Covalent functionalization of single-walled carbon nanotubes alters their densities allowing electronic and other types of separation

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Research areas:
  • Uncategorized
Year: 2008
Type of Publication: Article
  • Woo-Jae Kim, Chang Young Lee Nitish Nair
Journal: Journal of Physical Chemistry C Volume: 112
Number: 19 Pages: 7326-7331
Month: MAY 15 2008
PT: J; TC: 27; UT: WOS:000255649500004
We show that covalently attached functional groups can alter the densities of individual single-walled carbon nanotubes (SWNTs) in a predictable and highly controllable manner. A volume-additivity model based on molecular group contributions can be used to estimate the density difference between 4-hydroxyphenyl-functionalized and nonfunctionalized HiPco SWNTs as approximately 98.3 kg/m(3), compared with 97.9 kg/m(3) measured by density-gradient centrifugation. Conversely, the estimated density difference between the (6,5) (0.75 nm diameter) and (9,8) (1.17 nm diameter) SWNTs is smaller at 23.4 kg/m(3). We conclude that covalent functionalization can provide an effective handle to separate particular SWNTs from a typical diameter distribution. We show that SWNT mixtures in which metallic SWNTs have been selectively reacted produce two distinct density fractions corresponding to functionalized metallic and pure semiconducting SWNTs. The results were confirmed by Raman spectroscopy, where the high-density fractions exhibit an increased disorder mode with a corresponding decrease in intensity for the low-density fraction. This method also allows for the first independent measure of (n,m) SWNTs having different chemical conversions with functional groups, which will allow for a more rigorous analysis of SWNT chemistry than is possible with uncalibrated spectroscopies such as Raman or photoluminescence.