[en] Iron phthalocyanine (FePc), with its well-defined FeN4 active site, has attracted significant interest as a promising nonprecious catalyst in the oxygen reduction reaction (ORR). However, its rigid square-planar geometry hinders O═O bond activation and cleavage of the O═O bond, resulting in sluggish ORR kinetics. Herein, we introduce nitrogen-doped, defect-rich carbon nano-onions (CNO) (with positive Gaussian curvature) as a support to induce geometric distortion in FePc for enhancing the ORR activity. Magnetic measurements and theoretical calculations reveal that the introduction of CNO effectively promotes a spin state transition of Fe ions from low-spin (LS, t2g6 eg0) to intermediate-spin (IS, t2g5 eg1), which enables electron filling of the π* orbitals (via d-p orbital coupling), subsequently weakening the overadsorption of oxygenated intermediates on the FeN4 sites. The as-fabricated FePc/CNO electrocatalyst exhibits exceptional ORR performance in alkaline media. Furthermore, a configured FePc/CNO-based Zn-air battery exhibits excellent performance, as well, demonstrating its potential for practical energy applications.
Disciplines :
Chemistry
Author, co-author :
Li, Linfeng; School of Integrated Circuits, State Key Laboratory of New Textile Materials and Advanced Processing, Huazhong University of Science and Technology, Wuhan 430074, P.R. China
Liu, Yuxiao; School of Integrated Circuits, State Key Laboratory of New Textile Materials and Advanced Processing, Huazhong University of Science and Technology, Wuhan 430074, P.R. China
Zhang, Xia; School of Integrated Circuits, State Key Laboratory of New Textile Materials and Advanced Processing, Huazhong University of Science and Technology, Wuhan 430074, P.R. China
Humayun, Muhammad ; Energy, Water, and Environment Lab, College of Sciences and Humanities, Prince Sultan University, Riyadh 11586, Saudi Arabia
Yang, Haowei; School of Materials Science and Engineering, Central South University, Changsha 410083, P.R. China
Zeng, Jianrong; Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201204, P.R. China
Younus, Hussein A ; Nanotechnology Research Centre, Sultan Qaboos University, Muscat 123, Oman
Pang, Yuanjie ; School of Optical and Electronic Information, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, P.R. China
Wang, Deli ; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, P.R. China
Snyders, Rony ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des Interactions Plasma-Surface ; Materia Nova Research Center, Mons B-7000, Belgium
Wang, Chundong ; School of Integrated Circuits, State Key Laboratory of New Textile Materials and Advanced Processing, Huazhong University of Science and Technology, Wuhan 430074, P.R. China ; Energy, Water, and Environment Lab, College of Sciences and Humanities, Prince Sultan University, Riyadh 11586, Saudi Arabia
Language :
English
Title :
Curvature Strain-Induced Electron Spin Leveraging in d Orbitals toward Oxygen Reduction for Zn-Air Batteries.
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Funders :
Prince Sultan University Fonds Wetenschappelijk Onderzoek F.R.S.-FNRS - Fonds de la Recherche Scientifique National Natural Science Foundation of China
Funding text :
The study has been financially supported by the National Natural Science Foundation of China (Grants 52272202 and W2421027). R.S. acknowledges the Excellence of Science FWO-FNRS project (PLASyntH2, FNRS Grant O.0023.22, EOS ID 40007511). The authors acknowledge the assistance of SUSTech Core Research Facilities and the help of Dr. Yang Qiu at the Pico Center for the AC STEM Measurement. The computation was completed in the HPC Platform of Huazhong University of Science and Technology. We thank the BL13SSW beamline at the Shanghai Synchrotron Radiation Facility (https://cstr.cn/31124.02.SSRF.BL13SSW) for the XAFS. M.H. and C.W. acknowledge Prince Sultan University.
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