Ab initio insight into the electrolysis of water on basal and edge (fullerene C 20 ) surfaces of 4 Å single-walled carbon nanotubes.

The extreme surface reactivity of 4 Å single-walled carbon nanotubes (SWCNTs) makes for a very promising catalytic material, however, controlling it experimentally has been found to be challenging. Here, we employ ab initio calculations to investigate the extent of surface reactivity and functionalization of 4 Å SWCNTs. We study the kinetics of water dissociation and adsorption on the surface of 4 Å SWCNTs with three different configurations: armchair (3,3), chiral (4,2) and zigzag (5,0). We reveal that out of three different configurations of 4 Å SWCNTs, the surface of tube (5,0) is the most reactive due to its small HOMO-LUMO gap. The dissociation of 1 H 2 O molecule into an OH/H pair on the surface of tube (5,0) has an adsorption energy of -0.43 eV and an activation energy barrier of 0.66 eV at 298.15 K in pure aqueous solution, which is less than 10% of the activation energy barrier of the same reaction without the catalyst present. The four steps of H + /e - transfer in the oxygen evolution reaction have also been studied on the surface of tube (5,0). The low overpotential of 0.38 V indicates that tube (5,0) has the highest potential efficiency among all studied carbon-based catalysts. We also reveal that the armchair edge of tube (5,0) is reconstructed into fullerene C 20 . The dangling bonds on the surface of fullerene C 20 result in a more reactive surface than the basal surface of tube (5,0), however the catalytic ability was also inhibited in the later oxygen reduction processes.