Reproducibility and Efficiency of Carbon Nanotube End‐Group Generation and Functionalization

• Published in: European Journal of Organic Chemistry Vol. 2009; no. 26; pp. 4421 - 4428
• Main Authors: Andersson, Claes‐Henrik, Grennberg, Helena
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag 01.09.2009; Wiley-VCH
• Subjects: Amidation; Chemistry; Condensed matter: structure, mechanical and thermal properties; Esterification; Exact sciences and technology; Functionalization; Kemi; Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals; Nanotechnology; Nanotubes; NATURAL SCIENCES; NATURVETENSKAP; Physics; Structure of solids and liquids; crystallography; End group; Thermogravimetry; Nanotubes; Carbon nanotubes; Molecular interaction; Carboxylic acids; Experimental study; Raman spectroscopy; Nitric acid; Alkylation; Amidation; Esterification; Functionalization; Acyl chloride; Soluble compound; Oxidation; NMR spectroscopy; Chemical synthesis; Carboxylates; Nanotechnology
• ISSN: 1434-193X; 1099-0690; 1099-0690
• DOI: 10.1002/ejoc.200900534

In a systematic fashion, several methods for esterification and amidation of single‐walled carbon nanotubes have been evaluated with focus on efficiency and reproducibility in forming covalently functionalized products soluble in organic media. The outcome of transformations was determined using IR, Raman and NMR spectroscopy and by thermogravimetric analysis (TGA). Amidation proceeding via a SWNT‐(COCl)n intermediate yielded the expected covalent product, whereas carboxylate salt formation dominated with other attempted methods. Esterification was achieved via the acyl chloride method and via alkylation of SWNT‐(COO–)n, the latter being the more efficient method. A non‐covalent solubilizing interaction was obtained for RNH2 but not for ROH (R = octadecyl), proving that the most important non‐covalent interaction between oxidatively cleaned SWNTs and octadecylamine is a salt formation. The outcome of the secondary functionalization of carboxyl units is highly reproducible for experiments carried out on the same batch of SWNT‐(COOH)n. Normalization of the outcome of the secondary functionalization to the composition of the different batches of starting materials reveals an overall high reproducibility of the secondary functionalizations. The differences in outcome related to different commercial SWNT batches from the same synthetic procedure is negligible compared to that resulting from differences in overall carboxyl content after the primary HNO3 oxidative cleaning step. Hence, the composition of purified SWNT starting materials always needs to be assessed, in particular before drawing any conclusions concerning differences in outcome from reaction systems involving different sources of SWNT material. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) Can we trust chemistry? Numerous methods for covalent functionalization of SWNTs have been reported in the literature. However, only a few studies have been concerned with the reproducibility and relative efficiency of these methods. Moreover, the fact that all batches of SWNTs and oxidized SWNTs are essentially different is sometimes neglected. This surveydeals with these important topics.