Reversible, band-gap-selective protonation of single-walled carbon nanotubes in solution

In acidic solution between pH 6 and 2.5, protons react reversibly and selectively in the presence of preadsorbed oxygen at the sidewall of aqueous dispersed single-walled carbon nanotubes suspended in sodium dodecyl sulfate. This reactive complex, which protonates the nanotube sidewall, reversibly diminishes absorption intensity, fluorescent emission, and resonant Raman scattering intensity. The results document the first evidence of electronic selectivity with metallic nanotubes reacting initially near neutral pH, followed by successive protonation of nanotubes with increasing band gap as the solution is increasingly acidified. Preadsorption of molecular oxygen is shown to play a critical role in the interaction, and its desorption kinetics is followed using UV irradiation. The role of the charged electric double layer of the surfactant is discussed. This chemistry, which proceeds under relatively mild conditions, holds promise for separating nanotubes by metal and semiconducting types.