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Ethanol, O, and CO adsorption on Pt nanoparticles: effects of nanoparticle size and graphene support

Ethanol, O, and CO adsorption on Pt nanoparticles: effects of nanoparticle size and graphene support
Ethanol, O, and CO adsorption on Pt nanoparticles: effects of nanoparticle size and graphene support
Pt nanoparticles dispersed over carbonaceous supports are widely used as catalysts for different applications, making studies on the interplay between size and support effects indispensable for rational catalyst design. Here, we use DFT calculations to simulate the interaction between O, CO, and ethanol with free platinum cuboctahedral nanoparticles with up to 147 atoms and with the same Pt nanoparticles supported on a single layer of graphene with up to 720 carbon atoms. We compute adsorption energies for each adsorbate on different adsorption sites for supported and unsupported Pt nanoparticles. We show that as the Pt nanoparticle grows the adsorption energy decreases, and that the size effect is more important for O and CO adsorption than for ethanol. We observe that the generalized coordination number of each adsorption site controls the interaction strength for O and CO to a much larger extent than for ethanol. Electronic charge redistributions and density of states projected on the d band of the interacting Pt facets are used to obtain a better understanding of the differences between the electronic interactions for each adsorbate. For Pt nanoparticles supported on graphene, the support effects weaken the adsorption energies for all the adsorbates, but this effect rapidly decreases with larger nanoparticles, and it is only significant for our smallest nanoparticle Pt13. By demonstrating that the effects of nanoparticle size and support are different for ethanol as compared with O and CO, we conclude that it should be possible to modify different parameters in the catalyst design in order to tune the Pt nanoparticle to interact with specific adsorbates.
Pt nanoparticles, Heterogeneous Catalysis, Graphene, fuel cell catalysts, DFT calculations, ethanol adsorption
1463-9076
25918-25930
Verga, L.G.
681e0d2b-083d-4478-85f6-d2eca7673c24
Russell, A.E.
b6b7c748-efc1-4d5d-8a7a-8e4b69396169
Skylaris, C.-K.
8f593d13-3ace-4558-ba08-04e48211af61
Verga, L.G.
681e0d2b-083d-4478-85f6-d2eca7673c24
Russell, A.E.
b6b7c748-efc1-4d5d-8a7a-8e4b69396169
Skylaris, C.-K.
8f593d13-3ace-4558-ba08-04e48211af61

Verga, L.G., Russell, A.E. and Skylaris, C.-K. (2018) Ethanol, O, and CO adsorption on Pt nanoparticles: effects of nanoparticle size and graphene support. Physical Chemistry Chemical Physics, 20 (40), 25918-25930. (doi:10.1039/C8CP04798G).

Record type: Article

Abstract

Pt nanoparticles dispersed over carbonaceous supports are widely used as catalysts for different applications, making studies on the interplay between size and support effects indispensable for rational catalyst design. Here, we use DFT calculations to simulate the interaction between O, CO, and ethanol with free platinum cuboctahedral nanoparticles with up to 147 atoms and with the same Pt nanoparticles supported on a single layer of graphene with up to 720 carbon atoms. We compute adsorption energies for each adsorbate on different adsorption sites for supported and unsupported Pt nanoparticles. We show that as the Pt nanoparticle grows the adsorption energy decreases, and that the size effect is more important for O and CO adsorption than for ethanol. We observe that the generalized coordination number of each adsorption site controls the interaction strength for O and CO to a much larger extent than for ethanol. Electronic charge redistributions and density of states projected on the d band of the interacting Pt facets are used to obtain a better understanding of the differences between the electronic interactions for each adsorbate. For Pt nanoparticles supported on graphene, the support effects weaken the adsorption energies for all the adsorbates, but this effect rapidly decreases with larger nanoparticles, and it is only significant for our smallest nanoparticle Pt13. By demonstrating that the effects of nanoparticle size and support are different for ethanol as compared with O and CO, we conclude that it should be possible to modify different parameters in the catalyst design in order to tune the Pt nanoparticle to interact with specific adsorbates.

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Accepted/In Press date: 28 September 2018
e-pub ahead of print date: 1 October 2018
Published date: 28 October 2018
Keywords: Pt nanoparticles, Heterogeneous Catalysis, Graphene, fuel cell catalysts, DFT calculations, ethanol adsorption

Identifiers

Local EPrints ID: 425453
URI: http://eprints.soton.ac.uk/id/eprint/425453
ISSN: 1463-9076
PURE UUID: 8aef9e06-ed9e-42af-9b1a-531cb29ead82
ORCID for L.G. Verga: ORCID iD orcid.org/0000-0002-7453-238X
ORCID for A.E. Russell: ORCID iD orcid.org/0000-0002-8382-6443
ORCID for C.-K. Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 19 Oct 2018 16:30
Last modified: 07 Oct 2020 04:49

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