Atomically dispersed Fe-N4 modified with precisely located S for highly efficient oxygen reduction
journal contributionposted on 29.03.2021, 08:50 by Yin Jia, Xuya Xiong, Danni Wang, Xinxuan Duan, Kai Sun, Yajie Li, Lirong Zheng, Wen-Feng Lin, Mingdong Dong, Guoxin Zhang, Wen Liu, Xiaoming Sun
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.
National Natural Science Foundation of China, Beijing University of Chemical Technology (buctrc201901), National Natural Science Foundation of China and Ministry of Foreign Affairs and International Cooperation, Italy (NSFC–MAECI 51861135202), the National Key Research and Development Project (Grant No. 2018YFB1502401, 2018YFA0702002), the Royal Society and the Newton Fund through the Newton Advanced Fellowship award (NAF\R1\191294), the Program for Changjiang Scholars and Innovation Research Team in the University (No. IRT1205), the Fundamental Research Funds for the Central Universities, and the long–term subsidy mechanism from the Ministry of Finance and the Ministry of Education of PRC.
- Aeronautical, Automotive, Chemical and Materials Engineering
- Chemical Engineering