Synthesis of N-doped SWNT using the arc-discharge procedure

doi:10.1016/j.cplett.2004.02.005

Chemical Physics Letters

Volume 387, Issues 1–3, 21 March 2004, Pages 193-197

https://doi.org/10.1016/j.cplett.2004.02.005 Get rights and content

Abstract

Single-walled nitrogen doped nanotubes were prepared using two novel approaches in an arc-discharge process. In both cases a nitrogen-rich precursor was introduced into the anode rods together with graphite and the catalysts. The nitrogen rich precursors were organic and inorganic, respectively. Both synthesis routes gave nanotubes with a nitrogen concentration of a maximum of 1%, determined using electron energy loss spectroscopy (EELS) coupled with transmission electron microscopy (TEM). All samples were characterized with scanning electron microscopy (SEM), TEM, and high-resolution transmission electron microscopy (HRTEM).

Introduction

Carbon nanotubes have attracted much attention since their discovery by Iijima [1]. They are expected to bring significant breakthroughs in the electronic and mechanical engineering of materials. Doping carbon nanotubes with other chemical elements could be a particular interesting way for tuning these properties [2], [3]. The electronic properties of single-walled carbon nanotubes (SWNTs) vary between semiconducting and metallic, depending on their helicity [4]. Nitrogen-doped nanotubes are predicted to be either metallic or small gap semiconductors depending on the relative positions of the nitrogen and carbon atoms [5], [6]. SWNTs are known to have extraordinary mechanical properties with a Young’s modulus of 1.25 Tpa [7]. Based on theoretical calculations, canonical nanotube stoichiometries on CN and C₃N₄ have been predicted stable [8]. C₃N₄, iso-electronic to Si₃N₄, has been predicted to have hardness comparable to that of diamond [9].

Stéphan et al. [10] initiated the synthesis of doped multi-walled nanotubes (MWNT) in 1994; they produced boron–nitrogen doped multi-walled carbon nanotubes using the arc-discharge method. Since then, a lot of work has been carried out concerning the direct synthesis of nitrogen and/or boron doped MWNTs in arc-discharge experiments [11], [12], [13]. The synthesis of doped single-walled nanotubes in arc-discharge experiment is not easily achieved. A few reports deal with the synthesis of nitrogen-doped SWNTs; the tubes are made by evaporation of the graphite rod together with the catalyst in a nitrogen gas-containing atmosphere [14].

Otherwise, the formation of single-walled CB_x and CN_y using substitution reactions with single-walled carbon nanotubes (C-SWNT) as templates have been described up to now [15]. In this work, we have chosen to take new approaches for the synthesis of nitrogen and/or boron doped SWNTs in arc-discharge experiments. Instead of carrying out the experiment in a nitrogen rich atmosphere we have added nitrogen-rich organic- and inorganic precursors into the graphitic anode-rod.

Section snippets

Experimental

Three different processes have been worked out:

Synthesis process 1: the purpose of this series of experiments was to synthesize nitrogen doped SWNTs. Graphite (1–2 μm, Aldrich) was mixed with melamine (C₃N₆H₆, 99%, Aldrich) and Ni/Y catalyst (Ni: 99.999%, ∼100 mesh, Aldrich; Y: 99.9%, ∼40 mesh, Aldrich; Ni=Y=0.6 w/o) and packed into the drillings of the anode rods. Samples were produced with amounts of melamine corresponding to 1, 2, 4 and 8 at.% nitrogen (denoted sample 1, 2, 3 and 4). The

Results and discussion

In Fig. 1 are shown representative SEM images from the collaret (Fig. 1a) and for the soot (Fig. 1b) of sample 4. The soot consisted of white–greyish crystalline layer which was identified by means of medium-infrared spectroscopy (MIR) to consist of pure melamine (not shown here), indicating that a part of the melamine evaporates before participating in the reaction. This might not be that surprising since melamine has an evaporation temperature which is several thousand degrees lower than

Conclusion

It was shown that it is possible to directly synthesize nitrogen-doped nanotubes in an arc-discharge experiment using nitrogen-rich organic and inorganic precursors. This opens new routes for the synthesis of doped SWNTs in high temperature type experiments like arc-discharge and laser-ablation. This approach is seen to be promising though further work has to be carried out for the optimization of this type of experiments. This work demonstrates the possibility of designing experiments for

Acknowledgements

M.G. acknowledges the EC-TMR network FUNCARS for financial support. O.S. acknowledges the EC-IHP network ‘fullerene-like materials’ for financial support. Dr. M. Holzinger (UMII) is acknowledged for valuable discussions and D. Maurin (UMII) for the infrared measurements.

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Synthesis of N-doped SWNT using the arc-discharge procedure

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Conclusion

Acknowledgements

Synth. Met.

Solid State Commun.

Chem. Phys. Lett.

J. Non-Cryst. Solids

Nature

Appl. Phys. A

Phys. Rev. Lett.

Appl. Phys. Lett.

Phys. Rev. B

Solid State Commun.

Science