Variations in bile salt surfactant structure allow tuning of the sorting of single-wall carbon nanotubes by aqueous two-phase extraction.

Being some of the most efficient agents to individually solubilize single-wall carbon nanotubes (SWCNTs), bile salt surfactants (BSS) represent the foundation for the surfactant-based structure sorting and spectroscopic characterization of SWCNTs. In this work, we investigate three BSS in their ability to separate different SWCNT chiral structures by aqueous two-phase extraction (ATPE): sodium deoxycholate (DOC), sodium cholate (SC) and sodium chenodeoxycholate (CDOC). The small difference in their chemical structure (just one hydroxyl group) leads to significant differences in their stacking behavior on SWCNT walls with different diameter and chiral structure that, in turn, has direct consequences for the chiral sorting of SWCNTs using these BSS. By performing several series of systematic ATPE experiments, we reveal that, in general, the stacking of DOC and CDOC is more enantioselective than the stacking of SC on the SWCNT walls, while SC has a clear diameter preference for efficiently solubilizing the SWCNTs in comparison to DOC and CDOC. Moreover, combining sodium dodecylsulfate with SC allows for resolving the ATPE sorting transitions of empty and water-filled SWCNTs for a number of SWCNT chiralities. We also show that addition of SC to combinations of DOC and sodium dodecylbenzenesulfonate can enhance separations of particular chiralities.

Efficient Inner-to-Outer Wall Energy Transfer in Highly Pure Double-Wall Carbon Nanotubes Revealed by Detailed Spectroscopy.

The coaxial stacking of two single-wall carbon nanotubes (SWCNTs) into a double-wall carbon nanotube (DWCNT), forming a so-called one-dimensional van der Waals structure, leads to synergetic effects that dramatically affect the optical and electronic properties of both layers. In this work, we explore these effects in purified DWCNT samples by combining absorption, wavelength-dependent infrared fluorescence-excitation (PLE), and wavelength-dependent resonant Raman scattering (RRS) spectroscopy. Purified DWCNTs are obtained by careful solubilization that strictly avoids ultrasonication or by electronic-type sorting, both followed by a density gradient ultracentrifugation to remove unwanted SWCNTs that could obscure the DWCNT characterization. Chirality-dependent shifts of the radial breathing mode vibrational frequencies and transition energies of the inner and outer DWCNT walls with respect to their SWCNT analogues are determined by advanced two-dimensional fitting of RRS and PLE data of DWCNT and their reference SWCNT samples. This exhaustive data set verifies that fluorescence from the inner DWCNT walls of well-purified samples is severely quenched through efficient energy transfer from the inner to the outer DWCNT walls. Combined analysis of the PLE and RRS results further reveals that this transfer is dependent on the inner and outer wall chirality, and we identify the specific combinations dominant in our DWCNT samples. These obtained results demonstrate the necessity and value of a combined structural characterization approach including PLE and RRS spectroscopy for bulk DWCNT samples.

Chirality manifestation in elastic coupling between the layers of double-walled carbon nanotubes.

The search for new relatively easy physicochemical methods for the structural identification of carbon nanotubes represents a key challenge. Here, analyzing the experimental data on double-walled carbon nanotubes (DWCNTs) obtained by us and taken from the literature, we have expressed the magnitude of elastic coupling between two tubular walls forming a DWCNT as a simple function dependent not only on DWCNT diameters but also on the difference between the chirality angles of the constituent nanotubes. To get this quite unexpected result, which allows us to relate more precisely the structural parameters of a DWCNT with frequencies of its radial breathing-like modes (RBLM), we have developed a new model for the RBLM dynamics that takes into account a possible deposition of water molecules from ambient air onto the DWCNT surface. The model constructed allows us to predict the higher prevalence of DWCNTs comprising two walls with identical handedness. The application of the results obtained for the identification of DWCNTs is also considered.

Low-frequency phonon dynamics and related thermal properties of axially stressed single-walled carbon nanotubes.

Synthesis temperatures of composite materials are usually far less than the ones of their use, thus carbon nanotubes (CNTs) embedded into a polymer matrix undergo significant axial stress. We develop a continuous theory, which describes the dynamics of stressed single-walled (SW-) CNTs and predicts their low-frequency phonon spectra. The changes in dispersion laws of SWCNT low-frequency phonon modes due to the axial stress of different signs are discussed. Then, the results obtained are used to analyze low-temperature (T < 70 K) heat capacity and thermal conductivity of individual nanotubes. We demonstrate that compressive stress leads to increase in heat capacity C V of an individual SWCNT, while tensile stress causes C V to decrease. In the latter case at T → 0 heat capacity diminishes according to a linear law ~T instead of a power one ~T 1/2. Nevertheless, according to our results, axial stress hardly affects low-temperature thermal conductance of SWCNTs. Influence of investigated effects on the corresponding macroscopic properties of CNT-based composite materials are also discussed.