Oxygen Evolution Reaction Kinetic Barriers on Nitrogen-Doped Carbon Nanotubes

We investigate kinetic barriers for the oxygen evolution reaction (OER) on singly and doubly nitrogen-doped single-walled carbon nanotubes (NCNTs) using the climbing image nudged elastic band method with solvent effects represented by a 45-water-molecule droplet. The studied sites were chosen based on a previous study of the same systems utilizing a thermodynamic model which ignored both solvent effects and kinetic barriers. According to that model, the two studied sites, one on a singly nitrogen-doped CNT and the other on a doubly doped CNT, were
approximately equally suitable for OER. For the four-step OER process, however, our reaction barrier calculations showed a clear difference in the rate-determining *OOH formation step between the two systems, with barrier heights differing by more than 0.4 eV. Thus, the simple thermodynamic model may alone be insufficient for identifying optimal OER sites. Of the remaining three reaction steps, the two H2O forming ones were found to be barrierless in all cases. We also performed solvent-free barrier calculations on NCNTs and undoped CNTs.
Substantial differences were observed in the energies of the intermediates when the solvent was present. In general, the observed low activation energy barriers for these reactions corroborate both experimental and theoretical findings of the utility of NCNTs for OER catalysis.