[en] The interaction between oxygen species and metal sites of various orbitals exhibits intimate correlation with the oxygen reduction reaction (ORR) kinetics. Herein, a new approach for boosting the inherent ORR activity of atomically dispersed Fe-N-C matrix is represented by implanting Fe atomic clusters nearby. The as-prepared catalyst delivers excellent ORR activity with half-wave potentials of 0.78 and 0.90 V in acidic and alkaline solutions, respectively. The decent ORR activity can also be validated from the high-performance rechargeable Zn-air battery. The experiments and density functional theory calculations reveal that the electron spin-state of monodispersed Fe active sites is transferred from the low spin (LS, t2g 6 eg 0) to the medium spin (MS, t2g 5 eg 1) due to the involvement of Fe atomic clusters, leading to the spin electron filling in σ∗ orbit, by which it favors OH- desorption and in turn boosts the reaction kinetics of the rate-determining step. This work paves a solid way for rational design of high-performance Fe-based single atom catalysts through spin manipulation.
Disciplines :
Chemistry
Author, co-author :
Zhang, Huiwen; School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China
Chen, Hsiao-Chien; Center for Reliability Science and Technologies, Center for Sustainability and Energy Technologies, Chang Gung University, Taoyuan, 33302, Taiwan
Feizpoor, Solmaz; School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China
Li, Linfeng; School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China
Zhang, Xia; School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China
Xu, Xuefei; School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China
Zhuang, Zechao; Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China
Li, Zhishan; Faculty of Metallurgical and Energy Engineering, State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming, 650093, P. R. China
Hu, Wenyu; Department of Physics, Southern University of Science and Technology, ShenZhen, 518055, P. R. China
Snyders, Rony ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des Interactions Plasma-Surface
Wang, Dingsheng ; Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China
Wang, Chundong ; School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China
Language :
English
Title :
Tailoring Oxygen Reduction Reaction Kinetics of Fe-N-C Catalyst via Spin Manipulation for Efficient Zinc-Air Batteries.
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Funders :
National Natural Science Foundation of China National Basic Research Program of China Chang Gung University
Funding text :
H.Z., H.C.C., and S.F. contributed equally to this work. This work was finically supported by National Natural Science Foundation of China (Grants No. 52272202, 51972129, and 22325101), the National Key Research and Development Program of China (Grant No. 2022YFB3807201), Bintuan Science and Technology Program (Grants Nos. 2020DB002 and 2022DB009). C.C.H. thanked the funding support from Chang Gung University (No. URRPD2N0031). Z.L. acknowledged the finical support from Yunnan Major Scientific and Technological Projects (Grant No. 202202AG050017\u20102). The authors acknowledged the assistance of SUSTech Core Research Facilities and the help of Dr. Yang QIU at Pico Center for the aberration corrected TEM experiments. The authors thanked the BL14W1 station in Shanghai Synchrotron Radiation Facility (SSRF) and 1W1B station for XAFS measurement in Beijing Synchrotron Radiation Facility (BSRF).
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