Dioxygen and hydrogen peroxide reduction with hemocyanin model complexes

Matthew A. Thorseth; Christopher S. Letko; Thomas B. Rauchfuss; Andrew A. Gewirth

doi:10.1021/ic200386d

Dioxygen and hydrogen peroxide reduction with hemocyanin model complexes

Matthew A. Thorseth, Christopher S. Letko, Thomas B. Rauchfuss, Andrew A. Gewirth

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Abstract

Three copper polypyridyl complexes were examined as electrocatalysts for the oxygen reduction reaction (ORR): a Cu-N₃ complex, [Cu-[tris(6-methylpyridin-2-yl)methane]-(NCMe)]PF₆ (1); a related Cu₂N₆ derivative, [Cu₂-[1,2-bis(6-(bis(6- methylpyridin-2-yl)methyl)pyridin-2-yl)ethane]-(NCMe)₂](PF ₆)₂ (2); and the CuN₄ species [Cu-[tris(pyridin-2-ylmethyl)amine]](ClO₄)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 ₂N₆ hemocyanin model is more active than the CuN ₃, but both are less active than the CuN₄ complex. The results indicate that copper polypyridyl complexes are promising cathode catalysts for ORR.

Original language	English (US)
Pages (from-to)	6158-6162
Number of pages	5
Journal	Inorganic Chemistry
Volume	50
Issue number	13
DOIs	https://doi.org/10.1021/ic200386d
State	Published - Jul 4 2011

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic200386d

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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-N3 complex, [Cu-[tris(6-methylpyridin-2-yl)methane]-(NCMe)]PF6 (1); a related Cu2N6 derivative, [Cu2-[1,2-bis(6-(bis(6- methylpyridin-2-yl)methyl)pyridin-2-yl)ethane]-(NCMe)2](PF 6)2 (2); and the CuN4 species [Cu-[tris(pyridin-2-ylmethyl)amine]](ClO4)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 2N6 hemocyanin model is more active than the CuN 3, but both are less active than the CuN4 complex. The results indicate that copper polypyridyl complexes are promising cathode catalysts for ORR.",

author = "Thorseth, {Matthew A.} and Letko, {Christopher S.} and Rauchfuss, {Thomas B.} and Gewirth, {Andrew A.}",

year = "2011",

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doi = "10.1021/ic200386d",

language = "English (US)",

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journal = "Inorganic Chemistry",

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T1 - Dioxygen and hydrogen peroxide reduction with hemocyanin model complexes

AU - Thorseth, Matthew A.

AU - Letko, Christopher S.

AU - Rauchfuss, Thomas B.

AU - Gewirth, Andrew A.

PY - 2011/7/4

Y1 - 2011/7/4

N2 - Three copper polypyridyl complexes were examined as electrocatalysts for the oxygen reduction reaction (ORR): a Cu-N3 complex, [Cu-[tris(6-methylpyridin-2-yl)methane]-(NCMe)]PF6 (1); a related Cu2N6 derivative, [Cu2-[1,2-bis(6-(bis(6- methylpyridin-2-yl)methyl)pyridin-2-yl)ethane]-(NCMe)2](PF 6)2 (2); and the CuN4 species [Cu-[tris(pyridin-2-ylmethyl)amine]](ClO4)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 2N6 hemocyanin model is more active than the CuN 3, but both are less active than the CuN4 complex. The results indicate that copper polypyridyl complexes are promising cathode catalysts for ORR.

AB - Three copper polypyridyl complexes were examined as electrocatalysts for the oxygen reduction reaction (ORR): a Cu-N3 complex, [Cu-[tris(6-methylpyridin-2-yl)methane]-(NCMe)]PF6 (1); a related Cu2N6 derivative, [Cu2-[1,2-bis(6-(bis(6- methylpyridin-2-yl)methyl)pyridin-2-yl)ethane]-(NCMe)2](PF 6)2 (2); and the CuN4 species [Cu-[tris(pyridin-2-ylmethyl)amine]](ClO4)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 2N6 hemocyanin model is more active than the CuN 3, but both are less active than the CuN4 complex. The results indicate that copper polypyridyl complexes are promising cathode catalysts for ORR.

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Dioxygen and hydrogen peroxide reduction with hemocyanin model complexes

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