Synthesis and electrochemical properties of carbon nanotubes obtained by pyrolysis of acetylene using AB5 alloy

The paper discusses the efficiency of catalytic synthesis and structure of multi-wall carbon nanotubes obtained by acetylene decomposition over Mm (mischmetal)-based multi-component alloy of AB₅ type. Different parameters of catalytic chemical vapor deposition process have an influence on the efficiency. Some of them were changed to obtain the highest amount of carbon material. The samples were purified by acid and were characterized by BET surface area measurements, scanning electron microscopy, and transmission electron microscopy analysis. However, both catalyst and parameters of process (such as the flow rate of acetylene) need further examination to make it cost effective. The capacitance properties of carbon nanotubes as electrode materials for electrochemical capacitors are discussed. It has been shown that carbon nanotubes show moderate values of capacitance. In the form of a network, the material provides good charge propagation and can be used as a support and additive for different composite electrode materials.     

Synthesis,characterization and electrocatalytic properties of carbon nitride nanotubes for methanol electrooxidation

In this paper, carbon nitride nanotubes (CNNTs) have been synthesized with porous anodic aluminum oxide membrane as template by the thermal polymerization of sol–gel precursors for the first time. Field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis and X-ray photoelectron spectroscopy were applied to characterize the morphology and composition of the as-prepared nanotubes. The electrocatalytic activity and stability of CNNTs, towards methanol electrooxidation in 0.5 mol/dm³ H₂SO₄ solutions containing 1 mol/dm³ CH₃OH are presented at room temperature.     

Continuous production of single-wall carbon nanotubes by spray pyrolysis of alcohol with dissolved ferrocene

Ferrocene was dissolved in alcohol and such solution was used as the catalyst and carbon sources for the first time for producing single-walled carbon nanotubes (SWCNTs). This is different from the previous studies in which the catalyst was supported on either zeolite or a substrate when alcohol was used as the carbon source. Because of the use of a floating catalyst, SWCNTs could be produced continuously. Because of the use of alcohol, the formation of impurities, such as amorphous carbon, multi-walled carbon nanotubes and carbon nanoparticles were suppressed. Due to the simplicity of the present technique, it may be suitable for scale-up for mass production.     

Synthesis of straight and helical carbon nanotubes from catalytic pyrolysis of polyethylene

Straight and helical carbon nanotubes with diameter from 20 to 60 nm have been synthesized through catalytic decomposition of polyethylene in autoclave at 700 °C. The X-ray power diffraction pattern indicates that the products are hexagonal graphite, and transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM) images reveal the morphologies and structures of carbon nanotubes. The effects of reaction temperature, catalyst and maleated polypropylene on the growth of the carbon nanotubes were also discussed, and the growth mechanism of the CNTs was proposed. Pyrolysis of polyethylene is a promising green chemical method for economically producing carbon nanotubes.     

Synthesis and characterizations of amorphous carbon nanotubes by pyrolysis of ferrocene confined within AAM templates

Amorphous carbon nanotubes (a-CNTs) are synthesized by pyrolysis of ferrocene confined in the nanopores of the anodic alumina membrane (AAM) and characterized by field emission scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), and Raman spectroscopy. It is shown that the a-CNT has an ultrathin amorphous wall (approximately 3 nm) and a relatively large diameter (approximately 50 nm), and is capsulated with iron oxide nanoparticles. It is found that the growth of the a-CNTs is governed mainly by the template limitation effect. Electrical transport measurements on individual a-CNTs demonstrate that the a-CNT may be connected with electrodes via either ohmic or Schottky contacts, and the resisitivity of the a-CNTs was measured to be 4.5 x 10(-3) Omega cm.     

High-yield synthesis of single-wall carbon nanotubes on MCM41 using catalytic chemical vapor deposition of acetylene

High-quality single-wall carbon nanotubes (SWNTs) with narrow diameter distribution have been grown on Fe/Co-loaded MCM41 by using acetylene as the carbon source within a short reaction period, typically 10 min or less. The optimum temperature for SWNTs synthesis is 850 degrees C. Longer reaction time (i.e., 30 min) favors the formation of multiwall carbon nanotubes (MWNTs) and graphitic carbon. When the reaction time is reduced to less than 10 min, formation of MWNTs and graphitic carbon is greatly suppressed, and high-quality SWNTs dominates the yield. The surface of the as-grown SWNTs is found to be free from amorphous carbon, as observed from high-resolution transmission electron microscope (HRTEM) analysis. Raman spectral data show a G/D ratio above 10, indicating that the as-grown SWNTs have very few defects. Furthermore, radial breathing mode (RBM) analysis reveals that the diameter distribution of the current SWNTs is narrow and ranges from 0.64 to 1.36 nm.     

An innovative process for mass production of multi-wall carbon nanotubes by means of low-cost pyrolysis of polyolefins

An innovative process for a mass production of multi-wall carbon nanotubes (MWCNTs) by means of pyrolysis of virgin or recycled polyolefins is described. The technique uses solid-gas fluidised bed reactors, continuously operated under conditions which allow high heating rates of the polymers, high heat and material exchange coefficients and a reliable control of residence times in the reactor. The obtained MWCNTs have been characterized by TGA, SEM and TEM microscopy as well as X-ray diffractometry and Raman spectroscopy. The results demonstrate that the proposed process allows the production of MWCNTs compatible with most of the already known applications, in large quantities and at low cost. This makes extremely wider the field of possible applications of these nanostructured materials.     

Synthesis and characterization of monolithic carbon aerogel nanocomposites containing double-walled carbon nanotubes

We report the synthesis and characterization for the first examples of monolithic low-density carbon aerogel (CA) nanocomposites containing double-walled carbon nanotubes. The CA nancomposites were prepared by the sol-gel polymerization of resorcinol and formaldehyde in an aqueous surfactant-stabilized suspension of double-walled carbon nanotubes (DWNTs). The composite hydrogels were then dried with supercritical CO 2 and subsequently carbonized under an inert atmosphere to yield monolithic CA structures containing uniform dispersions of DWNTs. The microstructures and electrical conductivities of these CA nanocomposites were evaluated for different DWNT loadings. These materials exhibited high BET surface areas (>500 m (2)/g) and enhanced electrical conductivities relative to pristine CAs. The details of these results are discussed in comparison with theory and literature.     

Synthesis and characterization of high-quality double-walled carbon nanotubes by catalytic decomposition of alcohol

We report the synthesis of high-quality double-walled carbon nanotubes without defects by catalytic decomposition of alcohol over an Fe-Mo/Al2O3 catalyst; the synthesized DWNTs have outer diameters in the range of 1.52-3.54 nm and an average interlayer distance of 0.38 nm between graphene layers.     

Synthesis and characterization of conducting polythiophene/carbon nanotubes composites

Conducting polythiophene (PTh)/single‐wall carbon nanotubes (SWNTs) composites were synthesized by the in situ chemical oxidative polymerization method. The resulting cablelike morphology of the composite (SWNT–PTh) structures was characterized with elemental analysis, X‐ray photoelectron spectroscopy, Raman spectroscopy, Fourier transform infrared, ultraviolet–visible spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, X‐ray diffraction, and transmission electron microscopy. The standard four‐point‐probe method was used to measure the conductivity of the samples. Field emission scanning electron microscopy and transmission electron microscopy analysis revealed that the SWNT–PTh composites were core (SWNTs) and shell (PTh) hybrid structures. Spectroscopic analysis data for the composites were almost identical to those for PTh, supporting the idea that SWNTs served as templates in the formation of a coaxial nanostructure for the composites. The physical properties of the composites were measured and also showed that the SWNTs were modified by conducting PTh with an enhancement of various properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5283–5290, 2006     

Synthesis,structural characterization,and immunological properties of carbon nanotubes functionalized with peptides

Carbon nanotubes (NTs) are becoming highly attractive molecules for applications in medicinal chemistry. The main problem of insolubility in aqueous media has been solved by developing a synthetic protocol that allows highly water-soluble carbon NTs to be obtained. As a result, biologically active peptides can be easily linked through a stable covalent bond to carbon NTs. We have demonstrated that a bound peptide from the foot-and-mouth disease virus, corresponding to the 141-159 region of the viral envelope protein VP1, retained the structural integrity and was recognized by monoclonal and polyclonal antibodies. In addition, this peptide-NT conjugate is immunogenic, eliciting antibody responses of the right specificity. Such a system could be greatly advantageous for diagnostic purposes and could find future applications in vaccine delivery.     

Synthesis of carbon nanotubes by catalytic pyrolysis method with Feitknecht compound as precursor of NiZnAl catalyst

Carbon nanotubes are synthesized by catalytic pyrolysis method with a kind of new type catalyst--nickel-zinc-alumina catalyst prepared from Feitknecht compound. Tubular carbon nanotubes, bamboo-shaped carbon naotubes, herringbone carbon nanotubues and branched carbon nanotubes are all found formed at moderate temperature. It is important for the formation of quasi-liquid state of the metal nanoparticles at the tip of carbon naotubes during the growth of carbon nanotubes to lead to different kinds of carbon nanotubes. It is likely that the addition of zinc make the activity of nickel catalyst after calcinations and reduction changed strangely.     

Analytical pyrolysis as a characterization technique for monitoring the production of carbon nanofilaments

The main step in the production of carbon nanofilaments is the catalytic nucleation and lengthening of the filament. An undesired parallel step in the production of carbon nanofilaments is their thickening by pyrolitic carbon vapor deposition consisting in an ordered polycondensation of carbon over an existing catalytic carbon nanofilament. The regular characterization of the structure of carbon nanofilaments (coated or not) is by transmission electron microscopy. However, this technique is not affordable in many cases because is expensive and complex. In the present work, the analytical pyrolysis is proposed to obtain clues of the structure of carbon nanofilaments. Several commercial carbon nanofilaments have been analyzed. The samples with a thicker soot layer evolve a higher amount of heavy PAHs in the pyrolysis runs than the ones free of soot. It has been observed that pyrene is a key compound in the pyrolytic carbon vapor deposition process and the resulting formation of soot over the carbon nanofilaments. The aim of this work is to get useful information about the quality of the carbon filaments by a cheap technique, the analytical pyrolysis.     

Synthesis and physicochemical characterization of nanocomposites of calcium hydroxylapatite-chitosan-multiwall carbon nanotubes

The synthesis and physicochemical characterization of nanocomposites of calcium hydroxylapatite-chitosan-multiwall carbon nanotubes (CNTs) was performed. The CaCl₂-(NH₄)₂HPO₄-(C₆H₁₁NO₄) _n -CNT-NH₃-H₂O system was studied by the solubility (Tananaev’s residual concentration) method and pH measurements at 25°C. Conditions for the joint precipitation of nanocrystalline calcium hydroxylapatite, chitosan, and multiwall CNTs were found. Nanocomposites with the general formula Ca₁₀(PO₄)₆(OH)₂ · x(C₆H₁₁NO₄) · yCNT · zH₂O, where x = 0.1, 0.2, and 0.5; y = 0.5, 2.0, 4.0, and 5.0; and z = 5.9–7.9. The solid phases were characterized by chemical, thermogravimetric, and X-ray diffraction analysis and IR spectroscopy.     

Enhancing the pyrolysis of scrap rubber for carbon nanotubes/graphene production via chemical vapor deposition

Carbon nanostructures are considered nowadays as very important materials for both fundamental research and industrial applications because of their well-defined morphologies, which leads to excellent performance in various fields. This study presents the preparation of carbon nanostructures starting from cheap source represented by scrap rubber after pursuing optimized pyrolysis of scrap rubber at 500^oC as deduced from thermal gravimetric analysis (TGA). The resulting cracked hydrocarbons from pyrolysis were collected over a well-designed Fe-Ni-Cu/MgO as catalyst via chemical vapor deposition (CVD), in which a growth temperature of 750^oC was undertaken for 60 min. A further attempt was elaborated where the scrap rubber was exposed to thermal aging at 90^oC for 14 days prior to CVD of its pyrolysis products in order to enhance the cracking process and increase the yield of the lighter hydrocarbons produced which leads to formation of well-defined carbon nanostructures. Characterizations on the produced carbon nanostructures were achieved using transmission electron microscopy (TEM) and Raman spectroscopy. The adsorption of methylene blue on the carbon nanostructures was also studied. The characterizations confirmed that the morphology of the resulting carbon nanostructures derived from scrap rubber without prior thermal aging composed of graphene sheets wrapping carbon nanotubes (CNTs-A). After thermal aging of scrap rubber prior to pyrolysis and CVD, the produced carbon nanostructures composed principally of CNTs (CNTs-B) in a well-defined form in higher yield. The Langmuir model appeared to be best-fitting the adsorption of MB on both samples. High monolayer adsorption capacity of 95 mg MB/g was accomplished in case of CNTs-A versus 60 mg MB/g in case of CNTs-B, respectively. Ultraviolet-Visible (UV-Vis.) spectroscopic study revealed that the presence of MB molecules on the surface of CNTs may enhance the electronic properties of the prepared samples.     

Thermal stability of carbon nanotubes

Heat capacities of the carbon nanotubes (CNTs) with different sizes have been measured by modulated temperature differential scanning calorimetry (MDSC) and reported for the first time. The results indicated the values of C _p increased with shortening length of CNTs when the diameters of CNTs were between 60 and 100 nm. However, the values of C _p of CNTs were not affected by their diameter when the lengths of CNTs were 1–2 um, or not affected by the length of CNTs when their diameters were below 10 nm. The thermal stabilities of the CNTs have been studied by TG-DTG-DSC. The results of TG-DTG showed that thermal stabilities of CNTs were enhanced with their diameters increase. With lengths increase, the thermal stabilities of CNTs increased when their diameters were between 60 and 100 nm, but there is a slight decrease when their diameters were less than 60 nm. The further DSC analyses showed both released heat and T _onset increased with the increase of CNTs diameters, which confirms the consistency of the results from both TG-DTG and DSC on CNTs thermal stability.     

Generation of hydrophilic, bamboo-shaped multiwalled carbon nanotubes by solid-state pyrolysis and its electrochemical studies

A simple, efficient, and novel method was developed for the direct preparation of hydrophilic, bamboo-shaped carbon nanotubes by the pyrolysis of ruthenium(III) acetylacetonate in a Swagelock cell is reported. The obtained product exhibits mostly bamboo-shaped, straight, periodic twisted, multiwalled carbon nanotubes possessing diameters of 50-80 nm and lengths of around 10 microm. The pyrolyzed product was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), micro-Raman, and cyclic voltammetric techniques. HRTEM studies showed that the walls of bamboo-shaped carbon nanotubes consisted of oblique grapheme planes with respect to the tube axis. The interlayer spacing between two graphitic layers was found to be 0.342 nm. XPS measurements have suggested that as-prepared carbon nanotubes consist the surface functional groups on the surface of carbon nanotubes. The electrochemical properties of synthesized carbon nanotubes have been evaluated. Thermogravimetric analysis (TGA), IR, and cyclic voltammetric studies showed the presence of oxygen functionalities. Raman studies revealed the presence of disorder in the graphitic carbon and the presence of exposed edge plane defects in the generated carbon nanotubes for influencing the surface behavior and electrochemical properties. The electrochemical behavior of electrodes made of bamboo-shaped carbon nanotubes served for an oxygen reduction reaction.     

Catalyst and technology for production of carbon nanotubes

Modifying the iron-aluminum catalyst with molybdenum oxide affords a marked increase in the yield of carbon nanotubes from 1,3-butadiene diluted with hydrogen. The optimum catalyst composition is 6.5% MoO₃-52% Fe₂O₃-Al₂O₃. With this catalyst, it is possible to obtain over 100 g of carbon nanotubes per gram of catalyst in a reactor fitted with a McBain balance. Replacing expensive 1,3-butadiene with the cheaper commercial propane-butane mixture (80 mol % propane + 20 mol % butane) leads to a sharp decrease in the nanotube yield because of the lower reactivity of the latter. Based on the concept of the catalytic decomposition of hydrocarbons and the formation of nanosized carbon materials via the carbide cycle mechanism, a new, efficient, CoO-MoO₃-Fe₂O₃-Al₂O₃ catalyst has been developed. The enhancement of the activity of the MoO₃-Fe₂O₃-Al₂O₃ catalyst by promoting it with cobalt oxide is achieved without a change in the rate-limiting step of the process. The design of a continuous reactor for carbon nanotube synthesis is suggested. The characteristics of the resulting nanotubes are presented.     

Ethylenediamine-anchored gold nanoparticles on multi-walled carbon nanotubes: Synthesis and characterization

Binding of gold nanoparticles (Au-NP) at amine-functionalised multi-walled carbon nanotubes (MWNTs) is proposed. The MWNTs are functionalised with acylchloride groups, which further react with ethylenediamine to form amine-functionalised MWCNTs. These amines are able to bind preformed colloidal Au-NPs. The Au/MWNT composite material facilitates electron-transfer reactions with free-diffusing redox compounds.