Abstract
The thermodynamics of hydrogen evolution on MoS2 nanotubes is studied for the first time using periodic density functional theory calculations to obtain hydrogen adsorption free energies (Delta GHads) on pristine nanotubes and those with S-vacancy defects. Armchair and zigzag MoS2 nanotubes of different diameters, ranging from 12 to 22 angstrom, are examined. The H adsorption energy is observed to become more favourable (lower Delta GHads) as nanotube diameter decreases, with Delta GHads values ranging from 1.82 to 1.39 eV on the pristine nanotubes, and from 0.03 to -0.30 eV at the nanotube S-vacancy defect sites. An ideal thermoneutral Delta GHads value of nearly 0 eV is observed at the S-vacancy site on nanotubes around 20 to 22 angstrom in diameter. For the pristine nanotubes, density of states calculations reveal that electron transfer from S to Mo occurs during H adsorption, and the energy gap between these two states yields a highly reliable linear correlation with Delta GHads, where a smaller gap leads to a more favourable hydrogen adsorption. For the S-vacancy defect site the H adsorption resembles that on a pure metallic surface, meaning that a traditional d-band centre model can be applied to explain the trends in Delta GHads. A linear relation between the position of the Mo d-states and Delta GHads is found, with d-states closer to the Fermi level leading to strong hydrogen adsorption. Overall this work highlights the relevance of MoS2 nanotubes as promising hydrogen evolution catalysts and explains trends in their activity using the energies of the electronic states involved in binding hydrogen.