Reduction mechanisms of the CuO(111) surface through surface oxygen vacancy formation and hydrogen adsorption

Simple item page
dc.contributor.authorMaimaiti, Yasheng
dc.contributor.authorNolan, Michael
dc.contributor.authorElliott, Simon D.
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderScience Foundation Irelanden
dc.date.accessioned2016-03-08T17:06:15Z
dc.date.available2016-03-08T17:06:15Z
dc.date.issued2013-12-23
dc.date.updated2015-04-13T15:50:03Z
dc.description.abstractWe studied the reduction of CuO(111) surface using density functional theory (DFT) with the generalized gradient approximation corrected for on-site Coulomb interactions (GGA + U) and screened hybrid DFT (HSE06 functional). The surface reduction process by oxygen vacancy formation and H2 adsorption on the CuO(111) surface is investigated as two different reduction mechanisms. It is found that both GGA + U and HSE06 predict the same trend in the relative stability of oxygen vacancies. We found that loss of the subsurface oxygen is initially thermodynamically favourable. As the oxygen vacancy concentration increases, mixture of subsurface and surface vacancies is energetically preferred over full reduction of the surface or subsurface monolayer. The reduction of Cu2+ to Cu+ is found to be more favourable than that of Cu+ to Cu0 in the most stable vacancy structures at all concentrations. Consistent with the oxygen vacancy calculations, H2 adsorption occurs initially on under-coordinated surface oxygen. Water molecules are formed upon the adsorption of H2 and this gives a mechanism for H2 reduction of CuO to Cu. Ab initio atomistic thermodynamics shows that reducing CuO to metallic Cu at the surface is more energetically difficult than in the bulk so that the surface oxide protects the bulk from reduction. Using H2 as the reducing agent, it is found that the CuO surface is reduced to Cu2O at approximately 360 K and that complete reduction from Cu2O to metallic Cu occurs at 780 K.en
dc.description.sponsorshipScience Foundation Ireland (SFI ALDesign Project (grant number 09.IN1.I2628), SFI Starting Investigator Research Grant Program EMOIN (SIRG/09/I1620)); Higher Education Authority (HEA and SFI funded Irish Centre for High Performance Computing (ICHEC))en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationMAIMAITI, Y., NOLAN, M. & ELLIOTT, S. D. 2014. Reduction mechanisms of the CuO(111) surface through surface oxygen vacancy formation and hydrogen adsorption. Physical Chemistry Chemical Physics, 16, 3036-3046. http://dx.doi.org/10.1039/C3CP53991Aen
dc.identifier.doi10.1039/C3CP53991A
dc.identifier.endpage3046en
dc.identifier.issn1463-9076
dc.identifier.issued7en
dc.identifier.journaltitlePhysical Chemistry Chemical Physicsen
dc.identifier.otherhttp://pubs.rsc.org/en/content/articlepdf/2014/cp/c3cp53991aen
dc.identifier.startpage3036en
dc.identifier.urihttps://hdl.handle.net/10468/2420
dc.identifier.volume16en
dc.language.isoenen
dc.publisherThe Royal Society of Chemistryen
dc.rights© the Owner Societies 2014en
dc.subjectAtomic layer depositionen
dc.subjectCopper filmsen
dc.subjectElectronic propertiesen
dc.subjectOxide reductionen
dc.subjectNickel oxideen
dc.subjectThin filmen
dc.subjectCuOen
dc.subjectDensity functional theoryen
dc.subjectDFTen
dc.titleReduction mechanisms of the CuO(111) surface through surface oxygen vacancy formation and hydrogen adsorptionen
dc.typeArticle (peer-reviewed)en
Files
Original bundle
Now showing 1 - 2 of 2
Thumbnail Image
Name:
Maimaiti_Elliott_PCCP_16_3036_2014_submitted.pdf
Size:
1.38 MB
Format:
Adobe Portable Document Format
Description:
Accepted Version
Download
Thumbnail Image
Name:
YM_ReductionAV2014_Add_File.pdf
Size:
837.47 KB
Format:
Adobe Portable Document Format
Description:
Additional file: Supplementary Info
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