Reconstructing the Coordination Environment of Fe/Co Dual‐atom Sites towards Efficient Oxygen Electrocatalysis for Zn–Air Batteries

• Published in: Angewandte Chemie International Edition Vol. 64; no. 7; pp. e202419595 - n/a
• Main Authors: Liu, Hengqi, Huang, Jinzhen, Feng, Kun, Xiong, Rui, Ma, Shengyu, Wang, Ran, Fu, Qiang, Rafique, Moniba, Liu, Zhiguo, Han, Jiecai, Hua, Daxing, Li, Jiajie, Zhong, Jun, Wang, Xianjie, Zhao, Zhonglong, Yao, Tai, Jiang, Sida, Xu, Ping, Zhang, Zhihua, Song, Bo
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 10.02.2025
• Edition: International ed. in English
• Subjects: Catalysts; Coordination; Iron; lattice oxygen mechanism; Metal air batteries; Nitrogen; Oxygen; oxygen evolution reaction; oxygen reduction reaction; rechargeable zinc–air batteries; Tailoring coordination environment; Zinc-oxygen batteries; oxygen evolution reaction; rechargeable zinc–air batteries; Tailoring coordination environment; oxygen reduction reaction; lattice oxygen mechanism
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202419595

Dual‐atom catalysts with nitrogen‐coordinated metal sites embedded in carbon can drive the oxygen reduction and evolution reactions (ORR/OER) in rechargeable zinc–air batteries (ZABs), and the further improvement is limited by the linear scaling relationship of intermediate binding energies in the absorbate evolution mechanism (AEM). Triggering the lattice oxygen mechanism (LOM) is promising to overcome this challenge, but has yet been verified since the lacking of bridge oxygen (O) in the rigid coordination environment of the metal centers. Here, we demonstrate that suitably tailored dual‐atom catalysts of FeCo−N−C can undergo out‐plane and in‐plane reconstruction to form the both axial O and bridge O at the metal centers, and thus activate the LOM pathway. The tailored FeCo−N−C with shortened Fe−N bonds also favors the ORR process, therefore is a promising dual‐atom oxygen catalyst. The assembled rechargeable ZABs demonstrate a peak power density of 332 mW cm−2, and exhibit no notable decline after ~720 h of continuous cycling. The coordination environment of the Fe/Co dual‐atom site can be tuned by preferentially removing the pyrrolic nitrogen over the pyridinic nitrogen, resulting in a shorter Fe−N to enhance the oxygen reduction reaction, and promoting an in‐plane oxygen reconstruction to lower the energy barrier in the oxygen evolution reaction. The catalyst with the modified Fe/Co dual‐atom sites exhibits superior oxygen electrocatalysis in a Zn‐air battery.