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

Abstract

Density functional theory (DFT) was used to investigate O2 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 O2 molecule via a “two feet” geometry. For this most stable O2 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 O2 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.

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Acknowledgments

The authors gratefully acknowledge financial support from the U.S. Department of Energy-Basic Energy Sciences (DE-FG02-07ER15896). The Ohio Supercomputer Center (OSC) is also acknowledged for generous computational support of this research.

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Correspondence to Aravind Asthagiri or Umit S. Ozkan or Christopher M. Hadad.

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Bao, X., Nie, X., von Deak, D. et al. A First-Principles Study of the Role of Quaternary-N Doping on the Oxygen Reduction Reaction Activity and Selectivity of Graphene Edge Sites. Top Catal 56, 1623–1633 (2013). https://doi.org/10.1007/s11244-013-0097-z

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Keywords

  • Oxygen reduction of graphene
  • Oxygen reduction reaction
  • O2 chemisorption
  • N-graphene
  • Edge sites
  • Density functional theory