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

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.