dc.contributor.author |
Garrido-Barros, Pablo |
dc.contributor.author |
Gimbert-Suriñach, Carolina |
dc.contributor.author |
Moonshiram, Dooshaye |
dc.contributor.author |
Picón, Antonio |
dc.contributor.author |
Monge, Pere |
dc.contributor.author |
Batista, Victor S. |
dc.contributor.author |
Llobet, Antoni |
dc.date.accessioned |
2018-01-15T16:04:17Z |
dc.date.accessioned |
2018-02-15T10:27:33Z |
dc.date.available |
2018-01-15T16:04:17Z |
dc.date.available |
2018-02-15T10:27:33Z |
dc.date.issued |
2017 |
dc.identifier.uri |
http://hdl.handle.net/2072/226323 |
dc.identifier.uri |
http://hdl.handle.net/2072/305759 |
dc.language.iso |
eng |
dc.publisher |
American Chemical Society |
dc.relation |
MINECO with FEDER Funds |
dc.relation |
Proyectos I+D+i - Retos 2016 |
dc.relation |
Severo Ochoa Excellence Accreditation 2014-2018 |
dc.relation |
MC4WS |
dc.relation.ispartof |
Journal of the American Chemical Society 2017, Just Accepted |
dc.rights |
Copyright © 2017 American Chemical Society |
dc.title |
Electronic π-delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets |
dc.type |
info:eu-repo/semantics/article |
dc.relation.projectID |
CTQ2016-80058-R |
dc.relation.projectID |
SEV2013-0319, CTQ2016-81923-REDC |
dc.identifier.doi |
https://dx.doi.org/10.1021/jacs.7b06828 |
dc.rights.accessLevel |
info:eu-repo/semantics/openAccess |
dc.description.abstract |
A molecular water oxidation catalyst based on the copper complex of general formula [(Lpy)CuII]2-, 22-, (Lpy is 4-pyrenyl-1,2-phenylenebis(oxamidate) ligand) has been rationally designed and prepared to support a more extended π-conjugation through its structure in contrast with its homologue, the [(L)CuII]2- water oxi-dation catalyst, 12- (L is o-phenylenebis(oxamidate)). The catalytic performance of both catalysts has been comparatively studied in homogeneous phase and in heterogeneous phase by π-stacking anchorage to graphene-based electrodes. In the homogeneous sys-tem, the electronic perturbation provided by the pyrene functionality translates into a 150 mV lower overpotential for 22- respect to 12- and an impressive increase in the kcat from 6 s-1 to 128 s-1. Upon anchorage, π-stacking interactions with the graphene sheets provide further π-delocalization that improves the catalytic performance of both catalysts. In this sense, 22- turned out to be the most active catalyst due to the double influence of both the pyrene and the graphene, displaying an overpotential of 538 mV, a kcat of 540 s-1 and producing more than 5300 TONs |