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Applied Physics A
Materials Science & Processing
g.z. shen1,2, u d. chen1 k.-b. tang1 y.-t. qian1 c.-j. lee2
High-yield solvo-thermal synthesis of carbon nanotubes from sp3 hydrocarbons
of Chemistry and Structure Research Laboratory, University of Science and Technology of China, Hefei, 230026, P.R. China 2 Department of Nanotechnology, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791, Korea
Received: 10 March 2004/Accepted: 6 May 2004 Published online: 9 July 2004 • © Springer-Verlag 2004
ABSTRACT Carbon nanotubes have been successfully synthesized by a high-yield solvo-thermal process by using sp3 hydrocarbons as the carbon sources and solvents. Studies have shown that sp3 -hydrocarbons used in the process not only act as the carbon sources and solvents, but also increase the yield of carbon nanotubes dramatically. Besides carbon nanotubes, some interesting carbon materials, such as carbon “olives”, carbon hollow spheres, carbon microtubes and “crossed” carbon nanotubes, were also obtained by the present route. PACS 61.10.Nz;
Research in the ﬁeld of carbon nanotubes has undergone an explosive growth since their discovery by Iijima . In carbon nanotubes, the parallel layers of sp2 carbon atoms are arranged such that the long axis of the rolled-up cylinders is parallel to the layers. According to theoretical predictions, carbon nanotubes may process extraordinary physical and chemical properties. These include extremely high strength and ﬂexibility  as well as strong capillarity properties , and they may also be used as nanoscale electronic devices consisting entirely of carbon . Several techniques, such as electric arc-discharge , laser evaporation  and catalytic decomposition of hydrocarbons,  have been successfully developed to synthesize multi-wall nanotubes. One of the main challenges is to ﬁnd a way to produce nanotubes on a large scale and at low cost. In this respect, the catalyst method seems to be the best, because of the lower reaction temperature and the lower cost of production. Moreover, the puriﬁcation step has been optimised to eliminate the catalyst and the thermal decomposition of hydrocarbons . Unfortunately, complex equipments or procedures are needed to produce carbon nanotubes. As another important catalyst route, the solvo-thermal route avoids the above disadvantages and can be carried out under mild conditions [9–12].Most of the reports on the solvo-thermal process used sp2 -structural carbon as carbon stocks for the synthesis of sp2 hybrid carbon
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nanotubes. The yield of carbon nanotubes by using these sp2 hydrocarbons is very low (< 35%). Very recently, our group successfully synthesized carbon nanotubes using ethanol, an sp3 -structural carbon source in an ethanol thermal reduction process, and the yield of carbon nanotubes was largely improved (about 80%) by using sp3 -structural carbons . This result encouraged us to develop a more efﬁcient, simpler and higher yield route to obtain carbon nanotubes and other carbon nanomaterials. In this study, we report on the large-scale synthesis of sp2 carbon nanotubes via a high yield solvo-thermal route by using sp3 -hydrocarbons, such as pentane, hexane, heptane, octane, etc. as the carbon sources. In this process, the yield of carbon nanotubes can be increased to higher than 90%. The sp3 hydrocarbons not only act as the carbon sources and solvents to synthesize sp2 -carbon nanotubes, but also increase the yield of carbon nanotubes dramatically (> 90%). Some interesting carbon materials, such as carbon “olives”, carbon hollow spheres, carbon microtubes and “crossed” carbon nanotubes, were also obtained by using sp3 hydrocarbons.
The catalyzer precursors are prepared according to the literature . In a typical process, 0.15 g of catalyzer precursor was put into a 25-mL stainless steel tank, and then the tank was ﬁlled with hydrocarbons (pentane, hexane, heptane, octane, and so on) to about 70% of its total volume. The tank was soniﬁcated for about 10 min to make the catalyzer precursor disperse well. After soniﬁcation, 2 g of Na was added and the tank was maintained at 450 ◦ C for about 10 h. After cooling to room temperature, the resulting black precipitate was washed several times with alcohol, dilute acid, and distilled water. After washing the precipitate was then vacuum dried at 60 ◦ C for 4 h.
3 Results and discussion
The purity and phase structure of the as-prepared products were obtained by XRD (X-ray diffraction), which was recorded by a Philips Xpert Pro Super X-ray diffractometer with Cu K α radiation (λ = 1.5418 Å). Two intense peaks were observed in the XRD pattern (ﬁgure not shown here), which can be indexed to hexagonal graphite with cell constants comparable to the reported values (JCPDS 41-1487).
Table 1 lists the relationship between different carbon sources and the morphologies of the ﬁnal products. we can see that most of the carbon nanotubes produced from the solvo-thermal process are curved and some carbon nanotubes may even curve into ring-like structure (Fig. When hexane was used. b TEM image of carbon “olives”. The typical TEM images of the as-prepared products showed that the wire-like nanostructures under FE-SEM observation are actually carbon nanotubes (Fig. The FE-SEM image obtained (Fig. Figure 2d shows the TEM image of the “crossed” carbon nanotubes obtained. From the TEM images. Figure 2a shows the SEM image of a sample made by using pentane as the carbon source. that have a diameter of about 200 nm. c TEM image of several long curved carbon nanotubes. which reveals their hollow structures. some interesting carbon “olives” are also obtained. respectively. carbon hollow TABLE 1 Relationship between the carbon sources and the morphology of the products spheres. carbon hollow spheres and carbon microtubes were also observed in addition to carbon nanotubes. d TEM image of ring-like carbon nanotubes (the inset TEM image shows a catalyst particle present in the tip of the carbon nanotubes) FIGURE 2 a SEM image of obtained carbon “olives”. The grain size of a typical “olive” is about 5 µm. which shows the rod-like crystals under FE-SEM observation are actually carbon nanotubes. 1b and c). These carbon nanotubes can grow as long as 4 µm.524 Applied Physics A – Materials Science & Processing Hydrocarbons Products Pentane Carbon nanotubes Carbon olives Hexane Carbon nanotubes Hollow spheres and Microtubes Heptane Carbon nanotubes Octane Carbon nanotubes Crossed nanotubes The panoramic morphologies of the carbon nanotubes obtained were examined by FE-SEM. Further TEM images (Fig. 7500B) operated at an acceleration voltage of 10 kV. some interesting carbon materials. Further characterization about the prepared products was performed on a Hitachi H-800 transmission electron microscope with an accelerating voltage of 200 kV. Figure 2c shows the obtained carbon hollow spheres and carbon microtubes. and crossed carbon nanotubes. It can be seen that besides carbon nanotubes (marked with arrows). Besides carbon nanotubes. All these inter- FIGURE 1 a FE-SEM image of a prepared sample. b TEM image of prepared sample. such as micrometer carbon “olives”. These images reveal that the carbon nanotubes produced in the present solvothermal process are with an inner diameter of 10 – 40 nm and outer diameter of 40 – 60 nm. have also been obtained by the present solvo-thermal route. which was performed on a ﬁeld-emission microscope (JEOL. carbon microtubes. 1d). d TEM image of “crossed” carbon nanotubes . 1a) by mounting the solid samples on a copper mesh without any dispersion treatment. The sizes of the carbon hollow spheres range from 100 to 1000 nm and the diameter of the carbon microtubes is about 1 µm. c TEM images of carbon hollow spheres (shown with arrows) and carbon microtubes. which shows that largescale rod-like crystals are obtained from the present route. reveals that most of the prepared products (> 90%) are wire-like nanostructures with typical lengths in the range of 0. 2b) reveals the hollow structure of the carbon “olive”.5 – 5 µm and widths of about 40 nm.
which resolves the shortcoming of previously reported solvo-thermal process. the use of sp3 hydrocarbons also increases the yield of carbon nanotubes. The solution-based catalyst precursors routes have recently attracted much more attention due to their low-cost and the advantages of easily tuning the composition and concentration of the catalysts [14. FIGURE 4 TEM image of catalyst particles ﬁlled carbon nanorods .0 kJ mol−1 . 1d inset). heptane. this route can be used to prepare metal. it is reasonable to assume that the present solvo-thermal process involved the ﬁrst reduction of catalyst precursor by sodium to produce catalyst particles. and the formation of diamond is impossible and only carbon nanotubes are formed. So the present route may provide a novel onestep low-cost method to synthesize metal (alloy)-ﬁlled carbon nanotubes or carbon nanorods. simply by an choosing appropriate catalyst precursor. These results are in good agreement with our previous reports .25 kJ mol−1 . Without a catalyst. − 0. and 16. no carbon nanotubes were obtained. most of the reactions are not thermodynamically spontaneous. Based on the above analysis. respectively for pentane. the reduction of CCl4 by sodium is highly thermodynamically spontaneous (∆G 0 (diamond) = − 99. and further studies of them are under way. 4 Conclusions In summary. it is difﬁcult to say that the present route is controlled by the VLS mechanism as the reaction conducted in the closed system is quite complex and the detailed growth mechanism undoubtedly needs further study. These sp3 -hydrocarbons act not only as the carbon sources. By FE-SEM and TEM observations. the yield of carbon nanotubes was calculated to be as high as 90%. catalyst. according to the free energy calculations (∆G 0 are − 8. which can be produced by adjusting the amount of catalyst precursor. 15].4 kJ mol−1. 18]. But in the present synthetic process. etc. By choosing an appropriate catalyst precursor.(alloy-) ﬁlled carbon nanotubes and carbon nanorods. The successful production of sp2 carbon nanotubes from sp3 hydrocarbons provides a good example of the study of the transformation from sp3 -bonded carbon to sp2 bonded carbon. in which sp2 -hydrocarbons were used as the carbon sources.2 kJ mol−1 ). In the solvo-thermal process. but also as the solvent. Solvo-thermal synthesis of carbon nanotubes from sp3 hydrocarbons 525 esting carbon materials may have some interesting properties and may have great potential applications in various ﬁelds. 8. which decreases the cost of large-scale production of carbon nanotubes and allows the reaction to be performed under mild conditions. The typical phenomenon of the VLS mechanism is the presence of a catalyst particle at the end of each carbon nanotube . Figure 4 shows a typical TEM image of the as-prepared catalyst-particle-ﬁlled carbon nanorods. the yields of these novel carbon materials can be greatly increased and this work (and the characterization of these carbon materials) is still under way in our group.  reported the synthesis of diamond powder using CCl4 in a similar process. such as temperature. The advantage of the present solvo-thermal process is the use of sp3 -hydrocarbons.SHEN et al. The formation of sp2 -carbon nanotubes was further conﬁrmed by the Raman procedure. reaction time. according to free energy calculations. and there are two strong peaks at 1345 cm−1 and 1590 cm−1 . Another advantage of the present solvo-thermal process is the ability to produce catalyst-particle ﬁlled carbon nanotubes FIGURE 3 Raman spectrum of products which shows two graphite peaks at 1345 cm−1 and 1590 cm−1 and carbon nanorods. In our present process. although catalyst particles can be detected at the end of the carbon nanotubes (Fig. Li et al. a novel high-yield solvo-thermal route has been used to prepare carbon nanotubes by using sp3 -hydrocarbons as the carbon sources. By carefully optimizing the experimental factors. Previously. Figure 3 shows the Raman spectrum.. followed by the growth of carbon nanotubes from the catalyst particles by pyrolysis of hydrocarbons under self-generated high pressure. In the synthesis of diamond.4 kJ mol−1. The domain growth mechanism in this route is the well-known vapor-liquid-solid (VLS) mechanism. hexane. indicating the graphite structure of the carbon nanotubes [17. octane). which is favorable for the formation of diamond.
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