• 文献标题:   Oxygen reduction reaction mechanism on nitrogen-doped graphene: A density functional theory study
  • 文献类型:   Article
  • 作  者:   YU L, PAN XL, CAO XM, HU P, BAO XH
  • 作者关键词:   oxygen reduction reaction mechanism, nitrogendoped graphene, density functional theory, catalysi, reaction kinetic
  • 出版物名称:   JOURNAL OF CATALYSIS
  • ISSN:   0021-9517
  • 通讯作者地址:   Queens Univ Belfast
  • 被引频次:   335
  • DOI:   10.1016/j.jcat.2011.06.015
  • 出版年:   2011

▎ 摘  要

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.