Modification of TiO2 with Metal Chalcogenide Nanoclusters for Hydrogen Evolution

03 November 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Using density functional theory, corrected for on-site Coulomb interactions (DFT+U), we have investigated surface modification of TiO2 with metal chalcogenide nanoclusters for hydrogen evolution. The nanoclusters have composition M4X4 (M = Sn, Zn; X = S, Se) and are adsorbed at the rutile (110) surface. The nanoclusters adsorb exothermically, with adsorption energies in the range -3.00 eV to -2.70 eV. Computed density of states (DOS) plots show that cluster-derived states extend into the band-gap of the rutile support, which indicates that modification produces a redshift in light absorption. After modification, photoexcited electrons and holes are separated onto surface and cluster sites, respectively. The free energy of H adsorption is used to assess the performance of metal chalcogenide modified TiO2 as a catalyst for HER. Adsorption of H at nanocluster (S, Se) and surface (O) sites is considered, together with the effect of H coverage. Adsorption free energies at cluster sites in the range (-0.15 eV, 0.15 eV) are considered to be favourable for HER. The results of this analysis indicate that the sulphide modifiers are more active towards HER than the selenide modifiers and exhibit hydrogen adsorption free energies in the active range, for most coverages. Conversely, the adsorption free energies at the selenide nanoclusters are only in the active range at low H coverages. Our results indicate that surface modification with small, dispersed nanoclusters of appropriately selected materials can enhance the photocatalytic activity of TiO2 for HER applications.


hydrogen evolution
surface modification

Supplementary materials



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