Modification of TiO 2 with metal chalcogenide nanoclusters for hydrogen evolution

Stephen Rhatigan; Lorenzo Niemitz; Michael Nolan

doi:10.1088/2515-7655/abe424

Modification of TiO 2 with metal chalcogenide nanoclusters for hydrogen evolution

Stephen Rhatigan
, Lorenzo Niemitz
, Michael Nolan

Faculty Of Computing, Eng. & Built Env.

Tyndall National Institute Cork

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

121 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 language	English
Article number	025001
Pages (from-to)	1-14
Number of pages	14
Journal	Journal of Physics: Energy
Volume	3
Issue number	2
Early online date	3 Mar 2021
DOIs	https://doi.org/10.1088/2515-7655/abe424
Publication status	Published (in print/issue) - 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

Funding

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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10.1088/2515-7655/abe424

Rhatigan_2021_J._Phys._Energy_3_025001Final published version, 2.53 MBLicence: CC BY

Cite this

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title = "Modification of TiO 2 with metal chalcogenide nanoclusters for hydrogen evolution",

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.",

keywords = "Paper, Photocatalysis, photocatalysis, TiO2, sulphides, selenides, hydrogen evolution reaction, DFT + U, Hydrogen evolution reaction, Selenides, Sulphides",

author = "Stephen Rhatigan and Lorenzo Niemitz and Michael Nolan",

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 {\textquoteleft}Reducible Metal Oxides, Structure and Function{\textquoteright} 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: {\textcopyright} 2021 The Author(s). Published by IOP Publishing Ltd",

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doi = "10.1088/2515-7655/abe424",

language = "English",

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T1 - Modification of TiO 2 with metal chalcogenide nanoclusters for hydrogen evolution

AU - Rhatigan, Stephen

AU - Niemitz, Lorenzo

AU - Nolan, Michael

N1 - 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

PY - 2021/4/30

Y1 - 2021/4/30

N2 - 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.

AB - 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.

KW - Paper

KW - Photocatalysis

KW - photocatalysis

KW - TiO2

KW - sulphides

KW - selenides

KW - hydrogen evolution reaction

KW - DFT + U

KW - Hydrogen evolution reaction

KW - Selenides

KW - Sulphides

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DO - 10.1088/2515-7655/abe424

M3 - Article

SN - 2515-7655

VL - 3

SP - 1

EP - 14

JO - Journal of Physics: Energy

JF - Journal of Physics: Energy

IS - 2

M1 - 025001

ER -

Modification of TiO 2 with metal chalcogenide nanoclusters for hydrogen evolution

Abstract

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