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Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports

Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports
Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports
Metal oxide supports often play an active part in heterogeneous catalysis by moderating both the structure and the electronic properties of the metallic catalyst particle. In order to provide some fundamental understanding on these effects, we present here a density functional theory (DFT) investigation of the binding of O and CO on Pt nanoparticles supported on titania (anatase) surfaces. These systems are complex, and in order to develop realistic models, here, we needed to perform DFT calculations with up to ∼1000 atoms. By performing full geometry relaxations at each stage, we avoid any effects of “frozen geometry” approximations. In terms of the interaction of the Pt nanoparticles with the support, we find that the surface deformation of the anatase support contributes greatly to the adsorption of each nanoparticle, especially for the anatase (001) facet. We attempt to separate geometric and electronic effects and find a larger contribution to ligand binding energy arising from the former. Overall, we show an average weakening (compared to the isolated nanoparticle) of ∼0.1 eV across atop, bridge and hollow binding sites on supported Pt55 for O and CO, and a preservation of site preference. Stronger effects are seen for O on Pt13, which is heavily deformed by anatase supports. In order to rationalize our results and examine methods for faster characterization of metal catalysts, we make use of electronic descriptors, including the d-band center and an electronic density based descriptor. We expect that the approach followed in this study could be applied to study other supported metal catalysts.
0021-9606
Ellaby, Tom
7f85bf66-4204-49b1-a388-aff6cea19077
Briquet, Ludovic
710cd061-6781-4f4e-9a5a-4fb3ca929a00
Sarwar, Misbah
ae93ef8f-8a84-4a46-95ac-cd9352c44e56
Thompsett, David
2fba717f-67ed-4999-b400-3c3a0681778f
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Ellaby, Tom
7f85bf66-4204-49b1-a388-aff6cea19077
Briquet, Ludovic
710cd061-6781-4f4e-9a5a-4fb3ca929a00
Sarwar, Misbah
ae93ef8f-8a84-4a46-95ac-cd9352c44e56
Thompsett, David
2fba717f-67ed-4999-b400-3c3a0681778f
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61

Ellaby, Tom, Briquet, Ludovic, Sarwar, Misbah, Thompsett, David and Skylaris, Chris-Kriton (2019) Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports. The Journal of Chemical Physics, 151 (11), [114702]. (doi:10.1063/1.5120571).

Record type: Article

Abstract

Metal oxide supports often play an active part in heterogeneous catalysis by moderating both the structure and the electronic properties of the metallic catalyst particle. In order to provide some fundamental understanding on these effects, we present here a density functional theory (DFT) investigation of the binding of O and CO on Pt nanoparticles supported on titania (anatase) surfaces. These systems are complex, and in order to develop realistic models, here, we needed to perform DFT calculations with up to ∼1000 atoms. By performing full geometry relaxations at each stage, we avoid any effects of “frozen geometry” approximations. In terms of the interaction of the Pt nanoparticles with the support, we find that the surface deformation of the anatase support contributes greatly to the adsorption of each nanoparticle, especially for the anatase (001) facet. We attempt to separate geometric and electronic effects and find a larger contribution to ligand binding energy arising from the former. Overall, we show an average weakening (compared to the isolated nanoparticle) of ∼0.1 eV across atop, bridge and hollow binding sites on supported Pt55 for O and CO, and a preservation of site preference. Stronger effects are seen for O on Pt13, which is heavily deformed by anatase supports. In order to rationalize our results and examine methods for faster characterization of metal catalysts, we make use of electronic descriptors, including the d-band center and an electronic density based descriptor. We expect that the approach followed in this study could be applied to study other supported metal catalysts.

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Oxygen_Binding_on_Titania_Supported_Platinum_Nanoparticles_revised - Accepted Manuscript
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Accepted/In Press date: 21 August 2019
e-pub ahead of print date: 18 September 2019

Identifiers

Local EPrints ID: 434639
URI: http://eprints.soton.ac.uk/id/eprint/434639
ISSN: 0021-9606
PURE UUID: c872619b-cfb3-4fee-891c-fa6a3b62375f
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 04 Oct 2019 16:30
Last modified: 07 Oct 2020 04:34

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Author: Tom Ellaby
Author: Ludovic Briquet
Author: Misbah Sarwar
Author: David Thompsett

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