Axial Sulfur-Coordination Engineering Boosting Fe–N–C Catalysts for High-Performance Proton Exchange Membrane Fuel Cells

Authors

Lin Lin, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
Xiu-Xuan Hou, State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry Chinese Academy of Sciences, Changchun 130022, China.
Zhe-Chen Fan, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
Yi-Xuan Yin, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
Wei-Yi Zhao, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
Kai Wei, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
Yu-Die Zhou, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
Li-Na Hou, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
Ying Wang, State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry Chinese Academy of Sciences, Changchun 130022, China.Follow
Hao Wan, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.Follow
Jun-Jie Ge, State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.Follow

Document Type

Article

Corresponding Author(s)

Ying Wang(ywang_2012@ciac.ac.cn);
Hao Wan(wh1992@mail.ustc.edu.cn);
Jun-Jie Ge(gejunjie@ustc.edu.cn)

Abstract

Fe-N-C catalysts have long suffered from kinetically sluggish oxygen reduction reaction (ORR) due to excessive adsorption strength toward oxygen intermediates and low site utilization. Heteroatom doping effectively accelerates ORR reaction kinetics through electronic structure modulation of metal sites for optimal intermediate adsorption, while chemical vapor deposition (CVD) enhances the turnover frequency (TOF) of active sites. Herein, we develop an FeSNC catalyst featuring abundant FeS₁N₄ sites via a dual-precursor CVD strategy. Experimental and theoretical analyses reveal that S incorporation disrupts the symmetric coordination of active sites, which optimizes OH* adsorption energies from 0.212 eV to 1.194 eV. Moreover, the TOF increased from 1.98 e^-1·site^-1·s^-1 to 6.32 e^-1·site^-1·s^-1, significantly enhancing the intrinsic activity of the catalyst. More notably, the hydrophilic character of S-containing species substantially improved hydrophilicity in the S-doped catalyst, thereby promoting mass transport of oxygen and proton delivery. As a result, FeSNC catalyst exhibits an extremely high half-wave potential of 0.863 V in 0.1 M HClO₄ and achieves a peak power density of 1.2 W·cm^-2 in H₂-O₂ PEMFCs. This work highlight the critical role of coordination engineering.

Graphical Abstract

Keywords

Oxygen reduction reaction, Fe-N-C, Heteroatom doping, Electronic regulation, Mass transport

DOI

10.61558/2993-074X.3592

Online Date

11-5-2025

Recommended Citation

Lin Lin, Xiu-Xuan Hou, Zhe-Chen Fan, Yi-Xuan Yin, Wei-Yi Zhao, Kai Wei, Yu-Die Zhou, Li-Na Hou, Ying Wang, Hao Wan, Jun-Jie Ge. Axial Sulfur-Coordination Engineering Boosting Fe–N–C Catalysts for High-Performance Proton Exchange Membrane Fuel Cells[J]. Journal of Electrochemistry, doi: 10.61558/2993-074X.3592.