title: A soluble copper-bipyridine water-oxidation electrocatalyst.
abstract: The oxidation of water to O(2) is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for this reaction, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Reported here is the first copper-based catalyst for electrolytic water oxidation. Copper-bipyridine-hydroxo complexes rapidly form in situ from simple commercially available copper salts and bipyridine at high pH. Cyclic voltammetry of these solutions at pH 11.8-13.3 shows large, irreversible currents, indicative of catalysis. The production of O(2) is demonstrated both electrochemically and with a fluorescence probe. Catalysis occurs at about 750 mV overpotential. Electrochemical, electron paramagnetic resonance and other studies indicate that the catalyst is a soluble molecular species, that the dominant species in the catalytically active solutions is (2,2'-bipyridine)Cu(OH)(2) and that this is among the most rapid homogeneous water-oxidation catalysts, with a turnover frequency of ~100 s(-1).
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
authors.forename: Shoshanna M
authors.initials: SM
authors.lastname: Barnett
authors.forename: Karen I
authors.initials: KI
authors.lastname: Goldberg
authors.forename: James M
authors.initials: JM
authors.lastname: Mayer
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D055664:Electrochemical Techniques; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D011725:Pyridines; D014867:Water; D003300:Copper