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.
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Noffke, B.W., Li, Q., Li, Ls. et al. Oxygen Activation by N-doped Graphitic Carbon Nanostructures. MRS Online Proceedings Library 1725, 12–23 (2014). https://doi.org/10.1557/opl.2015.164
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DOI: https://doi.org/10.1557/opl.2015.164