Abstract

Highlights

  • Precisely located S doping of atomic Fe-N4 in Fe(N3)(N–C–S) motif was realized.

  • This S doping renders weakened *OH binding and faster charge transfer on Fe-N4.

  • Fe-NSC showed excellent oxygen reduction reaction performance with onset potential ~ 1.09 V and half-wave potential ~ 0.92 V.

Immobilizing metal atoms by multiple nitrogen atoms has triggered exceptional catalytic activity toward many critical electrochemical reactions due to their merits of highly unsaturated coordination and strong metal-substrate interaction. Herein, atomically dispersed Fe-NC material with precise sulfur modification to Fe periphery (termed as Fe-NSC) was synthesized, X-ray absorption near edge structure analysis confirmed the central Fe atom being stabilized in a specific configuration of Fe(N3)(N–C–S). By enabling precisely localized S doping, the electronic structure of Fe-N4 moiety could be mediated, leading to the beneficial adjustment of absorption/desorption properties of reactant/intermediate on Fe center. Density functional theory simulation suggested that more negative charge density would be localized over Fe-N4 moiety after S doping, allowing weakened binding capability to *OH intermediates and faster charge transfer from Fe center to O species. Electrochemical measurements revealed that the Fe-NSC sample exhibited significantly enhanced oxygen reduction reaction performance compared to the S-free Fe-NC material (termed as Fe-NC), showing an excellent onset potential of 1.09 V and half-wave potential of 0.92 V in 0.1 M KOH. Our work may enlighten relevant studies regarding to accessing improvement on the catalytic performance of atomically dispersed M-NC materials by managing precisely tuned local environments of M-Nx moiety.

Details

Title
Atomically Dispersed Fe-N4 Modified with Precisely Located S for Highly Efficient Oxygen Reduction
Author
Yin, Jia 1 ; Xiong Xuya 2 ; Wang, Danni 3 ; Duan Xinxuan 1 ; Sun, Kai 4 ; Li, Yajie 1 ; Zheng Lirong 5 ; Lin, Wenfeng 6 ; Dong Mingdong 2 ; Zhang Guoxin 3 ; Liu, Wen 1 ; Sun, Xiaoming 1 

1  Beijing University of Chemical Technology, State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing, People’s Republic of China (GRID:grid.48166.3d) (ISNI:0000 0000 9931 8406) 
2  Aarhus University, Interdisciplinary Nanoscience Center (INANO), Sino-Danish Center for Education and Research (SDC), Aarhus C, Denmark (GRID:grid.7048.b) (ISNI:0000 0001 1956 2722) 
3  Shandong University of Science and Technology, Electrical Engineering and Automation, Tsingtao, People’s Republic of China (GRID:grid.412508.a) (ISNI:0000 0004 1799 3811) 
4  Beijing University of Chemical Technology, State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing, People’s Republic of China (GRID:grid.48166.3d) (ISNI:0000 0000 9931 8406); Loughborough University, Department of Chemical Engineering, Loughborough, UK (GRID:grid.6571.5) (ISNI:0000 0004 1936 8542) 
5  Chinese Academy of Sciences, Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Beijing, People’s Republic of China (GRID:grid.9227.e) (ISNI:0000000119573309) 
6  Loughborough University, Department of Chemical Engineering, Loughborough, UK (GRID:grid.6571.5) (ISNI:0000 0004 1936 8542) 
Publication year
2020
Publication date
May 2020
Publisher
Springer Nature B.V.
ISSN
23116706
e-ISSN
21505551
Source type
Scholarly Journal
Language of publication
English
DOI
https://doi.org/10.1007/s40820-020-00456-8
ProQuest document ID
2406474266
Copyright
© The Author(s) 2020. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.