dc.contributor.author | Garcia Melchor, Max | en |
dc.contributor.author | Perova, Tatiana | en |
dc.contributor.author | Colavita, Paula | en |
dc.date.accessioned | 2019-08-20T08:16:07Z | |
dc.date.available | 2019-08-20T08:16:07Z | |
dc.date.issued | 2019 | en |
dc.date.submitted | 2019 | en |
dc.identifier.citation | Behan, J. A.; Mates-Torres, E.; Stamatin, S. N.; Domínguez, C.; Iannaci, A.; Fleischer, K.; Hoque, Md. K.; Perova, T. S.; García-Melchor, M.; Colavita, P. E., Untangling cooperative effects of pyridinic and graphitic nitrogen sites at metal-free N-doped carbon electrocatalysts for the oxygen reduction reaction, Small, 15, 2019, 1902081- | en |
dc.identifier.other | Y | en |
dc.identifier.uri | http://hdl.handle.net/2262/89232 | |
dc.description | PUBLISHED | en |
dc.description.abstract | Metal-free carbon electrodes with well-defined composition and smooth topography were prepared via sputter deposition followed by thermal treatment with inert and reactive gases. XPS and Raman spectroscopies show that three carbons of similar N/C content that differ in N-site composition were thus prepared: an electrode consisting of almost exclusively graphitic-N (NG), an electrode with predominantly pyridinic-N (NP) and one with ca. 1:1 NG:NP composition. These materials were used as model systems to investigate activity of N-doped carbons in the oxygen reduction reaction (ORR) using voltammetry. Results show that selectivity towards 4e-reduction of O2 is strongly influenced by the NG/NP site composition, with the material possessing nearly uniform NG/NP composition being the only one yielding a 4e-reduction. Computational studies on model graphene clusters were carried out to elucidate the effect of N-site homogeneity on the reaction pathway. Calculations show that for pure NG-doping or NP-doping of model graphene clusters, adsorption of hydroperoxide and hydroperoxyl radical intermediates, respectively, is weak thus favoring desorption prior to complete 4e-reduction to hydroxide. Clusters with mixed NG/NP sites display synergistic effects, suggesting that co-presence of these sites improves activity and selectivity by achieving high theoretical reduction potentials while facilitating retention of intermediates. | en |
dc.format.extent | 1902081 | en |
dc.language.iso | en | en |
dc.relation.ispartofseries | Small | en |
dc.relation.ispartofseries | 15 | en |
dc.rights | Y | en |
dc.subject | N-doped carbon | en |
dc.subject | Oxygen reduction reaction | en |
dc.subject | Electrocatalysis | en |
dc.subject | Density functional theory | en |
dc.subject | Synergistic | en |
dc.title | Untangling cooperative effects of pyridinic and graphitic nitrogen sites at metal-free N-doped carbon electrocatalysts for the oxygen reduction reaction | en |
dc.type | Journal Article | en |
dc.type.supercollection | scholarly_publications | en |
dc.type.supercollection | refereed_publications | en |
dc.identifier.peoplefinderurl | http://people.tcd.ie/garciamm | en |
dc.identifier.peoplefinderurl | http://people.tcd.ie/perovat | en |
dc.identifier.peoplefinderurl | http://people.tcd.ie/colavitp | en |
dc.identifier.rssinternalid | 203930 | en |
dc.identifier.doi | https://doi.org/10.1002/smll.201902081 | en |
dc.rights.ecaccessrights | openAccess | |
dc.subject.TCDTheme | Nanoscience & Materials | en |
dc.subject.TCDTheme | Smart & Sustainable Planet | en |
dc.identifier.orcid_id | 0000-0003-1348-4692 | en |
dc.status.accessible | N | en |
dc.contributor.sponsor | Irish Research Council (IRC) | en |
dc.contributor.sponsorGrantNumber | GOIPG/2014/399 | en |
dc.contributor.sponsor | Marie Curie | en |
dc.contributor.sponsorGrantNumber | 748968 (FREMAB) and 799175 (HiBriCarbon) | en |
dc.contributor.sponsor | Science Foundation Ireland (SFI) | en |
dc.contributor.sponsorGrantNumber | 13/CDA/2213 | en |