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Oxygen Activation by N-doped Graphitic Carbon Nanostructures

Published online by Cambridge University Press:  23 February 2015

Benjamin W. Noffke,
Qiqi Li,
Liang-shi Li and
Krishnan Raghavachari
Benjamin W. Noffke
Affiliation:
Department of Chemistry, Indiana University, Bloomington, IN 47405
Qiqi Li
Affiliation:
Department of Chemistry, Indiana University, Bloomington, IN 47405
Liang-shi Li
Affiliation:
Department of Chemistry, Indiana University, Bloomington, IN 47405
Krishnan Raghavachari
Affiliation:
Department of Chemistry, Indiana University, Bloomington, IN 47405
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Abstract

Fundamental understanding of the oxygen reduction reaction (ORR) electrocatalyzed by nitrogen-doped carbon requires a well-defined structure to correlate structure to function. Well-characterized N-doped graphitic nanostructures derived from benzene derivatives have been synthesized in our group, and shown to catalyze a four-electron ORR under alkaline conditions. Density functional theory calculations have been performed on a model N-doped graphitic nanostructure, C50N2H20, to determine an oxygen activation mechanism. With guidance through an experimentally determined Pourbaix diagram, DFT calculations clearly indicate that the catalyst must undergo a 2e−,1H+ reduction to generate a reactive carbanionic intermediate that activates oxygen with a spin inversion.

Keywords

electronic structurecatalyticdopant

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Articles
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MRS Online Proceedings Library (OPL) , Volume 1725: Symposium I – Emerging 1D and 2D Nanomaterials in Health Care , 2015, mrsf14-1725-i02-05
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Copyright © Materials Research Society 2015 

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