Ab initio molecular dynamics simulations investigating proton transfer in perfluorosulfonic acid functionalized carbon nanotubes

Proton dissociation and transfer were examined with ab initio molecular dynamics (AIMD) simulations of carbon nanotubes (CNT) functionalized with perfluorosulfonic acid (-CF ₂SO ₃H) groups with 1-3 H ₂O/SO ₃H. The CNT systems were constructed both with and without fluorine atoms covalently bound to the walls to elucidate the effects of the presence of a strongly hydrophobic environment, the fluorine, on proton dissociation, hydration, and stabilization. The simulations revealed that the dissociated proton was preferentially stabilized as a hydrated hydronium cation (i.e., Eigen like) in the fluorinated CNTs but as a Zundel (H ₅O ₂ ⁺) cation in the nonfluorinated CNTs. This feature is attributed to the fluorine atoms forming hydrogen bonds with the water molecules coordinated to the central hydronium ion.