Using X-ray induced photoelectron spectroscopy, the influence of Brønsted acids, namely sulfuric, nitric, and hydrochloric acid on the electronic properties of single-walled carbon nanotubes (SWCNTs) was investigated. Doping effects were monitored by changes in binding energy of the C 1s core level of the nanotubes. For all three acids, an acceptor type doping of the SWCNTs was observed by a shift of the C 1s core level towards lower binding energies. The inferred change of the Fermi-level position was 0.5 eV in the case of H 2 SO 4 , 0.2 eV in the case of HNO 3 , and 0.1 eV in the case of HCl. For HNO 3 and HCl the doping was found to be unstable. The S 2p, N 1s, and Cl 2p core level spectra of the corresponding acid showed spectral features which can be attributed to the respective oxidation state of these anions in the acid, indicating that doping was induced by intercalation.

A new reaction sequence for the chemical functionalization of single-wall carbon nanotubes (SWNTs) consisting of the nucleophilic addition of t-BuLi to the sidewalls of the tubes and the subsequent reoxidation of the intermediates t-Bu(n)SWNT(n-) leading to t-Bu(n)SWNT was developed. During the formation of the t-Bu(n)SWNT(n-), a homogeneous dispersion in benzene was formed due to the electrostatic repulsion of the negatively charged intermediates causing debundling. The entire reaction sequence can be repeated, and the degree of functionalization of the products (t-Bu(n))(m)SWNT (m = 1-3) increases with increasing m. Degrees of functionalization expressed as the carbon-to-addend ratio of up to 31 were reached. The reaction was studied in detail by photoelectron spectroscopy, Raman spectroscopy, and scanning tunneling microscopy (STM). The C 1s core level spectra reveal that the nucleophilic attack of the t-BuLi leads to negatively charged SWNTs. Upon oxidation, this negative charge is removed. The valence band spectra of the functionalized samples exhibit a significant reduction in the pi-derived density of states. In STM, the covalently bonded t-butyl groups attached to the sidewalls have been visualized. Raman spectroscopy reveals that addition of the nucleophile to metallic tubes is preferred over the addition to semiconducting tubes.

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