受限于膜孔道（碳管）中水分子的行为。采用分 子动力学模拟在300 K和1.01 * 10~5 Pa下对受限于（6，6）armchair型和（10， 0）zigzag型纳米碳管中的水进行了研究，得到了水分子在碳管中的局部密度分布 等静态性质以及水分子在碳管中的传递等动态性质，并对不同势能模型的模拟结果 作了比较。结果表明选择不同的势能模型并没有改变此体系的固有性质，即水分子 不仅能够进入到憎水性的（6，6）碳管中而且能形成一条稳定的由氢键相连的纵列 （single file），而且在管中以纵列的形式进行同歇传递。此外，碳管螺旋性对 受限水的静态性质影响不大但对动态性质则有一定程度的影响，水分子在（10，0 ）zigzag型碳管中的传递能力要强于在（6，6）armchair型碳管中的能力。     

Dispersions, novel nanomaterial sensors and nanoconjugates based on carbon nanotubes

Nanomaterials are structures with dimensions characteristically much below 100 nm. The unique physical properties (e.g., conductivity, reactivity) have placed these nanomaterials in the forefront of emerging technologies. Significant enhancement of optical, mechanical, electrical, structural, and magnetic properties are commonly found through the use of novel nanomaterials. One of the most exciting classes of nanomaterials is represented by the carbon nanotubes. Carbon nanotubes, including single-wall carbon nanotubes, multi-wall carbon nanotubes, and concentric tubes have been shown to possess superior electronic, thermal, and mechanical properties to be attractive for a wide range of potential applications They sometimes bunch to form “ropes” and show great potential for use as highly sensitive electronic (bio)sensors due to the very small diameter, directly comparable to the size of single analyte molecules and that every single carbon atom is in direct contact with the environment, allowing optimal interaction with nearby molecules. Composite materials based on integration of carbon nanotubes and some other materials to possess properties of the individual components with a synergistic effect have gained growing interest. Materials for such purposes include conducting polymers, redox mediators and metal nanoparticles. These tubes provide the necessary building blocks for electronic circuits and afford new opportunities for chip miniaturization, which can dramatically improve the scaling prospects for the semiconductor technologies and the fabrication of devices, including field-effect transistors and sensors. Carbon nanotubes are one of the ideal materials for the preparation of nanoelectronic devices and nanosensors due to the unique electrical properties, outstanding electrocatalytic properties, high chemical stability and larger specific surface area of nanotubes. Carbon nanotubes are attractive material for supercapacitors due to their unique one-dimensional mesoporous structure, high specific surface area, low resistivity and good chemical stability. Nanoscaled composite materials based on carbon nanotubes have been broadly used due to their high chemical inertness, non-swelling effect, high purity and rigidity. The integration of carbon nanotubes with organics, biomaterials and metal nanoparticles has led to the development of new hybrid materials and sensors. Hybrid nanoscale materials are well established in various processes such as organic and inorganic compounds, nucleic acid detachment, protein separation, and immobilization of enzymes. Those nanostructures can be used as the building blocks for electronics and nanodevices because uniform organic and metal coatings with the small and monodisperse domain sizes are crucial to optimize nanoparticle conductivity and to detect changes in conductivity and absorption induced by analyte adsorption on these surfaces. The highly ordered assembly of zero-dimensional and one-dimensional nanoparticles is not only necessary for making functional devices, but also presents an opportunity to develop novel collective properties.     

Heterostructured magnetic nanotubes

Heterostructured magnetic tubes with submicrometer dimensions were assembled by the layer-by-layer deposition of polyelectrolytes and nanoparticles in the pores of track-etched polycarbonate membranes. Multilayers composed of poly(allylamine hydrochloride) and poly(styrene sulfonate) assembled at high pH (pH > 9.0) were first assembled into the pores of track-etched polycarbonate membranes, and then multilayers of magnetite (Fe3O4) nanoparticles and PAH were deposited. Transmission electron microscopy (TEM) confirmed the formation of multilayer nanotubes with an inner shell of magnetite nanoparticles. These tubes exhibited superparamagnetic characteristics at room temperature (300 K) as determined by a SQUID magnetometer. The surface of the magnetic nanotubes could be further functionalized by adsorbing poly(ethylene oxide)-b-poly(methacrylic acid) block copolymers. The separation and release behavior of low molecular weight anionic molecules (i.e., ibuprofen, rose bengal, and acid red 8) by/from the multilayer nanotubes were studied because these tubes could potentially be used as separation or targeted delivery vehicles. The magnetic tubes could be successfully used to separate (or remove) a high concentration of dye molecules (i.e., rose bengal) from solution by activating the nanotubes in acidic solution. The release of the anionic molecules in physiologically relevant buffer solution showed that whereas bulky molecules (e.g., rose bengal) release slowly, small molecules (i.e., ibuprofen) release rapidly from the multilayers. The combination of the template method and layer-by-layer deposition of polyelectrolytes and nanoparticles provides a versatile means to create functional nanotubes with heterostructures that can be used for separation as well as targeted delivery.     

Effect of ozonolysis on the pore structure, surface chemistry, and bundling of single-walled carbon nanotubes

An ozonolysis protocol has recently been developed that cannot only purify nanotubes but also achieve rational spatial and molecular control over chemical derivatization in single-walled carbon nanotubes (SWCNTs). Ozonolysis likely opens end caps and introduces holes into the sidewalls of tubes, which may occur through an oxidation of carbon atoms located on the nanotube surface, resulting in the formation of oxygen-containing functional groups. Overall, it was demonstrated by analysis of nitrogen adsorption and TGA/DTG that the total surface area, micropore volume, and mesopore volume of SWCNTs depend on several, intertwined factors including the degree of purity, surface functionality, density of surface groups, as well as the state of aggregation of the carbon tubes. Hydrogen bonding in these systems plays a role too. Data suggest that complete removal of surface functionalities would lead to a greater total surface area and higher micropore volume.     

Effect of the initial state of carbon nanotubes on their ability to be dispersed in polar solvents upon liquid-phase oxidative treatments

Effect of the structural defectiveness of carbon nanotubes on the influence exerted on these nanotubes by their liquid-phase treatments with oxidizing agents (hydrogen peroxide, concentrated nitric acid, and its mixture with sulfuric acid) was studied. It was found that this factor affects changes in the structure of oxidized carbon nanotubes, their hydrophilicity, high-quality arrays of these tubes, and their ability to form stable dispersions in water, ethanol, isopropanol, and acetone.     

表面定向磁性印迹聚合物的制备及对槲皮素的选择性识别

利用硼酸功能化的磁性碳纳米管作为反应基质, 采用一种简便、 绿色的硼酸亲和表面定向印迹法制备了槲皮素磁性分子印迹聚合物, 并将其应用于银杏叶提取物中槲皮素的特异性识别. 透射电子显微镜、 X射线光电子能谱仪、 X射线衍射及振动样品磁强计测试结果表明, 制备的分子印迹聚合物具有良好的形貌和晶型结构. 吸附实验结果表明, 该分子印迹聚合物对模板分子槲皮素具有较好的吸附容量(4.57 μg/mg)、 良好的印迹效果(IF=8.44)和再生能力. 对实际中药样品银杏叶提取物的吸附实验结果表明, 所建立的方法能达到预期的槲皮素检测效果, 可作为中药有效成分槲皮素的特异性识别工具.     

Aspect ratio effects of multi‐walled carbon nanotubes on electrical,mechanical, and thermal properties of polycarbonate/MWCNT composites

Two multi‐walled carbon nanotubes (MWCNTs) having relatively high aspect ratios of 313 and 474 with approximately the same diameter were melt mixed with polycarbonate (PC) in a twin‐screw conical micro compounder. The effects of aspect ratio on the electrical, mechanical, and thermal properties of the PC/MWCNT composites were investigated. Electrical conductivities and storage moduli of the filled samples are found to be independent of the starting aspect ratio for these high aspect ratio tubes; although the conductivities and storage moduli are still significantly higher than values of composites made with nanotubes having more commercially common aspect ratios of ～100. Transmission electron microscopy results suggest that melt‐mixing reduces these longer nanotubes to the same length, but still approximately two times longer than the length of commercially common aspect ratio tubes after melt‐mixing. Molecular weight measurements show that during melt‐mixing the longer nanotubes significantly degrade the molecular weight of the polymer as compared to very similar nanotubes with aspect ratio ～100. Because of the molecular weight reduction glass transition temperatures predictably show a large decrease with increasing nanotube concentration. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 73–83     

Long synthetic nanotubes from calix[4]arenes

We report the synthesis and encapsulation properties of long (up to 5 nm) molecular nanotubes 1-4, which are based on calix[4]arenes and can be filled with multiple nitrosonium (NO(+)) ions upon reaction with NO(2)/N(2)O(4) gases. These are among the largest nanoscale molecular containers prepared to date and can entrap up to five guests. The structure and properties of tubular complexes 1(NO(+))(2)-4(NO(+))(5) were studied by UV/Vis, FTIR, and (1)H NMR spectroscopy in solution, and also by molecular modeling. Entrapment of NO(+) in 1(NO(+))(2)-4(NO(+))(5) is reversible, and addition of [18]crown-6 quickly recovers starting tubes 1-4. The FTIR and titration data revealed enhanced binding of NO(+) in longer tubes, which may be due to cooperativity. The described nanotubes may serve as materials for storing and converting NO(x) and also offer a promise to further develop supramolecular chemistry of molecular containers. These findings also open wider perspectives towards applications of synthetic nanotubes as alternatives to carbon nanotubes.     

Surface chemistry and structure of purified, ozonized, multiwalled carbon nanotubes probed by NEXAFS and vibrational spectroscopies.

Understanding of oxidative processes such as solution-phase ozonolysis in multiwalled carbon nanotubes (MWNTs) is of fundamental importance in devising applications of these tubes as components in composite materials, as well as for development of cutting and filling protocols. We present here an evaluation of various spectroscopic tools to study the structure and composition of functionalized nanotubes. We demonstrate near-edge X-ray absorption fine structure (NEXAFS) spectroscopy as a particularly useful and effective technique for studying the surface chemistry of carbon nanotubes.     

Theoretical study on the electronic structure nature of single and double walled carbon nanotubes and its role on the electron transport

Density functional theory and molecular dynamics (MD) calculations were used to evaluate electronic structure properties in a series of nanotubes with smallest possible diameters (both types: armchair and zigzag), and the corresponding chiral nanotubes (8,m) for 0 ≤ m ≤ 8. The calculations were performed considering a length of 16.5 Å. We evaluated a set of 26 combinations of dual nanotubes (armchair/armchair, zigzag/zigzag, armchair/zigzag, and zigzag/armchair), where the first label corresponds to the outer tube. We extended our study with nine additional systems of double-walled carbon nanotubes (DWCNT) with semiconductor nature. In this regard, we gave insight into the semiconductive or metallic nature inherited to the dual tubes. DWCNT systems were possible to construct by maintaining a radial distance of 3.392 Å for the armchair/armchair arrangement and 3.526 Å for the zigzag/zigzag type. It was considered as a reference, the interplanar distance of graphite (3.350 Å). Electronic transport calculations were also performed on selected DWCNT systems in order to understand the role played by the different symmetries under study. It was evidenced that the electronic structure nature of the systems rules the ability to transport electrons through the DWCNT interface.     

Effects of modified multi-walled carbon nanotubes on the curing behavior and thermal stability of boron phenolic resin

One kind of boron phenolic resin (BPR) was prepared from the solvent-less reaction of resoles with boric acid. X-ray photoelectron spectroscopy (XPS) showed that the reaction degree of boric acid was 83.8%. Multi-walled carbon nanotubes (MWCNTs) were modified by nitric acid, 4,4′-Diaminodiphenyl methane and boric acid. The effect of modification was determined by Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA) techniques and XPS. The cure kinetics and thermal behavior of BPR and modified multi-walled carbon nanotubes (m-MWCNTs)/BPR were studied. It was found that the curing apparent activation energy (E_a) decreased with the increasing amount of m-MWCNTs. But there was no obvious change in the orders of curing reactions. The results of TGA showed that 1.0 wt% of the m-MWCNTs could increase the thermal decomposition temperature (T_d) and the char yield of m-MWCNTs/BPR nanocomposites by 36.7 °C and 6.2%. These critical enhancements will definitely help to attract more researches on this area.     

Hydrogen adsorption in carbon nanostructures: comparison of nanotubes, fibers, and coals

Single-walled carbon nanotubes (SWNT) were reported to have record high hydrogen storage capacities at room temperature, indicating an interaction between hydrogen and carbon matrix that is stronger than known before. Here we present a study of the interaction of hydrogen with activated charcoal, carbon nanofibers, and SWNT that disproves these earlier reports. The hydrogen storage capacity of these materials correlates with the surface area of the material, the activated charcoal having the largest. The SWNT appear to have a relatively low accessible surface area due to bundling of the tubes; the hydrogen does not enter the voids between the tubes in the bundles. Pressure-temperature curves were used to estimate the interaction potential, which was found to be 580+/-60 K. Hydrogen gas was adsorbed in amounts up to 2 wt % only at low temperatures. Molecular rotations observed with neutron scattering indicate that molecular hydrogen is present, and no significant difference was found between the hydrogen molecules adsorbed in the different investigated materials. Results from density functional calculations show molecular hydrogen bonding to an aromatic C[bond]C that is present in the materials investigated. The claims of high storage capacities of SWNT related to their characteristic morphology are unjustified.     

Transport of a liquid water and methanol mixture through carbon nanotubes under a chemical potential gradient

In this work, we report a dual-control-volume grand canonical molecular dynamics simulation study of the transport of a water and methanol mixture under a fixed concentration gradient through nanotubes of various diameters and surface chemistries. Methanol and water are selected as fluid molecules since water represents a strongly polar molecule while methanol is intermediate between nonpolar and strongly polar molecules. Carboxyl acid (-COOH) groups are anchored onto the inner wall of a carbon nanotube to alter the hydrophobic surface into a hydrophilic one. Results show that the transport of the mixture through hydrophilic tubes is faster than through hydrophobic nanotubes although the diffusion of the mixture is slower inside hydrophilic than hydrophobic pores due to a hydrogen network. Thus, the transport of the liquid mixture through the nanotubes is controlled by the pore entrance effect for which hydrogen bonding plays an important role.     

Theoretical Investigation of Normal to Strong Hydrogen Bonds

We review our theoretical work done on a variety of different chemical systems, which show different H-bonding characteristics. The systems include water clusters, its interactions with polar molecules and π-systems, organic nanotubes, enzymes, and ionophores/receptors. Special features of normal, short, short strong, and π-type H-bonding interactions in these systems are discussed in terms of structures, interaction energies, and spectra.     

Self-sorting molecular clips

We report the synthesis and characterization of 12 C-shaped methylene-bridged glycoluril dimers (1-12) bearing H-bonding groups on their aromatic rings. Compounds 1, 2, (+/-)-4a, (+/-)-5, (+/-)-7, and 8 form tightly associated homodimers in CDCl3, due to the combined driving force of pi-pi and H-bonding interactions. Compounds 2, (+/-)-5, and 8, having disparate spatial distribution of their H-bonding groups, display the ability to efficiently distinguish between self and nonself even within three-component mixtures in CDCl3. When the spatial distributions of the H-bonding groups of the molecular clips are similar (e.g., 1 and 2), a mixture of homodimers and heterodimers is formed. The effect of various structural modifications (e.g., chirality, side chain steric bulk, number and pattern of H-bonds) on the strength of self-assembly and the fidelity of self-sorting are presented. On the basis of these results we prepared self-sorting systems comprising three (e.g., 1, (+/-)-5, and (+/-)-7) and even four ( 2, (+/-)-5, 9, and 10) components. The potential of molecular clips 1-12 as robust, functionalizable, self-sorting modules to control the noncovalent interaction network in systems chemistry studies is described.     

Synthesis and lyotropic liquid crystalline behaviour of a taper-shaped phosphonic acid amphiphile

A taper-shaped phosphonic acid, 3,4,5-tris(dodecyloxy)phenylmethylphosphonic acid ( 1 ), was synthesized; its lyotropic liquid crystalline (LLC) behaviour and its ability simultaneously to order and acid-dope polyaniline were examined. It was found that the ability of 1 to form LLC phases in the presence of several hydrophilic solvents is restricted by strong intermolecular interactions between the phosphonic acid head groups (presumably H-bonding). The amphiphile exhibits poor miscibility with pure water and even with strong H-bonding organic solvents such as DMF. However, it forms a lamellar mesophase in the presence of aqueous acid. Upon deprotonation of the phosphonic acid head group with NaOH, the resulting disodium salt of the amphiphile is able to form a well defined lamellar phase with pure water. The propensity of 1 to form lamellar phases is somewhat unusual since its tapered molecular shape should direct it to form an inverted hexagonal LLC phase. These results suggest that intermolecular head group interactions are more important in determining the overall LLC behaviour of this phosphonic acid amphiphile than are the hydrophobic character and shape of the organic tail system. Compound 1 was also found to be sufficiently acidic to act as an acid dopant for the conjugated polymer polyaniline in the emeraldine base form. LLC acid 1 induces the resulting polymeric salt to form an electrically conductive LLC complex with an extended lamellar microstructure. The bulk conductivity of the resulting nanostructured polyaniline salt was found to be only in the semiconducting regime (10 -5 Scm -1 ), due to an unfavourable polyaniline chain conformation in the LLC complex.     

Proximity-induced superconductivity in carbon nanotubes

Single wall carbon nanotubes (SWNT) are model systems for the study of electronic transport in one-dimensional conductors. They are expected to exhibit strong electronic correlations and non-Fermi liquid behavior as suggested by recent experiments. The possibility to induce supercurrents through such molecular wires is a challenging question both for experimentalists and theoreticians. In this paper we show experimental evidence of induced superconductivity in a SWNT. This proximity effect is observed in a single 1 nm diameter SWNT, in individual cristalline ropes containing about 100 nanotubes and also on multiwalled tubes. These samples are suspended as strings between two superconducting electrodes (double layer Au-Re, Au-Ta or Sn film) at a distance varying between 100 and 2 000 nm. This allows their structural study in a transmission electron microscope. When their resistance is low enough, SWNT become superconducting with surprisingly high critical currents (in the micro-Ampere range for a single tube of normal state resistance 25 kΩ). This critical current, extensively studied as function of temperature and magnetic field, exhibits unusual features which are not observed in conventional Superconducting-Normal-Superconducting junctions and can be related to the strong 1D character of these samples. We also show evidence of a huge sensitivity of dc transport properties of the tubes to electromagnetic radiation in the radio-frequency range.     

Structures and electronic transport of water molecular nanotubes embedded in carbon nanotubes

In this paper, ice nanotubes confined in carbon nanotubes are investigated by molecular dynamics. The trigonal, square, pentagonal, and hexagonal water tubes are obtained, respectively. The current-voltage (I-V) curves of water nanotubes are found to be nonlinear, and fluctuations of conductance spectra of these ice nanotubes show that the transport properties of ice nanotubes are quite different from those of bulk materials. Our studies indicate that the conductance gap of ice nanotube is related to the difference value from the Fermi energy EF to the nearest molecular energy level E0. Increasing the diameter of a water molecular nanostructure results in the increase of the conductance.