Role of non-covalent interactions at the oxidation of 2,5-di-Me-pyrazine-di-N-oxide at glassy carbon, single-walled and multi-walled carbon nanotube paper electrodes

Abstract

Recently in our work it was shown that the catalytic efficiency of organic compound oxidation in the presence of electrochemically generated radical cations of aromatic di-N-oxides was increased several times using single-walled (SWCNT) or multi-walled (MWCNT) carbon nanotube paper electrodes instead of glassy carbon (GC) electrode. It was found that, in the absence of substrate, the oxidation currents of di-N-oxides at SWCNT or MWCNT paper electrodes, in contrast to the GC electrode, exceeded the oxidation current of the ferrocene (Fc) reference several times. In this work, the study of 2,5-di-Me-pyrazine-di-N-oxide (Pyr1) and Fc oxidation in 0.1 M Bu4NClO4 solutions in acetonitrile (MeCN) at GC, SWCNT and MWCNT paper electrodes was performed by methods of cyclic voltammetry, electron paramagnetic resonance (EPR) electrolysis, and differential capacitance. Quantum chemical modeling of adsorption of Pyr1, Fc, and MeСN on CNT surface was carried out using a cluster model describing the surface of conducting and non-conducting carbon nanotubes. The adsorption energies, equilibrium distances for molecular location and orientation on CNT surface were obtained. The observed effects were explained on the basis of quantum chemical modeling of the non-covalent interaction of the components of the studied system with CNT surface.