title: Dioxygen and hydrogen peroxide reduction with hemocyanin model complexes.
abstract: Three copper polypyridyl complexes were examined as electrocatalysts for the oxygen reduction reaction (ORR): a Cu-N(3) complex, [Cu-[tris(6-methylpyridin-2-yl)methane]-(NCMe)]PF(6) (1); a related Cu(2)N(6) derivative, [Cu(2)-[1,2-bis(6-(bis(6-methylpyridin-2-yl)methyl)pyridin-2-yl)ethane]-(NCMe)(2)](PF(6))(2) (2); and the CuN(4) species [Cu-[tris(pyridin-2-ylmethyl)amine]](ClO(4))(2) [3](ClO(4))(2). Compared to other copper complexes, [3](ClO(4))(2) exhibits the highest reported ORR onset potential for a Cu complex of 0.53 V vs reversible hydrogen electrode at pH 1. The Cu(2)N(6) hemocyanin model is more active than the CuN(3), but both are less active than the CuN(4) complex. The results indicate that copper polypyridyl complexes are promising cathode catalysts for ORR.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, 600 S. Mathews Avenue, Urbana, Illinois 61801, USA.
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Thorseth
authors.forename: Christopher S
authors.initials: CS
authors.lastname: Letko
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Rauchfuss
authors.forename: Andrew A
authors.initials: AA
authors.lastname: Gewirth
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D004563:Electrochemistry; D006433:Hemocyanins / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D003300:Copper; D006433:Hemocyanins; D006861:Hydrogen Peroxide; D010100:Oxygen