Individually dispersing single-walled carbon nanotubes with novel neutral pH water-soluble chitosan derivatives

Chitosan and its various neutral pH water-soluble derivatives were investigated for dispersing single-walled carbon nanotubes (SWNTs). Chitosan (CS) can produce good dispersion of SWNTs, but only in acidic pH condition. Our two novel derivatives, O-carboxymethylchitosan (OC) and OC modified by polyethylene glycol) at the -COOH position (OPEG), were able to produce highly effective debundling and dispersion of SWNTs in neutral pH aqueous solution. Atomic force microscopy (AFM), transmission electron microscopy (TEM), photoluminescence, UV-vis-NIR spetroscopy, and Raman spectroscopy confirmed that SWNTs are present as individual nanotubes in the dispersions. The solubilities of individually dispersed SWNTs in neutral water are 0.021 and 0.032 g/L for OC and OPEG, respectively, which are comparable to 0.038 g/L for SWNTs using CS in acetic acid. Further, OC and OPEG aqueous solutions (1 wt %) do not significantly lower the surface tensions (65-67 mN/m). From the Fourier transform infrared spectroscopic results, we conclude that the free electron pair in the pendant amine groups of OC and OPEG plays a vital role in finely dispersing the SWNTs; the -NH₂ contributes to the adsorption of these two chitosan derivatives on the nanotubes. Quaternary ammonium chitosan (QC), with alkyl substitution at the protonated amine, was found to be unable to disperse SWNTs; possibly cation-π interaction with nanotubes is diminished due to steric hindrance.