Shell-Controlled Photoluminescence in CdSe/CNT Nanohybrids

A new type of nanohybrids containing carbon nanotubes (CNTs) and CdSe quantum dots (QDs) was prepared using an electrostatic self-assembly method. The CdSe QDs were capped by various mercaptocarboxylic acids, including thioglycolic acid (TGA), dihydrolipoic acid (DHLA) and mercaptoundecanoic acid (MUA), which provide shell thicknesses of ~5.2, 10.6 and 15.2 Å, respectively. The surface-modified CdSe QDs are then self-assembled onto aridine orange-modified CNTs via electrostatic interaction to give CdSe/CNT nanohybrids. The photoluminescence (PL) efficiencies of the obtained nanohybrids increase significantly with the increase of the shell thickness, which is attributed to a distance-dependent photo-induced charge-transfer mechanism. This work demonstrates a simple mean for fine tuning the PL properties of the CdSe/CNT nanohybrids and gains new insights to the photo-induced charge transfer in such nanostructures.     

Charge transfer properties and photoelectrocatalytic activity of TiO2/MWCNT hybrid

The vertically aligned multiwalled carbon nanotube (MWCNT) arrays on tantalum foils were successfully coated with TiO₂ nanoparticles by a hydrothermal process. The prepared TiO₂/MWCNT hybrid was characterized by scanning electron microscopy and transmission electron microscopy. The charge transfer properties and photocatalytic degradation of rhodamine B with and without bias potential under UV irradiation were investigated. The MWCNTs promoted the separation of photoinduced carriers in the TiO₂, thus enhanced photocatalytic activity. Applying bias potential on the photoanode further enhanced its catalytic activity. The efficient charge transportation and high photoelectrocatalytic activity towards degradation of rhodamine B made this hybrid material promising for photocatalyst and for the development of photoelectrical devices.     

Three-dimensional heterostructure of metallic nanoparticles and carbon nanotubes as potential nanofiller

ABSTRACT: The effect of the dimensionality of metallic nanoparticle-and carbon nanotube-based fillers on the mechanical properties of an acrylonitrile butadiene styrene (ABS) polymer matrix was examined. ABS composite films, reinforced with low dimensional metallic nanoparticles (MNPs, 0-D) and carbon nanotubes (CNTs, 1-D) as nanofillers, were fabricated by a combination of wet phase inversion and hot pressing. The tensile strength and elongation of the ABS composite were increased by 39% and 6%, respectively, by adding a mixture of MNPs and CNTs with a total concentration of 2 wt%. However, the tensile strength and elongation of the ABS composite were found to be significantly increased by 62% and 55%, respectively, upon addition of 3-D heterostructures with a total concentration of 2 wt%. The 3-D heterostructures were composed of multiple CNTs grown radially on the surface of MNP cores, resembling a sea urchin. The mechanical properties of the ABS/3-D heterostructured nanofiller composite films were much improved compared to those of an ABS/mixture of 0-D and 1-D nanofillers composite films at various filler concentrations. This suggests that the 3-D heterostructure of the MNPs and CNTs plays a key role as a strong reinforcing agent in supporting the polymer matrix and simultaneously serves as a discrete force-transfer medium to transfer the loaded tension throughout the polymer matrix.     

Stress transfer in polyacrylonitrile/carbon nanotube composite fibers

Gel spun polyacrylonitrile/carbon nanotube (PAN/CNT) composite fibers have been produced, and the stress-induced G′ Raman band shifts in the CNTs have been monitored to observe stress transfer during fiber strain. Improvements in CNT quality, CNT dispersion, and post-processing fiber drawing are shown to increase the stress transfer from the matrix to the CNT. Radial breathing mode (RBM) intensity of specific CNT chiralities confirms CNT debundling during fiber processing. During PAN/CNT fiber straining, there reaches a plateau in the CNT G′ downshift, signifying that the stress on the CNT is maintained despite continued straining of the PAN/CNT fiber. Correlating CNT strain with CNT modulus and volume fraction allows for the interfacial shear strength (τ_i) of the PAN-CNT interface to be determined. The as-spun and fully drawn PAN/CNT-A (99/1) nano composite fibers exhibit τ_i of 13.1 and 30.9 MPa, respectively, while an improved CNT dispersion (PAN/CNT-A (99.9/0.1)) results in τ_i equal to 44.3 MPa.     

Microwave-induced rapid chemical functionalization of single-walled carbon nanotubes

The microwave-induced chemical functionalization of single-walled carbon nanotubes (SWNTs) is reported. The major advantage of this high-energy procedure is that it reduced the reaction time to the order of minutes and the number of steps in the reaction procedure compared to that of conventional functionalization processes. Two successful model reactions, namely amidation and 1,3-dipolar cycloaddition of SWNTs were carried out. The amidation was completed in two steps as compared to three in the conventional approach. The step involving acid chloride formation was eliminated here, and the yield remained the same. The 1,3-dipolar cycloaddition of SWNTs was carried out in 15 min under microwave conditions, and the results were similar to what was achieved in 5 days using conventional methods. This finding opens the door to fast and inexpensive processing to produce functional SWNTs, which is extremely important for their use in real-world applications.     

Semi-continuous production of multiwalled carbon nanotubes using magnetic field assisted arc furnace

A high-temperature arc furnace with an applied external magnetic field has been used to grow carbon nanotubes. The magnetic field was able to spread and stabilize the plasma enabling the use of larger electrodes than could be used successfully with no magnetic field. By having a stable plasma across the entire anode surface, larger amounts of carbon black were able to be transformed into carbon nanotubes. In addition, a multiple-pronged anode was designed. The use of the pronged anode created a semi-continuous process which allowed for the amount of nanotubes produced per run to increase.     

Thin films of amorphous nitrogenated carbon a-CNx: Electron transfer and surface reactivity

The electrochemical behaviour of thin films of nitrogenated amorphous carbon a-CN_x is similar to that of boron-doped diamond, with a wide potential window in aqueous media. They are elaborated by cathodic sputtering of a graphite target in an Ar-N₂ active plasma for varying nitrogen contents, determined by XPS (0.06 ≤ x ≤ 0.39). Their electrochemical reactivity is sensitive to the surface state. The present study reports on the influence of electrochemical pre treatment on the electronic transfer rate of a fast redox system ferri-ferrocyanide, by focusing on the direction of the potential excursion. On the other hand, the role of both the pH and the potential on the interfacial capacitance in the presence of Na₂SO₄ without redox species is documented. The results show up the sensitivity of the film surface to the electrochemical conditions.     

The effect of the cobalt loading on the growth of single wall carbon nanotubes by CO disproportionation on Co-MCM-41 catalysts

Highly ordered MCM-41 mesoporous molecular sieves in which silicon was isomorphously substituted with 0.5-4 wt.% cobalt were synthesized using an alkyl template with a 16 carbon atoms alkyl chain length. These materials were used as catalysts for the synthesis of uniform diameter single wall carbon nanotubes (SWNT) by CO disproportionation (Boudouard reaction). The SWNT synthesis conditions were identical for all Co-MCM-41 samples, and consisted of pre-reduction of the Co-MCM-41 catalyst in hydrogen at 500 °C for 30 min followed by reaction with pure CO at 800 °C and 6 atm for 1 h (conditions previously optimized for 1 wt.% Co-MCM-41). The SWNT grown in the Co-MCM-41 catalysts were characterized by TGA, multi-excitation energy Raman spectroscopy and TEM. The state of the catalyst and the size of the metallic cobalt clusters formed in Co-MCM-41 during the SWNT synthesis were characterized by X-ray absorption spectroscopy. The mechanism controlling the diameter distribution of the SWNT produced is related to the size uniformity of the cobalt clusters nucleated in the Co-MCM-41 catalytic template: the SWNT growth selectivity and size uniformity is influenced by the cobalt concentration in the framework. If the cobalt is not initially strongly stabilized in the MCM-41 framework during template synthesis, the catalyst produces SWNT with a wider diameter distribution. Co-MCM-41 catalysts with up to 3 wt.% cobalt can be used to grow SWNT with a diameter distribution similar to that obtained with 1 wt.% Co-MCM-41, but at yields greater by a factor of approximately 2.4.     

End cap nucleation of carbon nanotubes

An easily applied graphical approach for facilitating precise tailoring during computational construction of model uncapped or capped single-wall nanotubes or fullerenes is delineated and utilized in this paper. The main enabling concepts are the commonly suggested growth mechanisms for single- and multi-walled carbon nanotubes mediated by end cap structures. The construction protocol described herein can be used to rapidly create any type of armchair, zigzag, chiral or nonchiral defect-free nanotube. Any desired, feasible combination of length and diameter, along with specific placement of hexagonal and pentagonal rings or end caps, can also be controlled. A classification system for end caps is also developed in order to help simplify choosing or describing the particular carbon system under investigation. The suggested methodology is used to systematically model heats of formation of a variety of carbon nanotubes and related fullerenes using AM1 semiempirical calculations. The main factors affecting the calculated physical properties, other than size, are the structures of the various base and terminating end caps. Finally, we comment on the possible relationship of the construction methodology to mechanisms for carbon nanotube nucleation.     

Multiwalled carbon nanotubes and nanofibers grafted with polyetherketones in mild and viscous polymeric acid

Direct covalent attachment of amorphous and semicrystalline polyetherketones onto the surface of either an as-received multi-walled carbon nanotube (MWNT) or a vapor-grown carbon nanofiber (VGCNF) in polyphosphoric acid (PPA) with optimized P₂O₅ content resulted in uniform grafting of polyetherketones to these carbon nanoscale materials. Soxhlet extraction experiment, the spectra from FT-IR spectroscopy and the clear images from high-resolution transmission electron microscopy showed that the covalent attachment is effective in uniformly coating the PEK grafts on the surfaces of both MWNT and VGCNF. Additionally, a drastic increase in solution viscosity due to the formation of giant molecules was monitored during polymerization. As such, the resulting nanocomposites were easily fabricated via a simple compression molding technique. The alignment possibility of MWNT and VGCNF grafted with semicrystalline PEK in these thermoplastic nanocomposites via solution fiber spinning was also demonstrated.     

Multi-step purification of carbon nanotubes

An efficient purification procedure for multi-walled carbon nanotubes (MWNTs) synthesized by the floating catalyst method was discussed. The process involves ultra-sonication, heat treatment in hot water, bromination, oxidation and acid treatment. Most of amorphous carbon, multishell carbon nanocapsules as well as metal particles were successfully removed from the MWNT product. With this procedure, MWNTs with purity of more than 94% were obtained and the yield could approach 50%. It was found that bromination took an important role in the purification of MWNTs. Transmission electron microscopy, XPS and thermo-gravimetric analysis were used to evaluate the purification process of MWNTs. The mechanism of bromination on purification of the MWNTs was also discussed.     

Size effect of X-shaped carbon nanotube junctions

Systematic calculations have been performed for X-shaped junctions formed between two crossed identical carbon nanotubes (armchair or zigzag tubes) with diameters ranging from 3.92 Å to 9.49 Å using an empirical potential method. The formation energy of X junctions is found to be a function of the diameter of the tubes. The formation temperature is dependent on the curvature of tubes. The calculations show that it is energetically favorable to form X junctions by the direct heating method if the tube diameter is less than 0.85 nm.     

In vitro studies of carbon nanotubes biocompatibility

Cellular tests have been applied to study the biocompatibility of high purity multiwalled carbon nanotubes (MWNTs). The viability of fibroblasts, osteoblasts and osteocalcin concentrations in osteoblasts cultures in the presence of nanotubes has been examined, as well as the degree of cells stimulation, based on the amount of released collagen type I, IL-6 and oxygen free radicals. The high level of viability of the examined cells in contact with the nanotubes, the slight increase of collagen formation, the lack of pro-inflammatory IL-6 cytokine as well as the induction of free radicals, confirm a good biocompatibility of nanotubes, which is similar to that of polysulfone currently used in medicine. The collagen synthesis induced on nanotubes by both fibroblasts and osteoblasts may be significant for future medical applications of nanotubes, in particular as substrates for the regeneration of tissues.     

Electrooxidation of DNA at glassy carbon electrodes modified with multiwall carbon nanotubes dispersed in polyethylenimine

This work reports the electrochemical response of the complex between dsDNA and PEI formed in solution and at the surface of glassy carbon electrodes (GCE) modified with a dispersion of multi-walled carbon nanotubes in polyethylenimine (CNT-PEI). Scanning Electron Microscopy and Scanning Electrochemical Microscopy demonstrate that the dispersion covers the whole surface of the electrode although there are areas with higher density of CNT and, consequently, with higher electrochemical reactivity. The adsorption of DNA at GCE/CNT-PEI is fast and it is mainly driven by electrostatic forces. A clear oxidation signal is obtained either for dsDNA or a heterooligonucleotide of 21 bases (oligoY) at potentials smaller than those for the oxidation at bare GCE. The comparison of the behavior of DNA before and after thermal treatment demonstrated that the electrochemical response highly depends on the 3D structure of the nucleic acid.     

Nitrogen-doped carbon nanotubes synthesized with carbon nanotubes as catalyst

Nitrogen-doped carbon (CN_x) nanotubes were synthesized with carbon nanotubes (CNTs) as catalyst by detonation-assisted chemical vapor deposition. CN_x nanotubes exhibited compartmentalized bamboo-like structure. Electron energy loss spectroscopy and elemental mapping studies indicated that the synthesized tubes contained high concentration of nitrogen (ca. 17.3 at.%), inhomogeneously distributed with an enrichment of nitrogen within the compartments. X-ray photoelectron spectroscopy analysis revealed the presence of pyridine-like N and graphitic N incorporated into the graphitic network. The catalytic activity of CNTs for CN_x nanotube growth was ascribed to the nanocurvature and opening edges of CNT tips, which adsorbed C_n/CN species and assembled them into CN_x nanotubes.     

Tensile properties of ultrathin double-walled carbon nanotube membranes

Direct tensile tests of double walled carbon nanotube (DWCNT) membranes with thickness of 40–80 nm were performed using a micro-stress-strain puller. The tensile strength and Young’s modulus are 4.8E2–8.4E2 MPa and 4.4–8.8 GPa, respectively. The deformation and fracture processes were analyzed using the stress vs. strain curves, and SEM observations of the fracture surface of a membrane. The membrane experienced elastic strain and plastic strain during tensile-loading to fracture, and the plastic process is due to the real plastic deformation of the membrane and the slippage between the DWCNT bundles. Cracks occur and spread during the tensile test which causes the membrane to be mangled. With these excellent mechanical properties, the DWCNT membranes can be used in nanotube-reinforced composites.