| Institution: | 1. Joint International Laboratory on Environmental and Energy Frontier Materials, School of Environmental and Chemical Engineering, Shanghai University, China
These authors contributed equally to this work.;2. Joint International Laboratory on Environmental and Energy Frontier Materials, School of Environmental and Chemical Engineering, Shanghai University, China;3. Department of Electrical and Computer Engineering, University of Toronto, 35 St George Street, Toronto, Ontario, M5S 1A4 Canada;4. School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China;5. Centre for Clean Energy Technology, University of Technology Sydney, Broadway, Sydney, NSW-2007 Australia |
| Abstract: | Electrocatalysts for highly efficient oxygen reduction reaction (ORR) are crucial for energy conversion and storage devices. Single-atom catalysts with maximized metal utilization and altered electronic structure are the most promising alternatives to replace current benchmark precious metals. However, the atomic level understanding of the functional role for each species at the anchoring sites is still unclear and poorly elucidated. Herein, we report Fe single atom catalysts with the sulfur and oxygen functional groups near the atomically dispersed metal centers (Fe1/NSOC) for highly efficient ORR. The Fe1/NSOC delivers a half-wave potential of 0.92 V vs. RHE, which is much better than those of commercial Pt/C (0.88 V), Fe single atoms on N-doped carbon (Fe1/NC, 0.89 V) and most reported nonprecious metal catalysts. The spectroscopic measurements reveal that the presence of sulfur group induces the formation of epoxy groups near the FeN4S2 centers, which not only modulate the electronic structure of Fe single atoms but also participate the catalytic process to improve the kinetics. The density functional theory calculations demonstrate the existence of sulfur and epoxy group engineer the charges of Fe reactive center and facilitate the reductive release of OH* (rate-limiting step), thus boosting the overall oxygen reduction efficiency. |
