Modification of TiO 2 with metal chalcogenide nanoclusters for hydrogen evolution

Stephen Rhatigan, Lorenzo Niemitz, Michael Nolan

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)
15 Downloads (Pure)

Abstract

Abstract: 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 −2.8 eV to −2.5 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 the hydrogen evolution reaction (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 to 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.
Original languageEnglish
Article number025001
Pages (from-to)1-14
Number of pages14
JournalJournal of Physics: Energy
Volume3
Issue number2
Early online date3 Mar 2021
DOIs
Publication statusPublished - 30 Apr 2021

Bibliographical note

Funding Information:
We acknowledge support from Science Foundation Ireland through the US-Ireland R&D Partnership Programme, Grant No. SFI/US/14/E2915 and the ERA.Net for Materials Research and Innovation (M-ERA.Net 2), Horizon 2020 Grant Agreement No. 685451, SFI Grant No. SFI/16/M-ERA/3418 (RATOCAT). We acknowledge access to SFI funded computing resources at Tyndall Institute and the SFI/HEA funded Irish Centre for High End Computing. We are grateful for support from the COST Action CM1104 ‘Reducible Metal Oxides, Structure and Function’

Funding Information:
We acknowledge support from Science Foundation Ireland through the US-Ireland R&D Partnership Programme, Grant No. SFI/US/14/E2915 and the ERA.Net for Materials Research and Innovation (M-ERA.Net 2), Horizon 2020 Grant Agreement No. 685451, SFI Grant No. SFI/16/M-ERA/3418 (RATOCAT). We acknowledge access to SFI funded computing resources at Tyndall Institute and the SFI/HEA funded Irish Centre for High End Computing. We are grateful for support from the COST Action CM1104 'Reducible Metal Oxides, Structure and Function'

Publisher Copyright:
© 2021 The Author(s). Published by IOP Publishing Ltd

Keywords

  • Paper
  • Photocatalysis
  • photocatalysis
  • TiO2
  • sulphides
  • selenides
  • hydrogen evolution reaction
  • DFT + U
  • Hydrogen evolution reaction
  • Selenides
  • Sulphides

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