期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 48, 页码 25404-25410出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202110243
关键词
iron; Mossbauer spectroscopy; oxygen reduction reaction; spin states; sulfur
资金
- National Natural Science Foundation of China [21974103]
- Wuhan University
- Ministry of Science and Technology, Taiwan [MOST 110-2113-M-009-007-MY2]
- National Yang Ming Chiao Tung University [109HDAC]
- Yushan Young Scholar Program, Ministry of Education, Taiwan
In this study, sulfur-doped Fe-1-NC catalyst was found to exhibit superior activity towards ORR compared to traditional Fe-NC materials. The incorporation of sulfur in the second coordination sphere of Fe-1-NC was shown to induce a transition of spin polarization configuration, with the low spin single-Fe3+-atom identified as the active site for ORR through operando Fe-57 Mossbauer spectra. Additionally, DFT calculations revealed that the lower spin state of the Fe center after sulfur doping promotes the OH* desorption process.
Heteroatom doped atomically dispersed Fe-1-NC catalysts have been found to show excellent activity toward oxygen reduction reaction (ORR). However, the origin of the enhanced activity is still controversial because the structure-function relationship governing the enhancement remains elusive. Herein, sulfur(S)-doped Fe-1-NC catalyst was obtained as a model, which displays a superior activity for ORR towards the traditional Fe-NC materials. Fe-57 Mossbauer spectroscopy and electron paramagnetic resonance spectroscopy revealed that incorporation of S in the second coordination sphere of Fe-1-NC can induce the transition of spin polarization configuration. Operando Fe-57 Mossbauer spectra definitively identified the low spin single-Fe3+-atom of C-FeN4-S moiety as the active site for ORR. Moreover, DFT calculations unveiled that lower spin state of the Fe center after the S doping promotes OH* desorption process. This work elucidates the underlying mechanisms towards S doping for enhancing ORR activity, and paves a way to investigate the function of broader heteroatom doped Fe-1-NC catalysts to offer a general guideline for spin-state-determined ORR.
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