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

• DOI: 10.1021/jacs.7b06828
• Publication Date: 2017-08-30T10:45:55Z
• Authors: Pablo Garrido-Barros; Carolina Gimbert-...; Dooshaye Moonshiram; Antonio Picón; Pere Monge; Victor S. Batista; Antoni Llobet
• Keywords: Molecular catalysts; 2304 Química Macromolecular; Electronic π‑Delocalization; 7. Clean energy; 01 natural sciences; Catalytic water oxidation; 0104 chemical sciences

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 homologue, [(L)CuII]2– catalyst, 12– (L o-phenylenebis(oxamidate)). The catalytic performance both catalysts comparatively studied homogeneous phase heterogeneous by π-stacking anchorage graphene-based electrodes. In system, electronic perturbation provided pyrene functionality translates into 150 mV lower overpotential for 22– respect an impressive increase kcat from 6 128 s–1. Upon anchorage, interactions graphene sheets provide further π-delocalization that improves catalysts. this sense, turned out be most active due double influence graphene, displaying 538 mV, 540 s–1 producing than 5300 TONs.