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

Simple item page
dc.check.date2018-04-04
dc.check.infoAccess to this article is restricted until 24 months after publication by request of the publisher.en
dc.contributor.authorCarey, John J.
dc.contributor.authorNolan, Michael
dc.contributor.funderSeventh Framework Programmeen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderEuropean Cooperation in Science and Technologyen
dc.date.accessioned2016-10-20T13:15:02Z
dc.date.available2016-10-20T13:15:02Z
dc.date.issued2016-04-04
dc.description.abstractThe 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.sponsorshipScience 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.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationCarey, 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.2016.04.004en
dc.identifier.doi10.1016/j.apcatb.2016.04.004
dc.identifier.endpage336en
dc.identifier.issn0926-3373
dc.identifier.journaltitleApplied Catalysis B: Environmentalen
dc.identifier.startpage324en
dc.identifier.urihttps://hdl.handle.net/10468/3199
dc.identifier.volume197en
dc.language.isoenen
dc.publisherElsevieren
dc.relation.projectinfo: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-PRODUCTIONen
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.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectMethane activationen
dc.subjectDensity functional theoryen
dc.subjectCeO2en
dc.subjectTransition metal dopingen
dc.titleDissociative adsorption of methane on the Cu and Zn doped (111) surface of CeO2en
dc.typeArticle (peer-reviewed)en
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
1493.pdf
Size:
1.45 MB
Format:
Adobe Portable Document Format
Description:
Accepted Version
Download
License bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
license.txt
Size:
2.71 KB
Format:
Item-specific license agreed upon to submission
Description:
Download
Collections
Tyndall National Institute - Journal Articles