A “Dual Spatial Confinement” Route to Tailor Efficient Dual‐Active Sites ORR Catalyst for Rechargeable Zn‐Air Batteries

• Published in: Small (Weinheim an der Bergstrasse, Germany) Vol. 21; no. 32; pp. e2504022 - n/a
• Main Authors: Xiang, Yang, Wen, Jing‐Hong, Zhao, Yun‐Xiu, Li, Ping, Li, Mei‐Qi, Ren, Yu‐Ting, Wang, Su‐Na, Dou, Jian‐Min, Li, Yun‐Wu, Ma, Hui‐Yan, Xu, Liqiang
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.08.2025
• Subjects: Carbon nanotubes; Catalysts; Chemical reduction; Confinement; dual spatial confinement; dual‐active centers; Iron; Metal air batteries; Metal-organic frameworks; oxygen reduction reaction; Oxygen reduction reactions; Pyrolysis; Synergistic effect; theoretical calculation; Zeolites; Zinc-oxygen batteries; Zn‐air battery; Zn‐air battery; dual spatial confinement; theoretical calculation; oxygen reduction reaction; dual‐active centers
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202504022

Dual active center catalysts (DACs) are effective for accelerating the sluggish kinetics of cathodic oxygen reduction reaction (ORR) in rechargeable zinc‐air batteries (ZABs). However, their tendency to aggregate severely restrict the catalytic efficiency. Herein, a “dual spatial confinement” route is conceived to develop a family of well‐dispersed DACs for boosting ORR activity and ZABs. During pyrolysis, the Zn vacancies generated from Zn‐Zeolitic imidazolate framework (Zn‐ZIF) precursors facilitate the initial incorporation and confinement of Fe/Co atoms, enabling the formation of uniformly dispersed metal sites. Subsequently, the in‐situ grown N‐doped carbon nanotubes (CNTs) further regulate the dual active centers (Co3Fe7 and Co5.47N), ultimately yielding a highly efficient ORR catalyst. Owing to the synergistic effect between the dual active centers, the optimized Co3Fe7/Co5.47N@CNT‐900 catalyst exhibits superior 4e− ORR activity. Theoretical calculations demystify that the Co3Fe7/Co5.47N sites co‐promote the generation of OH− on Co centers, greatly enhance the ORR activity. When applied in rechargeable ZABs, the catalyst delivers a high power density of 168.99 mW cm−2, a high specific capacity of 904.57 mAh gZn−1, and good cycling stability, along with fine rate capability. This work shall light a pathway towards dual active center catalysts with sterling ORR activity. A “dual spatial confinement” route is conceived to fabricate dual‐active center catalysts (Co3Fe7/Co5.47N@CNT‐900) with dispersed Co3Fe7 and Co5.47N sites. The optimal catalyst executes superior ORR activity and is applied in rechargeable Zn‐air batteries. Theoretical calculations demonstrate that the dual‐active sites synergistically promoted the formation of OH− intermediate and greatly boosted the performance.