Reusable Te‐Doped Sn‐P‐I Catalysts With Anti‐Healing P Vacancies and Stable I Sites for Efficient Black Phosphorus Growth

Abstract Black phosphorus (BP) holds significant potential for various applications, but its widespread use requires the development of efficient and cost‐effective preparation methods. Sn‐P‐I clathrates are identified as potential catalysts for BP growth; however, the intact Sn‐P‐I structure leads to prolonged preparation times, rapid deactivation, and an unclear catalytic mechanism. In this study, a Te‐doping strategy is proposed to simultaneously improve the activity and stability of Sn‐P‐I catalysts. Te doping induces the formation of Sn─Te bonds, creates intrinsic anti‐healing phosphorus vacancies, while also mitigates iodine loss due to the lower electronegativity of Te compared to P. This doping changes the deactivation mechanism of the Sn‐I‐P from phosphorus saturation to iodine loss in the Te‐doped Sn‐I‐P. To further improve catalyst reusability, an iodination treatment is introduced to reactivate the Te‐Sn‐P‐I catalysts. The optimized Te‐Sn‐P‐I catalyst reduced the reaction time for BP synthesis from 15 h to just 45 min, achieving a BP yield of 96.7%. The reactivation process restores 100% of the catalytic performance.