Axially Modified Square-Pyramidal CoN 4 –F 1 Sites Enabling High-Performance Zn–Air Batteries

作者：Daili Cao, Yuewen Mu, Lijia Liu, Zhixing Mou, Shuai Chen, Wenjun Yan, Haiqing Zhou, Ting‐Shan Chan, Lo‐Yueh Chang, Li Song, Hua‐Jin Zhai, Xiujun Fan · 发表于：ACS Nano · 年份：2024 · DOI：10.1021/acsnano.4c03261 · 被引用次数：52 · 研究领域：Electrocatalysts for Energy Conversion、Advanced battery technologies research、Catalytic Processes in Materials Science

Cobalt–nitrogen-carbon (Co–N–C) catalysts with a CoN 4 structure exhibit great potential for oxygen reduction reaction (ORR), but the imperfect adsorption energy toward oxygen species greatly limits their reduction efficiency and practical application potential. Here, F-coordinated Co–N–C catalysts with square-pyramidal CoN 4 –F 1 configuration are successfully synthesized using F atoms to regulate the axial coordination of Co centers via hydrothermal and chemical vapor deposition methods. During the synthesis process, the geometry structure of the Co atom converts from six-coordinated Co–F 6 to square-pyramidal CoN 4 –F 1 in the coordinatively unsaturated state, which provides an open binding site for the O 2 . The introduction of axial F atoms into the CoN 4 plane alters the local atomic environment around Co, significantly improving the ORR activity and Zn–air batteries performance. In situ spectroscopy proves that CoN 4 –F 1 sites strongly combine with the OOH* intermediate and facilitate the splitting of O–O bond, making OOH* readily decompose into O* and OH* via a dissociative pathway. Theoretical calculations confirm that the axial F atom effectively reduces the electronic density of the Co centers and facilitates the desorption of the OH* intermediate, efficiently accelerating the overall ORR kinetics. This work advances a feasible synthesis mechanism of axial ligands and provides a route to construct efficient high-coordination catalysts.