Dissociative adsorption of methane on the Cu and Zn doped (111) surface of CeO2

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dc.contributor.author Carey, John J.
dc.contributor.author Nolan, Michael
dc.date.accessioned 2016-10-20T13:15:02Z
dc.date.available 2016-10-20T13:15:02Z
dc.date.issued 2016-04-04
dc.identifier.citation Carey, J. J. and Nolan, M. (2016) ‘Dissociative adsorption of methane on the Cu and Zn doped (111) surface of CeO2’, Applied Catalysis B: Environmental, 197, pp. 324-336. doi: 10.1016/j.apcatb.2016.04.004 en
dc.identifier.volume 197 en
dc.identifier.startpage 324 en
dc.identifier.endpage 336 en
dc.identifier.issn 0926-3373
dc.identifier.uri http://hdl.handle.net/10468/3199
dc.identifier.doi 10.1016/j.apcatb.2016.04.004
dc.description.abstract The development of economical heterogeneous catalysts for the activation of methane is a major challenge for the chemical industry. Screening potential candidates becomes more feasible using rational catalyst design to understand the activity of potential catalysts for CH4 activation. The focus of the present paper is the use of density functional theory to examine and elucidate the properties of doped CeO2. We dope with Cu and Zn transition metals having variable oxidation state (Cu), and a single oxidation state (Zn), and study the activation of methane. Zn is a divalent dopant and Cu can have a +1 or +2 oxidation state. Both Cu and Zn dopants have an oxidation state of +2 after incorporation into the CeO2 (111) surface; however a Hubbard +U correction (+U = 7) on the Cu 3d states is required to maintain this oxidation state when the surface interacts with adsorbed species. Dissociation of methane is found to occur locally at the dopant cations, and is thermodynamically and kinetically more favorable on Zn-doped CeO2 than Cu-doped CeO2. The origins of this lie with the Zn(II) dopant moving towards a square pyramidal geometry in the sub surface layer which facilitates the formation of two-coordinated surface oxygen atoms, that are more beneficial for methane activation on a reducible oxide surface. These findings can aid in rational experimental catalyst design for further exploration in methane activation processes. en
dc.description.sponsorship Science Foundation Ireland (SFI funded Irish Centre for High-end Computing (ICHEC), and by SFI funded resources at Tyndall); European Cooperation in Science and Technology (CMST COST Action CM1104) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Elsevier en
dc.rights © 2016, Elsevier B.V. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0/ en
dc.rights.uri https://creativecommons.org/licenses/by-nc-nd/4.0/ en
dc.subject Methane activation en
dc.subject Density functional theory en
dc.subject CeO2 en
dc.subject Transition metal doping en
dc.title Dissociative adsorption of methane on the Cu and Zn doped (111) surface of CeO2 en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother John J. Carey, Tyndall National Institute, University College Cork, Cork, Ireland, +353-21-490-3000 Email: john.carey@tyndall.ie en
dc.internal.availability Full text available en
dc.check.info Access to this article is restricted until 24 months after publication by request of the publisher. en
dc.check.date 2018-04-04
dc.description.version Accepted Version en
dc.contributor.funder Seventh Framework Programme en
dc.contributor.funder Science Foundation Ireland en
dc.contributor.funder European Cooperation in Science and Technology en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Applied Catalysis B: Environmental en
dc.internal.copyrightchecked !!CORA!! en
dc.relation.project info:eu-repo/grantAgreement/EC/FP7::SP1::NMP/604296/EU/Catalytic Partial Oxidation of Bio Gas and Reforming of Pyrolysis Oil (Bio Oil) for an Autothermal Synthesis Gas Production and Conversion into Fuels/BIOGO-FOR-PRODUCTION en


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© 2016, Elsevier B.V. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0/ Except where otherwise noted, this item's license is described as © 2016, Elsevier B.V. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0/
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