Oxygen reduction reaction mechanism on nitrogen-doped graphene: A density functional theory study

Liang Yu, Xiulian Pan, Xiaoming Cao, P. Hu*, Xinhe Bao

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

416 Citations (Scopus)

Abstract

Nitrogen-doped graphene (N-graphene) was reported to exhibit a good activity experimentally as an electrocatalyst of oxygen reduction reaction (ORR) on the cathode of fuel cells under the condition of electropotential of similar to 0.04 V (vs. NNE) and pH of 14. This material is promising to replace or partially replace the conventionally used Pt. In order to understand the experimental results. ORR catalyzed by N-graphene is studied using density functional theory (DFT) calculations under experimental conditions taking the solvent, surface adsorbates, and coverages into consideration. Two mechanisms, i.e., dissociative and associative mechanisms, over different N-doping configurations are investigated. The results show that N-graphene surface is covered by O with 1/6 monolayer, which is used for reactions in this work. The transition state of each elementary step was identified using four different approaches, which give rise to a similar chemistry. A full energy profile including all the reaction barriers shows that the associative mechanism is more energetically favored than the dissociative one and the removal of O species from the surface is the rate-determining step. (C) 2011 Elsevier Inc. All rights reserved.

Original languageEnglish
Pages (from-to)183-190
Number of pages8
JournalJournal of Catalysis
Volume282
Issue number1
DOIs
Publication statusPublished - 15 Aug 2011

Keywords

  • Oxygen reduction reaction mechanism
  • Nitrogen-doped graphene
  • Density functional theory
  • Catalysis
  • Reaction kinetics
  • INITIO MOLECULAR-DYNAMICS
  • TRANSITION-METAL SURFACES
  • TOTAL-ENERGY CALCULATIONS
  • AUGMENTED-WAVE METHOD
  • MEMBRANE FUEL-CELLS
  • BASIS-SET
  • CARBON
  • PT(111)
  • CATALYSTS
  • WATER

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