Citation: Zhili Yang, Liqun Liu, Xuebi Rao, Zeyu Jin, Jialin Sun, Yongkang Zhu, Shiming Zhang. Deprotonation effect doubles active site density in Fe-N₄-C catalyst for oxygen reduction electrocatalysis[J]. Chinese Chemical Letters, ;2025, 36(11): 111440. doi: 10.1016/j.cclet.2025.111440 shu

Deprotonation effect doubles active site density in Fe-N₄-C catalyst for oxygen reduction electrocatalysis

Institute for Sustainable Energy/College of Sciences, Shanghai University, Shanghai 200444, China

smzhang@shu.edu.cn

Received Date: 24 January 2025
Revised Date: 7 June 2025
Accepted Date: 10 June 2025
Available Online: 11 June 2025

Figures(6)

Iron-nitrogen-carbon (Fe-N-C) materials with Fe-N₄ structures have been considered as the most promising alternatives of scarce and precious platinum (Pt) for oxygen reduction reaction. Particularly, the high-temperature pyrolysis of a precursor mixture of N-containing amine polymers, Fe salts, and carbon supports, has become a popular method for the synthesis of high-performance Fe-N-C catalysts. The oxidative polymerization of amine monomers can usually proceed under acidic conditions, however, the acid-caused protonation of N-groups is not conducive to their coordination with Fe ions for the formation of high-density Fe-N₄ sites. Here, we propose a protonation elimination strategy of soaking the polymerization products in alkaline solutions to increase Fe-N₄ active sites. Theoretical calculations display that the Gibbs free energy change values of binding reactions between Fe ions and N-groups are -3.70 and -26.99 kcal/mol at pH 0 and 7, respectively, suggesting that the deprotonation can facilitate the Fe-N coordination. There is a two-fold increase in the number of Fe-N₄ active sites for final Fe-N-C catalyst which exhibits significantly enhanced ORR activity and excellent Zn-air battery performance. This deprotonation effect can be applied to different amine compounds and transition-metal ions as a universal strategy for the development of preeminent non-precious metal carbon catalysts.
- Oxygen reduction reaction,
- Iron-nitrogen-carbon,
- Amine polymers,
- Fe-N₄ active sites,
- Deprotonation effect
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沈阳化工大学材料科学与工程学院沈阳 110142

Deprotonation effect doubles active site density in Fe-N4-C catalyst for oxygen reduction electrocatalysis

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通讯作者: 陈斌, bchen63@163.com

Deprotonation effect doubles active site density in Fe-N₄-C catalyst for oxygen reduction electrocatalysis