Surface modification of carbon nanotubes for enhancing BTEX adsorption from aqueous solutions

Carbon nanotubes (CNTs) were fabricated by the catalytic chemical vapor deposition method and oxidized by HCl, H₂SO₄, HNO₃ and NaOCl solutions for enhancing benzene, toluene, ethylbenzene and p-xylene (BTEX) adsorption in an aqueous solution. The surface nature of CNTs was changed after the H₂SO₄, HNO₃ and NaOCl oxidation, which makes CNTs that adsorb more BTEX. The NaOCl-oxidized CNTs show the greatest enhancement in BTEX adsorption, followed by the HNO₃-oxidized CNTs, and then the H₂SO₄-oxidized CNTs. The adsorption mechanism of BTEX via CNTs is mainly attributed to the π-π electron-donor-acceptor interaction between the aromatic ring of BTEX and the surface carboxylic groups of CNTs. The NaOCl-oxidized CNTs have superior adsorption performance of BTEX as compared to many types of carbon and silica adsorbents reported in the literature. This suggests that the NaOCl-oxidized CNTs are efficient BTEX adsorbents and that they possess good potential applications for BTEX removal in wastewater treatment.     

A comparative analysis of thin-film transistors using aligned and random-network carbon nanotubes

The purpose of this project is to investigate the characterization of carbon nanotube (CNT) thin-film transistors based on two solution-based fabrication methods: dielectrophoretic deposition of aligned CNTs and self-assembly of random-network CNTs. The electrical characteristics of aligned and random-network CNT transistors are studied comparatively. In particular, the selection effect of metallic and semiconducting CNTs in the dielectrophoresis process is evaluated experimentally by comparing the output characteristics of the two transistors. Our results demonstrate that the self-assembly method produces a stronger field effect with a much higher on/off ratio (I _on /I _off ). This phenomenon provides evidence that the metallic CNTs are more responsive to dielectrophoretic forces than their semiconducting counterparts under common deposition conditions. In addition, the nanotube–nanotube cross-junctions in random-network CNT films create additional energy barriers and result in a reduced electric current. Thus, additional consideration must be applied when using different fabrication methods in building CNT-based electronic devices.     

The interaction between unique hyperbranched polyaniline and carbon nanotubes,and its influence on the dielectric behavior of hyperbranched polyaniline/carbon nanotube/epoxy resin composites

Novel hybridized multi-walled carbon nanotubes (CNTs), consisting of a unique hyperbranched polyaniline (HSiPA) and CNTs, were prepared. The interaction between HSiPA and CNTs was investigated by many techniques, and results show that there are strong π–π and electrostatic interactions between HSiPA and CNTs, so HSiPA can stack firmly onto the surface of CNTs to form a coating. Based on this, a new kind of ternary composites made up of hybridized CNTs and epoxy (EP) resin was prepared, the influence of the ratio of HSiPA to CNTs on the structure and properties of the HSiPA/CNT/EP composites was intensively studied. The percolation threshold of HSiPA/CNT/EP composites is very low (1.26 wt%); besides, with a suitable ratio of HSiPA to CNTs, the HSiPA/CNT/EP composite has much higher dielectric constant and lower dielectric loss than the CNT/EP composite with the same loading of CNTs. When the ratio of HSiPA to CNTs is 0.5:1, the dielectric constant and loss at 100 Hz of the resultant HSiPA/CNT0.5/EP composite are 711 and 1.53, about 7.1 and 4.3 × 10^?3 times the corresponding value of CNT0.5/EP composite, respectively. In addition, compared with traditional CNT/EP composites, the HSiPA/CNT0.5/EP composites have different equivalent circuit models. These attractive results are attributed to unique structure of hybridized CNTs, and thus leading to greatly different structures between the CNT0.5/EP and HSiPA/CNT0.5/EP composites. This investigation reported herein suggests a new approach to prepare new CNTs and related composites with controllable dielectric properties.     

Deactivation of an excited charge-transfer complex II. Influence of rigidity of medium on radiative and radiationless transitions

Fluorescence spectra, quantum yields and decay times for charge-transfer complexes of tetracyanoethylene with benzene, toluene, ortho-xylene and para-xylene in low-temperature glassy solutions of different viscosities have been investigated. It was established that the influence of viscosity or rigidity of medium on charge-transfer fluorescence consists in the decrease of efficiency of radiationless processes when viscosity or rigidity increases. Fluorescence spectra of complexes of tetracyanoethylene with toluene, o-xylene and p-xylene have a composite double-band character at high viscosities of medium. The intensity of both subbands changes in a different way with change of viscosity. The excitation spectra of these complexes are dependent on the wavelength of observation. These facts are discussed in terms of an existence of different orientational isomers of a charge-transfer complex of low symmetry.     

Interaction mechanism between serine functional groups and single‐walled carbon nanotubes

The adsorption of serine (Ser) on the (8, 8) and (10, 0) single‐walled carbon nanotubes (CNTs) was studied by density‐functional tight‐binding calculations. For Ser, the two most stable configurations were chosen to research the interactions with the CNT. It found that the most stable Ser/(8, 8) and Ser/(10, 0) complexes have similar structures, in which the amino group, carboxyl, and side chain of serine directly interact with the CNT. The binding energies, charge transfer properties, the shortest distance (d₁) between the H atom and the corresponding benzene ring, distance (d₂) between the H atom and the center of benzene ring (HCB), and the angle (α) between the HCB line and the corresponding benzene ring plane were analyzed to explain the interactions. Because of the interaction, the ?CH of the main chain runs away from the surface of CNT, and the angles between the ?C?H bond of the main chain and the carboxyl, the amino group, and the side chain of the Ser become small. The strain energies and changes of angles and dihedral angles of the serine after adsorption were analyzed to illustrate the deformation. The interactions of Ser with the CNT were further illustrated by calculating the molecular orbitals and the partial density of states of the stable complexes. We further compared the binding energies of armchair (n, n) and zigzag (n, 0) CNTs to investigate the diameter dependence of binding energies. Copyright © 2015 John Wiley & Sons, Ltd.     

Increase of critical current density with doping carbon nano-tubes in YBa2Cu3O7−δ

The effects of carbon nano-tubes (CNTs) on the crystal structure and superconducting properties of YBa₂Cu₃O_7?δ (Y-123) compound were studied. Samples were synthesized using standard solid-state reaction technique by adding CNT up to 1 wt% and X-ray diffraction data confirm the single phase orthorhombic structure for all the samples. Current–voltage measurements in magnetic fields up to 9 T were used to study the pinning energy U_J and critical current density J_c as a function of magnetic field at fixed temperature. We find that while T_c does not change much with the CNT doping (91–92 K), both U_J and J_c increase systematically up to 0.7 wt% CNT doping in a broad magnetic field ranges between 0.1 and 9 T and J_c in the 0.7 wt% CNT doped sample is at least 10 times larger than that of the pure Y-123. The scanning electron microscope image shows that CNTs are forming an electrical-network between grains. These observations suggest that the CNT addition to the Y-123-compounds improve the electrical connection between superconducting grains to result in the J_c increase.     

Systematic investigation on the properties of carbon nanotube electrodes with different chemical treatments

The functionalization of carbon nanotubes (CNTs) was carried out by using different chemical treatment methods. These functionalized CNTs were characterized by TEM image and FT-IR spectra. The CNT electrodes are measured by thermal resistivity and cyclic voltammetry experiments. The results showed that two important factors controlled the electrochemical properties of the CNT film electrode: one is the active functional group; another is activation energy of the CNT film. From our experiments, we have found the electrode of 10 min nitric acid treated CNTs have the optimal peaks in relation to carboxylic acids, the highest redox peak currents, the biggest value of k⁰ and well-defined quasi-reversible voltammograms for redox of iron couples, in which the two factors best match.     

Advanced LiTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C anode by incorporation of carbon nanotubes for aqueous lithium-ion batteries

Inferior rate capability is a big challenge for LiTi₂(PO₄)₃ anode for aqueous lithium-ion batteries. Herein, to address such issue, we synthesized a high-performance LiTi₂(PO₄)₃/carbon/carbon nanotube (LTP/C/CNT) composite by virtue of high-quality carbon coating and incorporation of good conductive network. The as-prepared LTP/C/CNT composite exhibits excellent rate performance with discharge capacity of 80.1 and 59.1 mAh g^?1 at 10 C and 20 C (based on the mass of anode, 1 C = 150 mA g^?1), much larger than that of the LTP/C composite (53.4 mAh g^?1 at 10 C, and 31.7 mAh g^?1 at 20 C). LTP/C/CNT also demonstrates outstanding cycling stability with capacity retention of 83.3 % after 1000 cycles at 5 C, superior to LTP/C without incorporation of CNTs (60.1 %). As verified, the excellent electrochemical performance of the LTP/C/CNT composite is attributed to the enhanced electrical conductivity, rapid charge transfer, and Li-ion diffusion because of the incorporation of CNTs.     

Synthesis of carbon nanotubes on diamond-like carbon by the hot filament plasma-enhanced chemical vapor deposition method

Carbon nanotubes (CNTs) have attracted considerable attention as possible routes to device miniaturization due to their excellent mechanical, thermal, and electronic properties. These properties show great potential for devices such as field emission displays, transistors, and sensors. The growth of CNTs can be explained by interaction between small carbon patches and the metal catalyst. The metals such as nickel, cobalt, gold, iron, platinum, and palladium are used as the catalysts for the CNT growth. In this study, diamond-like carbon (DLC) was used for CNT growth as a nonmetallic catalyst layer. DLC films were deposited by a radio frequency (RF) plasma-enhanced chemical vapor deposition (RF-PECVD) method with a mixture of methane and hydrogen gases. CNTs were synthesized by a hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment gas and acetylene (C₂H₂) as a carbon source gas. The grown CNTs and the pretreated DLC films were observed using field emission scanning electron microscopy (FE-SEM) measurement, and the structure of the grown CNTs was analyzed by high resolution transmission scanning electron microscopy (HR-TEM). Also, using energy dispersive spectroscopy (EDS) measurement, we confirmed that only the carbon component remained on the substrate.     

Interface energy of faces of manganese and vanadium crystals at boundaries with organic liquids

The dependence of the interface energy at a boundary between a metallic crystal face and an organic liquid on the permittivity of the liquid is obtained using a modified version of the electron-statistical Frenkel’–Gombas–Zadumkin theory. The interface energies of faces with low Miller indices of α-Mn and V at boundaries with hexane, benzene, toluene, and o-xylene are calculated.     

Josephson current through randomly oriented CNTs

In this paper, we employ tunneling Hamiltonian formulation to obtain analytical expression for the Josephson current in (n, m) Carbon nanotubes (CNT) sandwiched between s-wave superconductors. For metallic tubes, we find that the dominant contribution to the Josephson current arises from modes crossing the Dirac points. Contribution from such conducting channels is independent of tube diameter of carbon nanotubes. Josephson current for each CNT is determined in terms of the spacing d between the superconductors, and the angle between the tube axis and the vector normal to the interface. Averaging over orientation angles gives the Josephson current through an assembly of randomly oriented CNTs, which turns out to be on the scale of 100 nA.     

An SCMO calculation of the spin densities in the methyl substituted benzene negative ions

Most of the many attempts to explain ‘hyperconjugation’ invoke an explicit delocalization of the electrons of the methyl group. This work is part of an attempt to calculate these effects by a method which requires no such delocalization. A calculation of the spin densities in the methyl substituted benzene negative ions is reported here.

In this work the methyl substituent is considered to exert a purely inductive effect which manifests itself in a change in the scale of the orbital exponent of the 2pπ atomic orbital at the carbon to which it is attached. (This is in contrast to previous ‘inductive’ treatments in the HMO method which alter only the α of the substituted carbon.) This change is evaluated by considering the change in the ionization potential of the methyl radical on successive methyl substitution. (There is no reference to any EPR data for the calibration of the parameters.)

A comparison with the EPR results for the toluene, m-xylene and p-xylene negative ions reveals excellent agreement for these compounds.

An open-shell SCMO procedure based on that of Roothaan is used in the calculations.     

Intrinsic energy loss mechanisms in a cantilevered carbon nanotube beam oscillator

Classical molecular dynamics is applied to study the energy dissipation (the Q factor) of the cantilever-type beam oscillators of single wall and double-walled carbon nanotubes (CNTs). The study finds that the Q factor of the CNT beam oscillator varies with the temperature T following the 1/T(0.36) dependence. For single wall CNT, the Q factor drops from 2 x 10(5) at 0.05 K to 1.5 x 10(3) at 293 K. The study further reveals that the weak interlayer binding strength and the interlayer commensurance significantly increases the energy dissipation in the double-walled CNT oscillator.     

Individuals, grasses, and forests of single- and multi-walled carbon nanotubes grown by supported Co catalysts of different nominal thicknesses

The relationships among the nominal thickness of Co catalyst, the structure of the catalyst particles, and the structure of carbon nanotubes (CNTs) growing from the catalyst during chemical vapor deposition were investigated. Various morphologies of CNTs such as individuals, random networks parallel to the surface of the substrate (‘grasses’), and vertically aligned forests of single- and multi-walled carbon nanotubes were grown by only varying the nominal thickness of catalyst under the same reaction condition. These different morphologies at the same growth time were due to the different areal density rather than to the length of CNTs. With increasing nominal thickness of catalyst, the catalyst particles changed in diameter while their areal density remained relatively almost constant. The change in diameter possibly affected the number ratio of active catalyst particles to the whole particles, which in turn affected the areal density of CNTs and yielded the various morphologies. Longer growth time increased the CNT length, which caused further change in CNT morphologies from individuals to grasses and grasses to forests.     

Preparation of NiO decorated CNT/ZnO core-shell hybrid nanocomposites with the aid of ultrasonication for enhancing the performance of hybrid supercapacitors

Supercapacitor (SC) electrodes fabricated with the combination of carbon nanotubes (CNTs) and metal oxides are showing remarkable advancements in the electrochemical properties. Herein, NiO decorated CNT/ZnO core-shell hybrid nanocomposites (CNT/ZnO/NiO HNCs) are facilely synthesized by a two-step solution-based technique for the utilization in hybrid supercapacitors. Benefitting from the synergistic advantages of three materials, the CNT/ZnO/NiO HNCs based electrode has evinced superior areal capacity of ~67 µAh cm⁻² at a current density of 3 mA cm⁻² with an exceptional cycling stability of 112% even after 3000 cycles of continuous operation. Highly conductive CNTs and electrochemically active ZnO contribute to the performance enhancement. Moreover, the decoration of NiO on the surface of CNT/ZnO core-shell increases the electro active sites and stimulates the faster redox reactions which play a vital role in augmenting the electrochemical properties. Making the use of high areal capacity and ultra-long stability, a hybrid supercapacitor (HSC) was assembled with CNT/ZnO/NiO HNCs coated nickel foam (CNT/ZnO/NiO HNCs/NF) as positive electrode and CNTs coated NF as negative electrode. The fabricated HSC delivered an areal capacitance of 287 mF cm⁻² with high areal energy density (67 µWh cm⁻²) and power density (16.25 mW cm⁻²). The combination of battery type CNT/ZnO/NiO HNCs/NF and EDLC type CNT/NF helped in holding the capacity for a long period of time. Thus, the systematic assembly of CNTs and ZnO along with the NiO decoration enlarges the application window with its high rate electrochemical properties.     

Growth of carbon nanotubes on stainless steel substrates by DC-PECVD

We report on the fabrication of carbon nanotubes (CNTs) on Ni-coated stainless steel (SUS) substrates by using dc plasma enhanced chemical vapor deposition. The synthesized CNTs have the diameter of about 30 nm and the length of about 1.2 μm. To verify the effects of SUS substrates on the growth of CNTs, CNTs had also been grown on Ni-coated Si substrates. CNTs grown on the SUS substrates were more uniform compared with those grown on the Si substrates. Field emission properties of the CNT films were measured in the diode configuration, and the turn-on electric field of 3.87 V/μm and field enhancement factor β of about 1737 were obtained from the synthesized CNTs at the gap of 500 μm between the SUS substrate and the anode. These results have not only clarified the effects of the substrate on the growth of CNTs, but also shown the potential of CNTs in field emission applications, especially CNT-based cold-cathode X-ray tubes.     

HIGH-YIELD PRODUCTION OF MULTI-WALLED CARBON NANOTUBES BY CATALYTIC DECOMPOSITION OF BENZENE VAPOR

Multi-walled carbon nanotubes (CNTs) have been synthesized on γ-Al₂O₃ supported unitary, binary or trinity metal (Fe, Co, Ni) catalysts with benzene as carbon source in the range of 600 to 810 ℃. The growth of CNTs was carried out in a fixed bed flow reactor and the quality of carbon deposits was characterized by transmission electron microscopy. The preparation was optimized and the high-yield production of CNTs has been achieved for three mixture catalysts with the yield of high-quality CNTs higher than 200% within 60 min, reaching a maximum of 278% for 1.51 mmol/g Fe-1.51 mmol/g Co/γ-Al₂O₃ catalyst. This provides a good alternative for future large scale and low cost production of CNTs for applications.     

Pyridine-thermal synthesis and high catalytic activity of CeO2/CuO/CNT nanocomposites

Carbon nanotubes (CNTs) were controllably coated with the uninterrupted CuO and CeO₂ composite nanoparticles by a facile pyridine-thermal method and the high catalytic performance for CO oxidation was also found. The obtained nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction as well as X-ray photoelectron spectroscopy. It is found that the CuO/CeO₂ composite nanoparticles are distributed uniformly on the surface of CNTs and the shell of CeO₂/CuO/CNT nanocomposites is made of nanoparticles with a diameter of 30-60 nm. The possible formation mechanism is suggest as follows: the surface of CNTs is modified by the pyridine due to the π-π conjugate role so that the alkaline of pyridine attached on the CNT surface is more enhanced as compared to the one in the bulk solvent, and thus, these pyridines accept the proton from the water molecular preferentially, which result in the formation of the OH⁻ ions around the surface of CNTs. Subsequently, the metal ions such as Ce³⁺ and Cu²⁺ in situ react with the OH⁻ ions and the resultant nanoparticles deposit on the surface of CNTs, and finally the CeO₂/CuO/CNT nanocomposites are obtained. The T₅₀ depicting the catalytic activity for CO oxidation over CeO₂/CuO/CNT nanocomposites can reach ∼113 °C, which is much lower than that of CeO₂/CNT or CuO/CNT nanocomposites or CNTs.     

Nanowire formation by coalescence of small gold clusters inside carbon nanotubes

The coalescence of Au₁₃, Au₅₅ and Au₁₄₇ icosahedral clusters encapsulated inside single walled carbon nanotubes (CNTs) of different diameters are investigated using molecular dynamics simulation with semi-empirical potentials. Three steps needed for the formation of encapsulated nanowires are followed in detail, namely, the penetration of clusters in CNTs, the coalescence between two clusters inside CNTs and their accumulation to form wires. It is suggested that no significant energy barrier is encountered during the penetration of free clusters into CNTs provided the CNT radius is large enough, that is, about 0.3 nm larger than the cluster radius. The relative orientation of clusters imposed by the CNT favors their spontaneous coalescence. After coalescence of two clusters, the Au atoms are rearranged to form new structures of cylindrical symmetry that may be seven fold, six fold, five fold, helical or fcc depending on the CNT diameter. The thermal stability of these structures is discussed and the structural properties of nanowires formed by accumulation of many clusters in CNTs are analyzed in detail. A geometrical method is presented which allows the prediction of the structure of multi-shell helical wires, when knowing only the CNT radius. These modeling results suggest the possibility of synthesizing metallic nanowires with controlled diameter and structure by embedding clusters into nanotubes with suitable diameters.     

Structural and morphological dependence of carbon nanotube arrays on catalyst aggregation

Catalyst aggregation affects the growth of carbon nanotube (CNT) arrays in terms of tubular structures, waviness, entanglement, lengths, and growth density etc., which are important issues for application developments. We present a systematic correlation between the aggregation of catalyst on the SiO₂/Si substrate and the structure and morphology of CNT arrays. The thickness of the catalyst film has a direct effect on the areal density of the catalytic particles and then the alignment of the CNT array. Introducing alumina as buffer layer and annealing the catalyst film at low pressure are two effective approaches to downsize the catalyst particles and then the diameter, wall number of the CNTs. Both the size and areal density of the catalyst also change with the CNT growth in accordance with Ostwald ripening process, with the bottom of the CNT array varying from well-aligned to disordered and adhesion between catalyst particles and the substrate getting enhanced. Strategies including tuning the thickness of the catalyst film, changing buffer layer, controlling on the growth time and the system pressure were used to regulate the aggregation of the catalyst. CNT arrays from disordered to well-aligned, from multi-walled to few-walled and further to single-walled were reproducibly synthesized by chemical vapor deposition of acetylene.