Role of Adsorbed Surfactant in the Reaction of Aryl Diazonium Salts with Single-Walled Carbon Nanotubes
| Autor: | Paul W. Barone, Michael S. Strano, Changsik Song, Thomas P. McNicholas, Qing Hua Wang, Jonathan D. Mendenhall, Shangchao Lin, Daniel Blankschtein, Jingqing Zhang, Andrew J. Hilmer, Daniel A. Heller |
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| Rok vydání: | 2012 |
| Předmět: |
Inorganic chemistry
Selective chemistry of single-walled nanotubes Salt (chemistry) chemistry.chemical_element Carbon nanotube Molecular Dynamics Simulation Photochemistry law.invention Surface-Active Agents chemistry.chemical_compound Bromide law Electrochemistry General Materials Science Sodium dodecyl sulfate Spectroscopy chemistry.chemical_classification Nanotubes Carbon Aryl Chemical modification Diazonium Compounds Surfaces and Interfaces Condensed Matter Physics chemistry Salts Adsorption Carbon |
| Zdroj: | Langmuir. 28:1309-1321 |
| ISSN: | 1520-5827 0743-7463 |
| Popis: | Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to stabilize the diazonium ion near the nanotube surface. Such Coulombic and surfactant packing effects offer promise toward employing surfactants to controllably functionalize carbon nanotubes. |
| Databáze: | OpenAIRE |
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