Josh Holt

Separation of Empty and Water-Filled Single-Wall Carbon Nanotubes

The separation of empty and water-filled laser ablation and electric arc synthesized nanotubes is reported. Centrifugation of these large-diameter nanotubes dispersed with sodium deoxycholate using specific conditions produces isolated bands of empty and water-filled nanotubes without significant diameter selection. This separation is shown to be consistent across multiple nanotube populations dispersed from different source soots. Detailed spectroscopic characterization of the resulting empty and filled fractions reveals that water filling leads to systematic changes to the optical and vibrational properties. Furthermore, sequential separation of the resolved fractions using cosurfactants and density gradient ultracentrifugation reveals that water filling strongly influences the optimal conditions for metallic and semiconducting separation.

Unraveling the 13C NMR Chemical Shifts in Single-Walled Carbon Nanotubes: Dependence on Diameter and Electronic Structure

The atomic specificity afforded by nuclear magnetic resonance (NMR) spectroscopy could enable detailed mechanistic information about single-walled carbon nanotube (SWCNT) functionalization as well as the noncovalent molecular interactions that dictate ground-state charge transfer and separation by electronic structure and diameter. However, to date, the polydispersity present in as-synthesized SWCNT populations has obscured the dependence of the SWCNT (13)C chemical shift on intrinsic parameters such as diameter and electronic structure, meaning that no information is gleaned for specific SWCNTs with unique chiral indices. In this article, we utilize a combination of (13)C labeling and density gradient ultracentrifugation (DGU) to produce an array of (13)C-labeled SWCNT populations with varying diameter, electronic structure, and chiral angle. We find that the SWCNT isotropic (13)C chemical shift decreases systematically with increasing diameter for semiconducting SWCNTs, in agreement with recent theoretical predictions that have heretofore gone unaddressed. Furthermore, we find that the (13)C chemical shifts for small diameter metallic and semiconducting SWCNTs differ significantly, and that the full-width of the isotropic peak for metallic SWCNTs is much larger than that of semiconducting nanotubes, irrespective of diameter.