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

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dc.contributor.author Maimaiti, Yasheng
dc.contributor.author Nolan, Michael
dc.contributor.author Elliott, Simon D.
dc.date.accessioned 2016-03-08T17:06:15Z
dc.date.available 2016-03-08T17:06:15Z
dc.date.issued 2013-12-23
dc.identifier.citation MAIMAITI, 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/C3CP53991A en
dc.identifier.volume 16 en
dc.identifier.issued 7 en
dc.identifier.startpage 3036 en
dc.identifier.endpage 3046 en
dc.identifier.issn 1463-9076
dc.identifier.other http://pubs.rsc.org/en/content/articlepdf/2014/cp/c3cp53991a en
dc.identifier.uri http://hdl.handle.net/10468/2420
dc.identifier.doi 10.1039/C3CP53991A
dc.description.abstract We 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.sponsorship Science 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.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher The Royal Society of Chemistry en
dc.rights © the Owner Societies 2014 en
dc.subject Atomic layer deposition en
dc.subject Copper films en
dc.subject Electronic properties en
dc.subject Oxide reduction en
dc.subject Nickel oxide en
dc.subject Thin film en
dc.subject CuO en
dc.subject Density functional theory en
dc.subject DFT en
dc.title Reduction mechanisms of the CuO(111) surface through surface oxygen vacancy formation and hydrogen adsorption en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Simon Elliott, Tyndall Theory Modelling & Design Centre, University College Cork, Cork, Ireland. +353-21-490-3000 Email: simon.elliott@tyndall.ie en
dc.internal.availability Full text available en
dc.date.updated 2015-04-13T15:50:03Z
dc.description.version Accepted Version en
dc.internal.rssid 283617567
dc.contributor.funder Higher Education Authority en
dc.contributor.funder Science Foundation Ireland en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Physical Chemistry Chemical Physics en
dc.internal.copyrightchecked Yes 12 month embargo now over. !!CORA!! AV+12 month embargo+link to pdf en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress simon.elliott@tyndall.ie en


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