<i>Ab Initio</i> Electrochemistry: Exploring the Hydrogen Evolution Reaction on Carbon Nanotubes

Density functional theory (DFT) was employed to investigate the hydrogen evolution reaction (HER) on pristine and nitrogen-doped carbon nanotubes (CNTs) in acidic solution. As the reaction is an electrocatalytic surface reaction, an accurate description of HER requires performing simulations under constant electrode potential conditions. To this end, we examined HER at several electrode charges allowing us to determine grand canonical activation energies as a continuous function of electrode potential. By studying the elementary steps of HERthe Volmer, Tafel, and Heyrovsky reactionsand by considering hydrogen coverage effects, we found that the Volmer–Heyrovsky mechanism is the predominant HER mechanism on CNTs with the Heyrovsky step being rate-determining. Our results indicated that CNTs are electrochemically active toward HER, which is seen as a decrease in activation energies with growing electrode potential, but that the activity is lower than on platinum matching experimental data. Substitutional nitrogen doping did not improve HER activity, and further research is required to determine which nitrogen configurations contribute to the enhanced catalytic activity observed for experimental NCNTs