Axial Chlorine Engineering of p-Block Antimony Atomic Sites Boosts Oxygen Reduction

作者：Yanmin Hu, Shuwen Niu, Zedong Zhang, Tingting Chao, Tonghui Zhao, Yu Ge, Fangyao Zhou, Xiao Liang, Huile Jin, Zhengkun Yang, Dingsheng Wang, Wei Chen, Yadong Li · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c07459 · 被引用次数：68 · 研究领域：Electrocatalysts for Energy Conversion、Fuel Cells and Related Materials、Advanced Photocatalysis Techniques

The main-group metals characterized by closed d shells are generally regarded as catalytically inert for oxygen reduction reactions (ORR) due to the delocalized valence orbitals. Modulating the coordination environment of metal sites is critical to gaining highly active electrocatalysts for ORR. Herein, atomically dispersed Sb site catalysts were successfully constructed with SbN 4 –Cl configuration for highly efficient ORR. Density functional theory (DFT) calculations reveal that the introduction of an axial Cl ligand regulates the p electron structure of the Sb active center, thereby alleviating the binding energy of the HO* intermediate and lowering the energy barrier of the ORR process. Remarkably, the as-prepared SbN 4 Cl/NC catalysts exhibited excellent ORR activity with a half-wave potential ( E 1/2 ) of 0.921 V and exceptional durability, superior to most 3d transition-metal-based single-atom catalysts and commercial Pt/C. Moreover, Zn–air battery tests also verified the outstanding discharge performance and ultralong charge/discharge durability of SbN 4 Cl/NC catalysts, demonstrating significant promise for energy storage and conversion applications.