title: A Million Turnover Molecular Anode for Catalytic Water Oxidation.
abstract: Molecular ruthenium-based water oxidation catalyst precursors of general formula [Ru(tda)(Li)2] (tda2-is [2,2':6',2''-terpyridine]-6,6''-dicarboxylato; L1=4-(pyren-1-yl)-N-(pyridin-4-ylmethyl)butanamide, 1 b; L2=4-(pyren-1-yl)pyridine), 1 c), have been prepared and thoroughly characterized. Both complexes contain a pyrene group allowing ready and efficiently anchoring via π interactions on multi-walled carbon nanotubes (MWCNT). These hybrid solid state materials are exceptionally stable molecular water-oxidation anodes capable of carrying out more than a million turnover numbers (TNs) at pH 7 with an Eapp=1.45 V vs. NHE without any sign of degradation. XAS spectroscopy analysis before, during, and after catalysis together with electrochemical techniques allow their unprecedented oxidative ruggedness to be monitored and verified.
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, Carrer dels Til⋅lers s/n, 08193, Cerdanyola del Vallès, Spain.|Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Carrer Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
authors.forename: Jordi
authors.initials: J
authors.lastname: Creus
authors.affiliation: Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Carrer Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.|Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Roc
authors.initials: R
authors.lastname: Matheu
authors.affiliation: Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Carrer Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
authors.forename: Itziar
authors.initials: I
authors.lastname: Peñafiel
authors.affiliation: Chemical Science and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL, 60439, USA.
authors.forename: Dooshaye
authors.initials: D
authors.lastname: Moonshiram
authors.affiliation: Departament de Química Orgànica i Analítica, Universitat Rovira i Virgili, Carrer Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
authors.forename: Pascal
authors.initials: P
authors.lastname: Blondeau
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, Carrer dels Til⋅lers s/n, 08193, Cerdanyola del Vallès, Spain.
authors.forename: Jordi
authors.initials: J
authors.lastname: García-Antón
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, Carrer dels Til⋅lers s/n, 08193, Cerdanyola del Vallès, Spain.
authors.forename: Xavier
authors.initials: X
authors.lastname: Sala
authors.affiliation: Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Carrer Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
authors.forename: Cyril
authors.initials: C
authors.lastname: Godard
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, Carrer dels Til⋅lers s/n, 08193, Cerdanyola del Vallès, Spain.|Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Antoni
authors.identifier: 0000-0002-6176-5272
authors.initials: A
authors.lastname: Llobet
keywords: electrocatalysis; redox properties; transition metal complexes; water oxidation catalysis; water splitting