dc.creator | Kyriakou, Georgios | es |
dc.creator | Márquez Cruz, Antonio Marcial | es |
dc.creator | Holgado, Juan Pedro | es |
dc.creator | Taylor, Martin J. | es |
dc.creator | Wheatley, Andrew E.H. | es |
dc.creator | Mehta, Joshua P. | es |
dc.creator | Fernández Sanz, Javier | es |
dc.creator | Beaumont, Simon K. | es |
dc.creator | Lambert, Richard M. | es |
dc.date.accessioned | 2020-09-29T07:53:24Z | |
dc.date.available | 2020-09-29T07:53:24Z | |
dc.date.issued | 2019 | |
dc.identifier.citation | Kyriakou, G., Márquez Cruz, A.M., Holgado, J.P., Taylor, M.J., Wheatley, A.E.H., Mehta, J.P.,...,Lambert, R.M. (2019). Comprehensive Experimental and Theoretical Study of the CO + NO Reaction Catalyzed by Au/Ni Nanoparticles. ACS Catalysis, 4919-4929. | |
dc.identifier.issn | 2155-5435 | es |
dc.identifier.uri | https://hdl.handle.net/11441/101553 | |
dc.description.abstract | The catalytic and structural properties of five different nanoparticle catalysts with varying Au/Ni composition were studied by six different methods, including in situ X-ray absorption spectroscopy and density functional theory (DFT) calculations. The as-prepared materials contained substantial amounts of residual capping agent arising from the commonly used synthetic procedure. Thorough removal of this material by oxidation was essential for the acquisition of valid catalytic data. All catalysts were highly selective toward N2 formation, with 50–50 Au:Ni material being best of all. In situ X-ray absorption near edge structure spectroscopy showed that although Au acted to moderate the oxidation state of Ni, there was no clear correlation between catalytic activity and nickel oxidation state. However, in situ extended X-ray absorption fine structure spectroscopy showed a good correlation between Au–Ni coordination number (highest for Ni50Au50) and catalytic activity. Importantly, these measurements also demonstrated substantial and reversible Au/Ni intermixing as a function of temperature between 550 °C (reaction temperature) and 150 °C, underlining the importance of in situ methods to the correct interpretation of reaction data. DFT calculations on smooth, stepped, monometallic and bimetallic surfaces showed that N + N recombination rather than NO dissociation was always rate-determining and that the activation barrier to recombination reaction decreased with increased Au content, thus accounting for the experimental observations. Across the entire composition range, the oxidation state of Ni did not correlate with activity, in disagreement with earlier work, and theory showed that NiO itself should be catalytically inert. Au–Ni interactions were of paramount importance in promoting N + N recombination, the rate-limiting step. | es |
dc.description.sponsorship | España, MINECO under Project CTQ2015-64669-P | es |
dc.description.sponsorship | European Union FEDER Program and MINECO under Project CTQ2014-60524-R and ENE2017-88818-C2-1-R | es |
dc.format | application/pdf | es |
dc.format.extent | 10 p. | es |
dc.language.iso | eng | es |
dc.publisher | American Chemical Society | es |
dc.relation.ispartof | ACS Catalysis, 4919-4929. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.subject | Bimetallic catalysts | es |
dc.subject | in situ measurements, DFT | es |
dc.subject | active species | es |
dc.subject | effect of Au | es |
dc.subject | reaction mechanism | es |
dc.title | Comprehensive Experimental and Theoretical Study of the CO + NO Reaction Catalyzed by Au/Ni Nanoparticles | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/publishedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Física | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Inorgánica | es |
dc.relation.projectID | Project CTQ2015-64669-P | es |
dc.relation.projectID | Project CTQ2014-60524-R | es |
dc.relation.projectID | ENE2017-88818-C2-1-R | es |
dc.relation.publisherversion | https://doi.org/10.1021/acscatal.8b05154 | es |
dc.identifier.doi | 10.1021/acscatal.8b05154 | es |
dc.journaltitle | ACS Catalysis | es |
dc.publication.initialPage | 4919 | es |
dc.publication.endPage | 4929 | es |
dc.contributor.funder | Ministerio de Economía y Competitividad (MINECO). España | es |
dc.contributor.funder | European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER) | es |