NDLI: A First-Principles Study of the Role of Quaternary-N Doping on the Oxygen Reduction Reaction Activity and Selectivity of Graphene Edge Sites

Content Provider	Springer Nature Link
Author	Bao, Xiaoguang Nie, Xiaowa Deak, Dieter Biddinger, Elizabeth J. Luo, Wenjia Asthagiri, Aravind Ozkan, Umit S. Hadad, Christopher M.
Copyright Year	2013
Abstract	Density functional theory (DFT) was used to investigate O$_{2}$ chemisorption on the edge sites of graphene doped with quaternary nitrogen (N-graphene). The location of the doped quaternary N within the graphene cluster was systematically varied to determine the effect of interior versus edge doping on the reactivity of the edge graphene sites. Model 1b, where a quaternary-N atom is at the zigzag edge of the graphene cluster, is found to be the most favored structure and strongly adsorbs O$_{2}$ molecule via a “two feet” geometry. For this most stable O$_{2}$ binding configuration, the potential-dependent free energy of reaction for the subsequent oxygen reduction reaction (ORR) steps was evaluated. The favored four electron-proton transfer mechanism passes through a dissociative O+OH state instead of an OOH* intermediate, followed by a series of reduction steps to produce water. At the equilibrium potential for ORR of 1.23 V-NHE, the protonation of O* and OH* both show uphill steps, but the production of O* is facile with a small overpotential. An applied potential of −0.15 V-NHE is required to facilitate the protonation of OH* to water, a larger overpotential than observed experimentally. While solvent effects may reduce this overpotential, our results suggest that the edge of the N-graphene is very active towards activation of O$_{2}$ and production of O* and OH* but because of strong binding of the oxygen atom, the subsequent steps of the ORR reaction will be hindered. Mechanisms that have OH* formed at the edge site and then move to adjacent sites for more facile protonation will have to be explored in the future.
Starting Page	1623
Ending Page	1633
Page Count	11
File Format	PDF
ISSN	10225528
Journal	Topics in Catalysis
Volume Number	56
Issue Number	18-20
e-ISSN	15729028
Language	English
Publisher	Springer US
Publisher Date	2013-06-27
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Oxygen reduction of graphene Oxygen reduction reaction O$_{2}$ chemisorption N-graphene Edge sites Density functional theory Catalysis Physical Chemistry Pharmacy Industrial Chemistry/Chemical Engineering Characterization and Evaluation of Materials
Content Type	Text
Resource Type	Article
Subject	Chemistry Catalysis

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