Chemical Dopants on Edge of Holey Graphene Accelerate Electrochemical Hydrogen Evolution Reaction

Akichika Kumatani, Chiho Miura, Hirotaka Kuramochi, Tatsuhiko Ohto, Mitsuru Wakisaka, Yuki Nagata, Hiroki Ida, Yasufumi Takahashi, Kailong Hu, Samuel Jeong, Jun ichi Fujita, Tomokazu Matsue, Yoshikazu Ito

Research output: Contribution to journalArticlepeer-review

76 Citations (Scopus)


Carbon-based metal-free catalysts for the hydrogen evolution reaction (HER) are essential for the development of a sustainable hydrogen society. Identification of the active sites in heterogeneous catalysis is key for the rational design of low-cost and efficient catalysts. Here, by fabricating holey graphene with chemically dopants, the atomic-level mechanism for accelerating HER by chemical dopants is unveiled, through elemental mapping with atomistic characterizations, scanning electrochemical cell microscopy (SECCM), and density functional theory (DFT) calculations. It is found that the synergetic effects of two important factors—edge structure of graphene and nitrogen/phosphorous codoping—enhance HER activity. SECCM evidences that graphene edges with chemical dopants are electrochemically very active. Indeed, DFT calculation suggests that the pyridinic nitrogen atom could be the catalytically active sites. The HER activity is enhanced due to phosphorus dopants, because phosphorus dopants promote the charge accumulations on the catalytically active nitrogen atoms. These findings pave a path for engineering the edge structure of graphene in graphene-based catalysts.

Original languageEnglish
Article number1900119
JournalAdvanced Science
Issue number10
Publication statusPublished - 2019 May 17


  • chemical doping
  • electrochemical water splitting
  • graphene edge
  • noble metal-free catalysts
  • scanning electrochemical cell microscopy


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