Oxygen Activation by N-doped Graphitic Carbon Nanostructures. Issue 1725 (23rd February 2015)

• Record Type: Journal Article
• Authors: Noffke, Benjamin W.; Li, Qiqi; Li, Liang-shi; Raghavachari, Krishnan
• Editors: Ajayan, P.M.; Koester, S.J.; McDevitt, M.R.; Renugopalakrishnan, V.
• Is Part Of: MRS proceedings. Issue 1725:(2015)
• Publication Date: 2015-02-23
• Subjects: electronic structure, -- catalytic, -- dopant; Electrical engineering -- Congresses; Physics -- Congresses; Materials -- Research -- Congresses; Materials science -- Congresses; 620.11
• DOI: 10.1557/opl.2015.164
• Languages: English
• ISSNs: 0272-9172

Abstract

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, C50 N2 H20, 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.