Circumventing radical generation on Fe–V atomic pair catalyst for robust oxygen reduction and zinc–air batteries

Ran, Lan, Zhang, Yichen, Tong, Wenming, Chen, Long, Wang, Maoyu, Zhou, Hua, et al. Circumventing Radical Generation on Fe–V Atomic Pair Catalyst for Robust Oxygen Reduction and Zinc–Air Batteries. Angewandte Chemie International Edition, e202514542. https://doi.org/10.1002/anie.202514542

Abstract

Iron–nitrogen–carbon (Fe–N–C) catalysts are considered the most active platinum-free alternative for oxygen reduction reaction (ORR), yet the generated reactive oxygen species (ROS) from general mechanistic pathway rapidly impair the ORR activity and stability of Fe–N–C. Herein, we establish and report an ORR pathway-switching strategy to circumvent ROS generation and fundamentally improve the activity and stability of Fe–N–C via DFT guided catalyst design. The constructed Fe–V atomic pair catalyst (Fe1V1-NC) with N2Fe-N2-VN2 configuration enables side-on adsorption of O2 and subsequent direct-breaking of the O═O bond to form O*, thereby avoiding the formation of ROS radicals. Importantly, there is intersite electron interaction between FeN4 and VN4, which further boosts the ORR activity. Consequently, Fe1V1-NC exhibits outstanding ORR activity with onset and half-wave (E1/2) potentials at 1.02 and 0.89 V versus RHE, respectively, in 0.1 M KOH. Record-high stability is achieved on Fe1V1-NC with a minimal decay in E1/2 by 16 mV over 50000 cycles, surpassing Fe–N–C counterpart and most of the catalysts reported to date. The Fe1V1-NC-based zinc-air battery reported here demonstrates exceptional durability up to 400 h at 10 mA·cm−2. This work identifies the intrinsic correlation between ORR pathway, activity, and stability, advancing development of stable catalytic systems.

Funder

Natural Science Foundation of China
Guangdong Basic and Applied Basic Research Foundation
Shanghai Advanced Research Institute
Chinese Academy of Sciences
European Union
Central Universities of Central South University

Publisher

Wiley and Gesellschaft Deutscher Chemiker

Rights

CC BY

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