Li Yifan, Wang Hanlin, Chen Chang, Xie Xuesong, Yang Yang, Tan Xuehai, Jiang Keren, Chen Ning, Zhang Hao, Li Zhi
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada.
Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing, China.
Nat Commun. 2025 Aug 29;16(1):8085. doi: 10.1038/s41467-025-63540-w.
Durable and highly active oxygen electrocatalysts are crucial to the large-scale application of rechargeable zinc-air batteries. Here we utilize the N unit in phthalocyanine molecule to trap the tungsten atoms scratched off from the tungsten carbide milling balls and place the obtained W-N unit adjacent to the Fe-N units from iron (Ⅱ) phthalocyanine, resulting in highly active Fe-N/W-N diatomic sites with well-pronounced 3d-5d hybrid for efficient and durable oxygen electrocatalysis. The electron distribution of the Fe-N site is optimized by the neighboring W-N site, which facilitates the O activation and the desorption of *OH and enhances the catalytic activity of the Fe-N site. Meanwhile, the unsaturated 5 d orbitals and tunable valence of the W atoms could modulate the electronic state of the Fe species, prevent leaching, and further enhance the catalytic stability. The resulting zinc-air battery with Fe,W-N-C air cathode exhibits notable cycling stability and repeatability for over 10,000 h. This enhanced stability highlights the possibility of developing 5 d metal-boosted 3 d metal active sites for the fabrication of efficient oxygen electrocatalysts and stable zinc-air batteries.
耐用且高活性的氧电催化剂对于可充电锌空气电池的大规模应用至关重要。在此，我们利用酞菁分子中的N单元捕获从碳化钨研磨球上刮下的钨原子，并将所得的W-N单元置于来自铁（Ⅱ）酞菁的Fe-N单元附近，从而形成具有明显3d-5d杂化的高活性Fe-N/W-N双原子位点，用于高效且耐用的氧电催化。相邻的W-N位点优化了Fe-N位点的电子分布，这有利于O的活化以及*OH的脱附，并增强了Fe-N位点的催化活性。同时，W原子的不饱和5d轨道和可调节的价态可以调节Fe物种的电子状态，防止浸出，并进一步提高催化稳定性。所得的具有Fe,W-N-C空气阴极的锌空气电池在超过10000小时内表现出显著的循环稳定性和可重复性。这种增强的稳定性突出了开发5d金属增强的3d金属活性位点以制造高效氧电催化剂和稳定锌空气电池的可能性。
