dc.contributor.author | Mangoufis-Giasin, Iosif | |
dc.contributor.author | Piqué, Oriol | |
dc.contributor.author | Khanipour, Peyman | |
dc.contributor.author | Mayrhofer, Karl J. J. | |
dc.contributor.author | Calle Vallejo, Federico | |
dc.contributor.author | Katsounaros, Ioannis | |
dc.date.accessioned | 2023-03-22T16:04:06Z | |
dc.date.available | 2023-03-22T16:04:06Z | |
dc.date.issued | 2021-06-17 | |
dc.identifier.citation | Journal of Catalysis 400 : 166-172 (2021) | es_ES |
dc.identifier.issn | 0021-9517 | |
dc.identifier.issn | 1090-2694 | |
dc.identifier.uri | http://hdl.handle.net/10810/60444 | |
dc.description.abstract | This study shows remarkably different features between the oxidation of secondary and primary C3-C5 alcohols. The oxidation of primary alcohols is controlled by the oxidative removal of blocking adsorbates, such as CO, formed after the dissociative adsorption of alcohol molecules. Conversely, secondary alcohols do not undergo dissociative adsorption and therefore their oxidation is purely controlled by the energetics of the elementary reaction steps. In this respect, a different role of ruthenium is revealed for the electrooxidation of primary and secondary alcohols on bimetallic platinum-ruthenium catalysts. Ruthenium enhances the oxidation of primary alcohols via the established bifunctional mechanism, in which the adsorption of (hydr)oxide species that are necessary to remove the blocking adsorbates is favored. In contrast, the oxidation of secondary alcohols is enhanced by the Ru-assisted stabilization of an O-bound intermediate that is involved in the potential-limiting step. This alternative pathway enables the oxidation of secondary alcohols close to the equilibrium potential. | es_ES |
dc.description.sponsorship | This work was funded by the Bavarian Ministry of Economic Affairs, Regional Development and Energy. F.C.-V. acknowledges funding from Spanish MICIUN RTI2018-095460-B-I00, Ramón y Cajal RyC-2015-18996 and María de Maeztu MDM-2017-0767 grants and partly by Generalitat de Catalunya 2017SGR13. O.P. thanks the Spanish MICIUN for a PhD grant (PRE2018-083811). We thank Red Española de Supercomputación (RES) for supercomputing time at SCAYLE (projects QS-2019-3-0018, QS-2019-2-0023, and QCM-2019-1-0034), MareNostrum (project QS-2020-1-0012), and CENITS (project QS-2020-2-0021). The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Elsevier | es_ES |
dc.relation | info:eu-repo/grantAgreement/MICIUN/RTI2018-095460-B-I00 | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/3.0/es/ | * |
dc.subject | electrocatalysis | es_ES |
dc.subject | electrochemical energy conversion | es_ES |
dc.subject | direct alcohol fuel cells | es_ES |
dc.subject | alcohol electrooxidation | es_ES |
dc.subject | secondary alcohols 2-propanol oxidation | es_ES |
dc.subject | electrochemical real-time mass spectrometry | es_ES |
dc.subject | density functional theory | es_ES |
dc.title | Different promoting roles of ruthenium for the oxidation of primary and secondary alcohols on PtRu electrocatalysts | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | © 2021 This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ | es_ES |
dc.relation.publisherversion | https://www.sciencedirect.com/science/article/pii/S0021951721002207 | es_ES |
dc.identifier.doi | 10.1016/j.jcat.2021.05.028 | |
dc.departamentoes | Polímeros y Materiales Avanzados: Física, Química y Tecnología | es_ES |
dc.departamentoeu | Polimero eta Material Aurreratuak: Fisika, Kimika eta Teknologia | es_ES |