A Million Turnover Molecular Anode for Catalytic Water Oxidation

Jordi Creus; Roc Matheu; Itziar Peñafiel; Dooshaye Moonshiram; Pascal Blondeau; Jordi Benet-Buchholz; Jordi García-Antón; Xavier Sala; Cyril Godard; Antoni Llobet

doi:10.1002/anie.201609167

A Million Turnover Molecular Anode for Catalytic Water Oxidation

Angew Chem Int Ed Engl. 2016 Dec 5;55(49):15382-15386. doi: 10.1002/anie.201609167. Epub 2016 Nov 7.

Authors

Jordi Creus^{1

2}, Roc Matheu^{2

3}, Itziar Peñafiel², Dooshaye Moonshiram⁴, Pascal Blondeau⁵, Jordi Benet-Buchholz³, Jordi García-Antón¹, Xavier Sala¹, Cyril Godard², Antoni Llobet^{1

3}

Affiliations

¹ Departament de Química, Universitat Autònoma de Barcelona, Carrer dels Til⋅lers s/n, 08193, Cerdanyola del Vallès, Spain.
² Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Carrer Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
³ Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Països Catalans 16, 43007, Tarragona, Spain.
⁴ Chemical Science and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL, 60439, USA.
⁵ Departament de Química Orgànica i Analítica, Universitat Rovira i Virgili, Carrer Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.

PMID: 27897422
DOI: 10.1002/anie.201609167

Abstract

Molecular ruthenium-based water oxidation catalyst precursors of general formula [Ru(tda)(Lⁱ )₂ ] (tda^2- 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 E_app =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.

Keywords: electrocatalysis; redox properties; transition metal complexes; water oxidation catalysis; water splitting.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't