Electronic Perturbation of Isolated Fe Coordination Structure for Enhanced Nitrogen Fixation

Bin Chang, Zhen Cao, Yuanfu Ren, Cailing Chen, Luigi Cavallo*, Fazal Raziq, Shouwei Zuo, Weijia Zhou, Yu Han, Huabin Zhang*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Modulation of the local electronic structure of isolated coordination structures plays a critical role in electrocatalysis yet remains a grand challenge. Herein, we have achieved electron perturbation for the isolated iron coordination structure via tuning the iron spin state from a high spin state (FeN4) to a medium state (FeN2B2). The transition of spin polarization facilitates electron penetration into the antibonding π orbitals of nitrogen and effectively activates nitrogen molecules, thereby achieving an ammonia yield of 115 μg h-1 mg-1cat. and a Faradaic efficiency of 24.8%. In situ spectroscopic studies and theoretical calculations indicate that boron coordinate sites, as electron acceptors, can regulate the adsorption energy of NxHy intermediates on the Fe center. FeN2B2 sites favor the NNH* intermediate formation and reduce the energy barrier of rate-determining steps, thus accounting for excellent nitrogen fixation performance. Our strategy provides an effective approach for designing efficient electrocatalysts via precise electronic perturbation.

Original languageEnglish (US)
Pages (from-to)288-298
Number of pages11
JournalACS Nano
Issue number1
StatePublished - Jan 9 2024

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society.


  • ammonia synthesis
  • coordination structure optimization
  • electrochemical nitrogen reduction
  • Electronic perturbation
  • single-atom iron site

ASJC Scopus subject areas

  • General Materials Science
  • General Engineering
  • General Physics and Astronomy


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