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Direct functionalization of pristine single-walled carbon nanotubes by diazonium-based method with various five-membered S- or N- heteroaromatic amines

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Abstract

Reactivity of five-membered, variously substituted, heteroaromatic diazonium salts was studied toward pristine single-walled carbon nanotubes (SWCNTs), prepared by high-pressure CO conversion (HiPCO) method. Average size range of individual HiPCO SWCNTs was 0.8–1.2 nm (diameter) and 100–1,000 nm (length). Functionalizations were performed by a one-pot diazotization–dediazotization method with methyl-2-aminothiophene-3-carboxylate, 2-aminothiophene-3-carbonitrile, 2-aminoimidazole sulfate, or 3-aminopyrazole in acetic acid using sodium nitrite at room temperature or by heating. According to Raman and Fourier transform infrared spectroscopy, all used heterocyclic diazonium salts formed a covalent bond with SWCNTs and yielded new kinds of five-membered heterocycle-functionalized SWCNTs. Methyl-2-thiophenyl-3-carboxylate-functionalized SWCNTs formed a highly soluble, stable dispersion in tetrahydrofuran (THF), 3-pyrazoyl-functionalized SWCNTs in ethanol, and 2-imidazoyl- or 2-thiophenyl-3-carbonitrile-functionalized SWCNTs in ethanol and THF. The thermogravimetric analysis as well as energy-filtered transmission electron microscopy imaging of the products confirmed the successful functionalization of SWCNTs.

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Acknowledgments

Authors thank the Academy of Finland, Finnish Foundation for Technology Promotion (TEKES), the Tauno Tönning Foundation and the Faculty of Science of the University of Oulu for the financial support. Jouko Paaso is thanked for the help with EFTEM imaging and Riku Mattila for the TGA measurements.

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  1. Department of Chemistry, University of Oulu, P. O. Box 3000, 90014, Oulu, Finland

    Heli Leinonen & Marja Lajunen

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  1. Heli Leinonen
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  2. Marja Lajunen
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Correspondence to Marja Lajunen.

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Leinonen, H., Lajunen, M. Direct functionalization of pristine single-walled carbon nanotubes by diazonium-based method with various five-membered S- or N- heteroaromatic amines. J Nanopart Res 14, 1064 (2012). https://doi.org/10.1007/s11051-012-1064-5

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