Self-Adjusting Activity Induced by Intrinsic Reaction Intermediate in Fe-N-C Single-Atom Catalysts.

Fe-N-C single-atom catalysts (SACs) exhibit high activity for oxygen reduction reaction (ORR). However, it remains con-troversial how the active center mediates catalysis, and the predicted potential deviates from experimental results, hin-dering development of ideal SACs. Here, using first-principles calculations, we present a microkinetic model for ORR on Fe-N-C SACs, disclosing a self-adjusting mechanism induced by its intrinsic intermediate. The modelling results show that the single-atom Fe site of the FeN4 center of Fe-N-C is covered with an intermediate OH* from 0.28 to 1.00 V. Remarkably, such OH* becomes part of the active moiety, Fe(OH)N4, and can optimize intermediate bindings on the Fe site, exhibiting a theoretical half-wave potential of ~0.88 V. Partial current density analysis reveals the dominating associative path over the dissociative ones. In addition, ORR on Mn-N-C and Co-N-C SACs is unveiled. This work demonstrates the necessity of assessing the effect of intrinsic intermediates in single-atom catalysis and provides practical guidance for rational design of high-performance SACs.

• Publication year

  2019

• Venue

  Journal of the American Chemical Society

• Publication date

  2019-08-30

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/jacs.9b07712PMID 31468961
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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