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Published on: December 4, 2017
Electronic modulation of Fe-N4 sites by second-shell sulfur for enhanced oxygen reduction electrocatalysis
Jiayun Wu1, Xiangxiong Chen1, Jing Hu2
1College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China. 30663804@qq.com.
Chemical Communications (Cambridge, England)
|June 16, 2026
Summary
Single-atom catalysts with iron and sulfur show enhanced oxygen reduction reaction activity. This breakthrough improves zinc-air battery performance and clarifies sulfur's role in catalyst design.
Area of Science:
- Materials Science
- Electrochemistry
- Catalysis
Background:
- Single-atom catalysts (SACs) offer high efficiency but their performance is sensitive to the coordination environment.
- The role of non-metal heteroatoms, like sulfur (S), in the second coordination shell of iron (Fe) SACs for oxygen reduction reaction (ORR) remains debated.
- Optimizing the catalyst's local structure is crucial for advancing energy storage technologies.
Purpose of the Study:
- To engineer atomically dispersed Fe single-atom catalysts (SACs) using sulfur (S) as a second-shell modulator.
- To investigate the impact of this S modulation on the oxygen reduction reaction (ORR) activity.
- To evaluate the performance of these engineered catalysts in zinc-air batteries and resolve mechanistic questions regarding S's coordination role.
Main Methods:
- Synthesis of Fe single-atom catalysts with precisely controlled S incorporation in the second coordination shell.
- Electrochemical characterization to assess ORR activity, including cyclic voltammetry and rotating disk electrode measurements.
- Operando X-ray spectroscopy and density functional theory (DFT) calculations to elucidate the coordination environment and reaction mechanism.
Main Results:
- The engineered Fe SACs with S as a second-shell modulator exhibited significantly enhanced ORR activity compared to catalysts with direct S ligation.
- The optimized catalyst demonstrated excellent rate capability and long-term stability in zinc-air battery tests.
- Spectroscopic and computational analyses confirmed that S acts as an environmental modulator, influencing the Fe active site's electronic structure without direct coordination.
Conclusions:
- Atomically dispersed Fe single-atom catalysts modulated by second-shell sulfur achieve superior ORR performance.
- This S modulation strategy effectively enhances zinc-air battery efficiency.
- The study clarifies the non-ligand coordination role of sulfur in Fe-based SACs, providing critical insights for future catalyst design.
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