2024-03-28T13:00:12Zhttps://gredos.usal.es/oai/requestoai:gredos.usal.es:10366/1451962022-02-07T15:38:29Zcom_10366_133237com_10366_4512com_10366_3823col_10366_133238
Garrido-Barros, Pablo
Gimbert-Suriñach, Carolina
Moonshiram, Dooshaye
Picón, Antonio
Monge, Pere
Batista, Victor S.
Llobet, Antoni
2021-02-09T09:46:15Z
2021-02-09T09:46:15Z
2017
Garrido Barrios, P.; Gimbert Suriñach, C. [et al.] (2017). Electronic π-Delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets. Journal of the American Chemical Society, 139(37), pp. 12907-12910. doi:10.1021/jacs.7b06828
0002-7863
http://hdl.handle.net/10366/145196
10.1021/jacs.7b06828
1520-5126
[EN] 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 oxidation 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 graphenebased electrodes. In the homogeneous system, the electronic perturbation provided by the pyrene functionality translates into a 150 mV lower overpotential for 22−
with respect to 12− and an impressive increase in the kcat from 6 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.
eng
http://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
Molecular catalysts
Electronic π‑Delocalization
Catalytic water oxidation
Electronic π-Delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets
info:eu-repo/semantics/article