Relationship between carbon nanotube structure and electrochemical behavior: heterogeneous electron transfer at electrochemically activated carbon nanotubes.

The electrochemical activation of multiwalled carbon nanotubes (MWCNTs) (at potentials of 1.5-2.0 V vs Ag/AgCl for 60-360 s) results in significantly increased rate constants (k(0)((obs))) for heterogeneous electron-transfer with [Fe(CN)(6)](3-/4-) (from 8.34 x 10(-5) cm s(-1) for as-received MWCNTs to 3.67 x 10(-3) cm s(-1) for MWCNTs that were electrochemically activated at 2.0 V for 180 s). The increase in the value of k(0)((obs)) arises from the introduction of wall defects exposing edge planes of the MWCNTs, as observed by high-resolution TEM. The density of the edge plane defects increases from almost zero (for as-received MWCNTs) to 3.7 % (for MWCNTs electrochemically activated at 2.0 V for 180 s). High-resolution X-ray photoelectron spectroscopy (HR-XPS), Raman spectroscopy, and electrochemical impedance spectroscopy were used to gain a better understanding of the phenomena. HR-XPS revealed that the increase in electrochemical activation potential increases the number of oxygen-containing groups on the surface of carbon nanotubes.