Carbon 44 (2006) 18451869 www.elsevier.

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Letters to the Editor

In situ synthesis of super-long Cu nanowires inside carbon nanotubes with coal as carbon source
Zhiyu Wang, Zongbin Zhao, Jieshan Qiu
*
Carbon Research Laboratory, School of Chemical Engineering, Center for Nano Materials and Science, State Key Lab of Fine Chemicals, Dalian University of Technology, 158 Zhongshan Road, P.O. Box 49, Dalian 116012, China Received 23 July 2005; accepted 1 April 2006

Keywords: Carbon nanotubes; Coal; Arc discharge; Electron diraction; Transmission electron microscopy

Nano-sized copper wires have received considerable attention because of their potential applications in next generation electronic nanodevices in future [1,2]. Up to now, a number of approaches including vapor depositions [1], template synthesis [2,3], solution-phase reactions [4,5] and vaporsolid reaction growth (VSRG) [6] have been developed for making copper nanowires. Despite of the great progresses, some tough problems related to the quality of copper nanowires such as poor oxidation resistance and crystallinity, short length, and nonlinear morphology still need to be addressed [17]. Carbon nanotubes (CNTs) are believed to be a good template for making Cu nanowires with perfect 1D morphology and good stability, and this idea has been tested by arc discharge in hydrogen [8] or microwave plasma-assisted CVD [9]. Here, we report a simple arc-discharge method for in situ synthesis of Cu-lled CNTs with coal as carbon precursor. It has been found that super-long crystalline Cu nanowires, of which the average length is over several tens of micrometers and the aspect ratio is ca. 200360, can be directly fabricated inside the CNTs in large quantity. The preparation experiments were conducted in a traditional DC arc-discharge reactor in argon atmosphere. A high purity graphite tube (10 mm OD, 6 mm ID) lled with

Corresponding author. Fax: +86 411 8899 3991. E-mail address: jqiu@dlut.edu.cn (J. Qiu).

a mixture of anthracite coal (from Yunnan Province, China) and CuO powders (6150 lm in size) was used as consuming anode while the cathode was a high purity graphite rod (15 mm OD). The weight ratio of CuO to coal powder in the mixture was 1:9. For each run that normally lasted about 15 min, the arc discharge was conducted with DC current of 70 A and voltage of 20 V in argon at 0.08 0.09 MPa. After the arc discharge was over, the deposits on the cathode were collected and examined using transmission electron microscopy (TEM, JEM-2000EX; HRTEM, Philips Tecnai G2 20). Fig. 1a shows a typical low magnication TEM image of the as-prepared sample, revealing the successful synthesis of CNT-encapsulated nanowires with a length of over several tens of micrometers. It has been found that in some nanowires there are several distorted defects such as kinks and curls, between which the distance varies in a range from hundreds of nanometers to several micrometers. Further high magnication TEM examination (see Fig. 1b) shows that the CNTs are completely lled with continuous nanowires with a diameter ca. 3080 nm. The aspect ratio of these carbon coated nanowires is 200360, which is much higher than those reported previously in the literature [8,9]. The repeated experiments indicate that on average, more than 4050% of the as-prepared CNTs are lled with nanowires, as can be seen in Fig. 2. The selected area electron diraction (SAED) patterns taken from the nanowires between the distorted section are shown in insets of Figs. 2b and d, showing the diraction as regular arrays of sharp spots together with the short arc due to the

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Letters to the Editor / Carbon 44 (2006) 18451869

Fig. 1. TEM images of Cu-lled CNTs prepared with coal as carbon source: (a) low magnication image showing super-long Cu nanowires in the central cavity of CNTs; (b) high magnication image of three Cu-lled CNTs displayed in (a), indicated by white arrow.

Fig. 3. HRTEM image of one Cu-lled carbon nanotube.

Fig. 2. TEM images and SAED patterns of the Cu-lled CNTs: (a,c) showing most of the CNTs are lled with Cu nanowires. Corresponding magnied images of the section marked by a rectangle in (a) and (c) are shown in (b) and (d), respectively; Insets in (b) and (d) are corresponding SAED patterns of the Cu-lled CNTs.

(0 0 2) diraction of hexagonal graphite, which gives evidence of the presence of well-developed monocrystalline

structure in the nanowires. These patterns are in good agreement with the typical diraction pattern of a face-centered cubic (fcc) Cu along the h0 1 1i zone axis, for clarity reasons, some diraction spots are indexed and labeled in the gures. Further HRTEM examination on a typical 30 nm diameter Cu-lled CNT is shown in Fig. 3, in which monocrystals have been observed in long-range order, as well as the outside coating consisting of well-oriented graphite layers (about 20 layers with a separation of ca. 0.34 nm). The distance between the lattice fringes of encapsulated crystals is measured to be ca. 0.21 nm that is

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identical to the d-spacing of (1 1 1) atomic plane of Cu (fcc, d1 1 1 = 0.2087 nm). The results presented above lead one to believe that the nanowires encapsulated inside the CNTs are pure copper nanowires consisting of several long monocrystals. The formation and growth of the Cu-lled CNTs does not follow the well-accepted dissolutionprecipitation scheme for graphitization [10] simply because copper does not form stable carbide phase [11] and carbon solubility in bulk copper is rather poor [12]. With the aim of working out and understanding the mechanism involved in the formation process of Cu-lled CNTs, comparison tests with high purity graphite powders as carbon source instead of coal powders were performed under identical conditions, however, few lled CNTs were observed in the nal products. This means that coal plays a crucial role in the growth of Cu-lled CNTs in the present work. It is known that coal is a molecular solid consisting of a great number of irregular polymerized polycyclic aromatic hydrocarbon units [13,14], which are joined together by aliphatic benzylic or alkyl ether links or other bridging functional groups [1315]. It can be easily envisaged that these weak binding linkages can be readily broken once the coal is injected into the high temperature zone of the arc plasma [1417], releasing a large quantity of reactive fragments of hydrocarbon molecules such as alkyne and aromatic species [8,13,15,16]. These reactive species would serve as building blocks for CNT formation and would enhance the growth rate of CNTs [17,18]. In addition, it has been proposed that the aromatic species could interact with Cu clusters at high temperature to form carbon layers around copper particles because of the dehydrogenation reactions [19]. With these information in mind, it is reasonable for one to assume that various reactive aromatic species generated in situ from the fast pyrolysis of coal in arc plasma may be responsible for the in situ formation of hollow and Cu-lled CNTs. We believe that the approach described here, after being further optimized, will lead to mass production of Cu nanowires with excellent performance, which will oer more opportunities for studying the physical and electronic properties of Cu nanowires.

Century Excellent Talents in University by the Education Ministry of China (No. NCET-04-0274). References
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Acknowledgements This work was partly supported by the National Science Foundation of China (Nos. 20276012 and 20376011), the Natural Science Foundation of Liaoning Province of China (No. 2001101003), and the Program for New