Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO2

Samira Siahrostami*, Kun Jiang, Mohammadreza Karamad, Karen Chan, Haotian Wang, Jens Nørskov

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review


Despite numerous experimental efforts that have been dedicated to studying carbon-based materials for electrochemical reduction of CO2, a rationalization of the associated trends in the intrinsic activity of different active motifs has so far been elusive. In the present work, we employ density functional theory calculations to examine a variety of different active sites in N-doped graphene to give a comprehensive outline of the trends in activity. We find that adsorption energies of COOH∗ and CO∗ do not follow the linear scaling relationships observed for the pure transition metals, and this unique scaling is rationalized through differences in electronic structure between transition metals and defected graphene. This finding rationalizes most of the experimental observations on the carbon-based materials which present promising catalysts for the two-electron reduction of CO2 to CO. With this simple thermodynamic analysis, we identify several active sites that are expected to exhibit a comparable or even better activity to the state-of-the-art gold catalyst, and several configurations are suggested to be selective for CO2RR over HER.

Original languageEnglish
JournalACS Sustainable Chemistry and Engineering
Issue number11
Pages (from-to)11080-11085
Number of pages6
Publication statusPublished - 2017
Externally publishedYes


  • Calculated limiting potential
  • Density functional theory (DFT)
  • Free energy diagram
  • Hydrogen evolution reaction (HER)
  • Scaling relation

Cite this