Evaluation of affinity of molecules for carbon nanotubes

Recent developments of non-covalent functionalization of carbon nanotubes (CNTs) require a systematic understanding of the interaction between molecule and CNTs (CNT-molecular interaction); however, it has been difficult to evaluate the "net" interaction between the CNTs and molecules. We now use silica gel particles coated with the pristine single-walled carbon nanotubes (SWNTs) in a monolayer fashion as the stationary phase of a HPLC column. The newly developed column (SWNT-column) worked as a powerful tool for ranking the interactions between the SWNTs and molecules with a high precision. We describe the binding affinity analysis of polyaromatic hydrocarbons onto the surfaces of SWNTs. The obtained ranking is determined in the order of benzene < naphthalene < biphenyl < fluorene < phenanthrene < anthracene ～ pyrene < triphenylene < p-terphenyl < tetraphene < tetracene.     

Synthesis of carbon nanotubes by microwave plasma-enhanced hot filament chemical vapor deposition

A combined system of microwave plasma-enhanced chemical vapor deposition (MPECVD) and hot filament CVD (HFCVD) has been developed for the growth of various carbon nanotubes, where the source gas (methane) can be decomposed independently through microwave plasma and hot tungsten filament. It is found that microwave plasma provides more efficiently carbon sources for the growth of carbon nanotubes (CNTs). By the help of microwave plasma, long CNTs array with length of 0.3 mm and high-density single-walled carbon nanotubes (SWNTs) have been grown by thermal CVD and hot filament CVD, respectively. Raman spectra of the SWNTs reveal high crystalline as well as narrow diameter distribution.     

Possible tactics to improve the growth of single-walled carbon nanotubes by chemical vapor deposition

The growth time, growth mode and the method of preparing the supported catalysts play an important role in the growth of single-walled nanotubes (SWNTs). Their effects on the chemical vapor deposition (CVD) growth of SWNTs with MgO-supported catalysts were investigated in this study. It is shown that the growth rate of SWNTs was large during the initial few minutes of growth, however the quality of the tubes was low owing to the formation of many defects. Long term growth may favor the formation of tubes with high quality and high yield, but the introduction of other forms of carbon (impurities) is also unavoidable. There was a balance between the increase in yield and quality and sacrifice of the purity during growth of SWNTs. MgO-supported catalysts prepared by the co-precipitation method were found to be more effective for the synthesis of SWNTs than those prepared by the widely used impregnation method. The size and dispersion state of the catalyst were found to be crucial in enhancing the growth of SWNTs. In addition, growth on the surface of SWNTs over nanosized catalyst films was shown to be more favorable for the synthesis of tube products with higher quality, yield and purity.     

Thionine-mediated chemistry of carbon nanotubes

Thionine can be employed as a kind of useful functional molecule for the non-covalent functionalization of carbon nanotubes, as it shows a strong interaction with either SWNTs or MWNTs. Attachment of thionine molecules onto the sidewalls of carbon nanotubes would improve the solubility and lower the thermal stability of original carbon nanotubes. More importantly, it may functionalize the surface of carbon nanotubes with rich NH₂ groups and therefore open up more opportunities for the surface chemistry of carbon nanotubes. It has been proved that through the modification of small thionine molecules, other kinds of species such as cytochrome C and TiO₂ nanoparticles could be easily and selectively introduced onto the surface of carbon nanotubes. With this approach, SWNTs or MWNTs can be tailored with desired functional structures and properties.     

化学气相沉积法制备单壁碳纳米管研究进展

单壁碳纳米管的独特性能使其成为一种有着极大应用前景的新兴纳米材料,本文主要介绍了催化剂、裂解温度、载气等因素对化学气相沉积法（CVD）制备单壁碳纳米管的影响和采用化学气相沉积制备定向单壁碳纳米管方面的研究进展情况。     

Synthesis of Y-junction single-wall carbon nanotubes

Y-junction single-wall carbon nanotubes (SWNTs) are synthesized using controlled catalysts by chemical vapor deposition. Mo-doped Fe nanoparticles supported by aluminum oxide particles are used as catalysts for growing Y-junction single-wall carbon nanotubes. Distribution of Mo-doped Fe particles plays an important role in Y-junction formation. Transmission electron microscopy confirmed the formation of single-walled structures of Y-junctions with diameters of 2-5 nm. Radial breathing mode peaks in Raman spectra show that our sample has both metallic and semiconducting nanotubes, indicating the possible formation of Y-branching with different electrical properties. The different electrical properties of branch and stem can be utilized in nanoscale three terminal electronic devices. The growth mechanism of Y-junction SWNTs is proposed.     

Chemical modification of single-walled carbon nanotubes with peroxytrifluoroacetic acid

A new and simple method for chemical modification of single-walled carbon nanotubes (SWNTs) is presented. Purified SWNTs ropes prepared by CVD growth were reacted with peroxytrifluoroacetic acid (PTFAA) under ultrasonication. Samples before and after treatment were characterized using Raman, FTIR, UV/Vis/NIR, XPS, and AFM. Data from these experiments conclusively showed that, in addition to oxygen-based functional groups, trifluoroacetic groups were covalently attached to the SWNTs. Moreover, these modified SWNTs were shortened into ca. 300 nm in length in the same step of functionalization, resulting in exfoliation of nanotube ropes to yield small bundles and individual nanotubes. The resultant SWNTs were easily dispersed in polar solvents such as dimethylformamide, water and ethanol. The PTFAA treatment described herein should be useful to tailor SWNTs’ chemical and physical properties and to broaden their chemical processibility and reactivity.     

Growth and physical properties of individual single-walled carbon nanotubes

We have developed a versatile catalyst-assisted chemical vapor deposition (CVD) technique for the synthesis of single-walled carbon nanotubes (SWNTs) from discrete nickel nanoparticles (average diameter of 4.7 ± 1.4 nm). Atomic force microscopy (AFM), transmission electron microscopy (TEM) and micro-Raman spectroscopy are used to characterize these as-grown nanotubes. Using a conventional set-up, we are able to produce isolated SWNTs with a narrow diameter distribution (1.5 ± 0.5 nm). The advantages of such a versatile CVD method for the study of physical properties at the single nanotube level are illustrated by means of two prospective studies on vibrational and electrostatic properties of SWNTs.     

Catalyst deactivation in CVD synthesis of carbon nanotubes

A computational fluid dynamics (CFD) model with multistep chemical reactions was applied to predict the yield of multiwalled carbon nanotubes produced from our xylene-based chemical vapor deposition (CVD) reactor. Two-step xylene decomposition in the gas phase and catalytic decomposition of hydrocarbons to nanotubes on the growth surfaces were adopted based on exhaust-gas composition measurements. Using the experimentally obtained exhaust-gas concentrations, we conducted inverse calculations to determine apparent rate constants of the catalytic surface reactions. During the CVD process, catalyst deactivation was observed probably due to carbon formation on the catalyst surface. Its effect on the apparent rate constant was empirically correlated with a simple exponential equation. Applying the CFD model, we predicted the local yielding rate of nanotubes along the axis of the reactor. The total yield was then computed by integrating the local yielding rate over the growth surfaces and compared favorably (∼95%) with the experimental results. The proposed model is expected to help researchers optimize the process parameters to achieve the maximum nanotube yield.     

Online BET analysis of single-wall carbon nanotube growth and its effect on catalyst reactivation

A system combining pulse chemical vapor deposition (CVD) reaction and cryogenic gas sorption (BET) measurement capabilities was designed to allow the sequential synthesis and online analysis of single-wall carbon nanotubes (SWNTs). Cooling treatment in liquid nitrogen (77 K) during BET measurement was found to be efficient for restoring catalysts when deactivation occurs after carbon deposition. By this treatment, the methane conversion could be enhanced by up to seven times, such as from 5.8% to 42.6% mol. When the temperature changes from 850 °C to 77 K, the metal particles on the tip of nanotubes might contract and be separated from the graphite layer of the nanotubes, leading to more active sites on metal particles being exposed. The single point BET analysis of SWNT has been tested as an efficient method for the rapid online analysis of SWNTs produced by CVD.     

Liquid reagent CVD of carbon. I. Processing and microstructure

The processing and microstructure of carbon coatings deposited using liquid reagent CVD were studied. High density pyrolytic carbon coatings were successfully deposited on graphite and molybdenum substrates from benzene and cyclohexane precursors. Very high deposition rates were obtained. Examination via transmission electron microscopy showed that the deposits were of the desired turbostratic nodular structure with low texture.     

Materials science of carbon nanotubes: fabrication,integration, and properties of macroscopic structures of carbon nanotubes

In this Account, we summarize some of our recent studies on the materials properties of the carbon nanotubes (CNTs). The focus is on single-wall carbon nanotubes (SWNTs). We describe experiments on synthesis of SWNTs with controlled molecular structures and assembly of functional macroscopic structures. In addition, we present results on the electron field emission properties of macroscopic CNT cathodes.     

Improvement in growth yield of single-walled carbon nanotubes with narrow chirality distribution by pulse plasma CVD

A pulse plasma chemical vapor deposition (CVD) technique was developed for improving the growth yield of single-walled carbon nanotubes (SWNTs) with a narrow chirality distribution. The growth yield of the SWNTs could be improved by repetitive short duration pulse plasma CVD, while maintaining the initial narrow chirality distribution. Detailed growth dynamics is discussed based on a systematic investigation by changing the pulse parameters. The growth of SWNTs with a narrow chirality distribution could be controlled by the difference in the nucleation time required using catalysts comprising relatively small or large particles as the key factor. The nucleation can be controlled by adjusting the pulse on/ofF time ratio and the total processing time.     

Prediction of elastic properties for single-walled carbon nanotubes

Based on a link between molecular and solid mechanics, an analytical method was developed for modeling the elastic properties of single-walled carbon nanotubes (SWNTs). A SWNT is regarded as a continuum-shell model which is composed of the discrete molecular structures linked by the carbon-to-carbon bonds. The elastic properties were investigated for the SWNTs as a function of the nanotube size in terms of the chiral vector integers (n,m). The theoretical prediction on elastic properties agreed reasonably with the existing experiment and theoretical results. The present formulas are able to serve as a good approximation of the elastic properties for SWNTs.     

Controlling the diameter distribution of carbon nanotubes grown from camphor on a zeolite support

Single-wall and multi-wall carbon nanotubes (SWNTs and MWNTs, respectively) of controlled diameter distribution were selectively grown by thermal decomposition of a botanical hydrocarbon, camphor, on a high-silica zeolite support impregnated with Fe-Co catalyst. Effects of catalyst concentration, growth temperature and camphor vapor pressure were investigated in wide ranges, and diameter distribution statistics of as-grown nanotubes was analyzed. High yields of metal-free MWNTs of fairly uniform diameter (∼10 nm) were grown at 600-700 °C, whereas significant amounts (∼30%) of SWNTs were formed at 850-900 °C within a narrow diameter range of 0.86-1.23 nm. Transmission electron microscopy and micro-Raman spectroscopy reveal that camphor-grown nanotubes are highly graphitized as compared to those grown from conventional CNT precursors used in chemical vapor deposition.     

Effect of the reaction atmosphere on the diameter of single-walled carbon nanotubes produced by chemical vapor deposition

The influence of the reaction atmosphere on the type of single-walled carbon nanotubes (SWNT) grown during chemical vapor deposition (CVD) was investigated. Methane decomposition was catalyzed by Fe/MgO and Fe-Mo/MgO catalysts in argon, nitrogen and their mixtures. Nitrogen influences the carbon species significantly. The aggregation of iron nanoparticles in nitrogen results in the growth of N-doped carbon nanofibers on the Fe/MgO catalyst. A limited iron nanoparticle aggregation in nitrogen occurred on a Fe-Mo/MgO catalyst, on which there was an increase in the diameter of the SWNTs as the reaction atmosphere was more enriched in nitrogen, which was characterized by Raman spectroscopy. These results provide an experimental basis for the rational selection of the reaction atmosphere, and suggest an approach to control the size of the SWNTs in a CVD method.     

Synthesis of carbon nanotubes filled with Fe3C nanowires by CVD with titanate modified palygorskite as catalyst

Multi-walled carbon nanotubes (MWCNTs) have been successfully synthesized with titanate-modified palygorskite as catalyst and acetylene as carbon source by chemical vapor deposition (CVD) at high temperature. Transmission electron microscopy (TEM) studies showed that there were a lot of carbon nanotubes partially filled with elongated foreign material in their inner cavities. X-ray energy dispersive spectrum (EDS) analyses and selected area electron diffraction (SAED) investigations on the encapsulated material revealed that it was single crystalline iron carbide (Fe₃C) derived from ferric precursors in the mineral. The yield of carbon nanotubes was influenced by preparation temperature based on thermal gravimetric analyses (TGA). The relative quantity of Fe₃C nanowires was influenced by the temperature and the local structure of nanotubes upon TEM observations. A growth mechanism is also proposed in the paper.     

Chemical kinetics of catalytic chemical vapor deposition of an acetylene/xylene mixture for improved carbon nanotube production

Carbon nanotubes (CNTs) are synthesized by catalytic chemical vapor deposition (CCVD) from xylene, acetylene and their mixture. The addition of acetylene significantly increases the decomposition rate of xylene and decreases the benzene concentration in the effluent gas, as well as improving the quality of the CNTs obtained. There is a strong interaction between acetylene and xylene during the CCVD process. Various chemical components at different positions of the CVD reactor are classified and identified by mass spectrometry. Reaction kinetics constants are determined numerically based on the in situ measurement. Chemical kinetics of CCVD process is analyzed based on a detailed mechanism (88 species and 322 reactions), which successfully demonstrates the decomposition of the used carbon sources, and the synergistic effect of the addition of acetylene. The generation of hexagonal carbon rings from the dehydrogenation of benzene rings is described and discussed combined with the formation of CNT structures.     

Dysprosium-Catalyzed Growth of Single-Walled Carbon Nanotube Arrays on Substrates

In this letter, we report that dysprosium is an effective catalyst for single-walled carbon nanotubes (SWNTs) growth via a chemical vapor deposition (CVD) process for the first time. Horizontally superlong well-oriented SWNT arrays on SiO₂/Si wafer can be fabricated by EtOH-CVD under suitable conditions. The structure and properties are characterized by scanning electron microscopy, transition electron microscopy, Raman spectroscopy and atomic force microscopy. The results show that the SWNTs from dysprosium have better structural uniformity and better conductivity with fewer defects. This rare earth metal provides not only an alternative catalyst for SWNTs growth, but also a possible method to generate high percentage of superlong semiconducting SWNT arrays for various applications of nanoelectronic device.     

Selective synthesis of carbon nanotubes and nanocapsules using naphthalene pyrolysis assisted with ferrocene

Selective synthesis of well aligned multi-walled carbon nanotubes (MW-CNT) and multi-shelled carbon nanocapsule (MS-CNC) using pyrolysis of naphthalene with the presence of ferrocene was experimentally examined. With higher mole fraction of naphthalene to ferrocene, more MW-CNTs could be synthesized due to higher concentration of carbonaceous precursors emerging from the decomposed naphthalene. Based on kinetic analysis, at lower temperature, MW-CNTs could preferably be synthesized due to the controlled supply of carbonaceous clusters to get onto the surface of Fe clusters. On the other hand, at temperature higher than 900 °C the Fe clusters become more active to catalyze carbonaceous precursors to undergo self assembling process of MS-CNCs. With cheaper cost of naphthalene compared with other high-value hydrocarbons, usage of naphthalene would provide an advantage of reasonably economical synthesis of MW-CNT or MS-CNC.