Robust Molecular Anodes for Electrocatalytic Water Oxidation Based on Electropolymerized Molecular Cu Complexes.

Autor: Amthor S; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, Tarragona, 43007, Spain., Ranu K; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, Tarragona, 43007, Spain., Bellido CG; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, Tarragona, 43007, Spain., Salomón FF; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, Tarragona, 43007, Spain., Piccioni A; Department of Physics and Astronomy, Alma Mater Studiorum - Università di Bologna, viale C. Berti Pichat 6/2, Bologna, 40127, Italy., Mazzaro R; Department of Physics and Astronomy, Alma Mater Studiorum - Università di Bologna, viale C. Berti Pichat 6/2, Bologna, 40127, Italy., Boscherini F; Department of Physics and Astronomy, Alma Mater Studiorum - Università di Bologna, viale C. Berti Pichat 6/2, Bologna, 40127, Italy., Pasquini L; Department of Physics and Astronomy, Alma Mater Studiorum - Università di Bologna, viale C. Berti Pichat 6/2, Bologna, 40127, Italy., Gil-Sepulcre M; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, Tarragona, 43007, Spain., Llobet A; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, Tarragona, 43007, Spain.; Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, Barcelona, 08193, Spain.
Jazyk: angličtina
Zdroj: Advanced materials (Deerfield Beach, Fla.) [Adv Mater] 2024 Feb; Vol. 36 (7), pp. e2308392. Date of Electronic Publication: 2023 Dec 07.
DOI: 10.1002/adma.202308392
Abstrakt: A multistep synthesis of a new tetra-amidate macrocyclic ligand functionalized with alkyl-thiophene moieties, 15,15-bis(6-(thiophen-3-yl)hexyl)-8,13-dihydro-5H-dibenzo[b,h][1,4,7,10]tetraazacyclotridecine-6,7,14,16(15H,17H)-tetraone, H 4 L, is reported. The reaction of the deprotonated ligand, L 4- , and Cu(II) generates the complex [LCu] 2- , that can be further oxidized to Cu(III) with iodine to generate [LCu] - . The H 4 L ligand and their Cu complexes have been thoroughly characterized by analytic and spectroscopic techniques (including X-ray Absorption Spectroscopy, XAS). Under oxidative conditions, the thiophene group of [LCu] 2- complex polymerizes on the surface of graphitic electrodes (glassy carbon disks (GC), glassy carbon plates (GC p ), carbon nanotubes (CNT), or graphite felts (GF)) generating highly stable thin films. With CNTs deposited on a GC by drop casting, hybrid molecular materials labeled as GC/CNT@p-[LCu] 2- are obtained. The latter are characterized by electrochemical techniques that show their capacity to electrocatalytically oxidize water to dioxygen at neutral pH. These new molecular anodes achieve current densities in the range of 0.4 mA cm -2 at 1.30 V versus NHE with an onset overpotential at ≈250 mV. Bulk electrolysis experiments show an excellent stability achieving TONs in the range of 7600 during 24 h with no apparent loss of catalytic activity and maintaining the molecular catalyst integrity, as evidenced by electrochemical techniques and XAS spectroscopy.
(© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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