• 文献标题:   Single and Multiple Doping in Graphene Quantum Dots: Unraveling the Origin of Selectivity in the Oxygen Reduction Reaction
  • 文献类型:   Article
  • 作  者:   FAVARO M, FERRIGHI L, FAZIO G, COLAZZO L, DI VAENTIN C, DURANTE C, SEDONA F, GENNARO A, AGNOLI S, GRANOZZI G
  • 作者关键词:   graphene, graphene oxide quantum dot, dopedquantum dot, multidoping, electrochemical preparation, oxygen reduction reaction, density functional theory
  • 出版物名称:   ACS CATALYSIS
  • ISSN:   2155-5435
  • 通讯作者地址:   Univ Milano Bicocca
  • 被引频次:   99
  • DOI:   10.1021/cs501211h
  • 出版年:   2015

▎ 摘  要

Singly and multiply doped graphene oxide quantum dots have been synthesized by a simple electrochemical method using water as solvent. The obtained materials have been characterized by photoemission spectroscopy and scanning tunneling microscopy, in order to get a detailed picture of their chemical and structural properties. The electrochemical activity toward the oxygen reduction reaction of the doped graphene oxide quantum dots has been investigated by cyclic voltammetry and rotating disk electrode measurements, showing a clear decrease of the overpotential as a function of the dopant according to the sequence: N similar to B > B,N. Moreover, assisted by density functional calculations of the Gibbs free energy associated with every electron transfer, we demonstrate that the selectivity of the reaction is controlled by the oxidation states of the dopants: as-prepared graphene oxide quantum dots follow a two-electron reduction path that leads to the formation of hydrogen peroxide, whereas after the reduction with NaBH4, the same materials favor a four-electron reduction of oxygen to water.