Electronic I-Delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets

Pablo Garrido-Barros, Carolina Gimbert-Surinifach, Dooshaye Moonshiram, Antonio Picón, Pere Monge, Victor S. Batista, Antoni Llobet

Research output: Contribution to journalArticleResearchpeer-review

73 Citations (Scopus)

Abstract

© 2017 American Chemical Society. 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 I-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 I-stacking anchorage to graphene-based 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, I-stacking interactions with the graphene sheets provide further I-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.
Original languageEnglish
Pages (from-to)12907-12910
JournalJournal of the American Chemical Society
Volume139
Issue number37
DOIs
Publication statusPublished - 1 Jan 2017

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