The Innovation (Jul 2022)

Spin engineering of single-site metal catalysts

  • Zichuang Li,
  • Ruguang Ma,
  • Qiangjian Ju,
  • Qian Liu,
  • Lijia Liu,
  • Yufang Zhu,
  • Minghui Yang,
  • Jiacheng Wang

Journal volume & issue
Vol. 3, no. 4
p. 100268

Abstract

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Single-site metal atoms (SMAs) on supports are attracting extensive interest as new catalytic systems because of maximized atom utilization and superior performance. However, rational design of configuration-optimized SMAs with high activity from the perspectives of fundamental electron spin is highly challenging. Herein, N-coordinated Fe single atoms are successfully distributed over axial carbon micropores to form dangling-FeN4 centers (d-FeN4). This unique d-FeN4 demonstrates much higher intrinsic activity toward oxygen reduction reaction (ORR) in HClO4 than FeN4 without micropore underneath and commercial Pt/C. Both theoretical calculation and electronic structure characterization imply that d-FeN4 endows central Fe with medium spin (t2g4 eg1), which provides a spin channel for electron transition compared with FeN4 with low spin. This leads to the facile formation of the singlet state of oxygen-containing species from triplet oxygen during the ORR, thus showing faster kinetics than FeN4. This work provides an in-depth understanding of spin tuning on SMAs for advanced energy catalysis.

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