The Hydroxylated Carbon Nanotubes as the Hole Oxidation System in Electrocatalysis.

The hydroxylated carbon nanotubes (CNTs-OH), due to their propensity to trap electrons, are considered in many applications. Despite many case studies, the effect of the electronic structure of the CNT-OH electrode on its oxidation properties has not received in-depth analysis. In the present study, we used Fe(CN) and Ru(NH) as redox probes, which differ in charge. The CNT-OH and CNT electrodes used in the cyclic voltammetry were in the form of freestanding films. The concentration of holes in the CNTs-OH, estimated from the upshift of the Raman G-feature, was 2.9×1013 cm-2. The standard rate constant of the heterogeneous electron transfer (HET) between Fe(CN) and the CNTs-OH electrode was 25.9×10-4 cm·s-1. The value was more than four times higher than the HET rate on the CNT electrode (ks=6.3×10-4 cm·s-1), which proves excellent boosting of the redox reaction by the holes. The opposite effect was observed for the Ru(NH) redox couple. While the redox reaction rate constant at the CNT electrode was 1.4×10-4 cm·s-1, there was a significant suppression of the redox reaction at the CNT-OH electrode (ks<0.1×10-4 cm·s-1). Based on the DFT calculations and the Gerischer model, we find that the boosting of the HET from the reduced form of the redox couple to CNT-OH occurs when the reduced forms of the redox couples are negatively charged and the occupied reduced states are aligned with acceptor states of the nanotube electrode.