Electrochemical opening of single-walled carbon nanotubes filled with metal halides and with closed ends

The electrochemical opening of closed-ended, pristine single-walled carbon nanotubes (SWCNTs) upon the application of either a sufficiently oxidizing or reducing electrode potential is reported. Hitherto, it has been unclear whether the side walls of SWCNTs are electrochemically active, or whether, like their multiwalled counterparts (MWCNTs), the electroactive sites on SWCNTs also reside at the edge-plane-like defects at the open ends of the tubes. Evidence is presented herein that suggests the latter case is true, i.e., that SWCNTs require edge-plane sites to be electroactive. Comparisons of the voltammetric response of end-closed SWCNTs (EC-SWCNTs), end-open (EO-SWCNTs), and SWCNTs encapsulating a metal halide filling (MX@SWCNTs, where MX represents either NaI or CuI) in aqueous electrolytes indicate that SWCNTs undergo electrochemical opening if the applied electrode potential is greater than +1.2 V vs SCE or less than -1.5 V vs SCE. This was further confirmed using ex situ X-ray photoelectron spectroscopy. The nonaqueous voltammetry of NaCl@SWCNTs, NaI@SWCNTs, CuI@SWCNTs, and ZnCl₂@SWCNTs in dimethyl formamide (DMF) containing 0.1 M tetrabutyl ammonium perchlorate (TBAP) all exhibited voltammetric responses identical to that of EC-SWCNTs unless the potential was cycled beyond ca. +1.6 V vs Ag (+2.129 V vs the cobaltocene/cobaltocenium redox couple) whereupon voltammetry corresponding to the filling material was observed, again indicating that the SWCNTs had become open-ended. Evidence for quantized charging of the EC-SWCNTs is presented in terms of the unusual “bow-tie” shape of the background charging current in DMF is also presented.