Increasing studies have been conducted to explore strategies for enhancing the catalytic performance of metal-doped C-N-based materials (e.g., cobalt (Co)-doped C₃N₅) via heteroatomic doping. However, such materials have been rarely doped by phosphorus (P) with the higher electronegativity and coordination capacity. In current study, a novel P and Co co-doped C₃N₅ (Co-xP-C₃N₅) was developed for peroxymonosulfate (PMS) activation and 2,4,4′-trichlorobiphenyl (PCB28) degradation. The PCB28 degradation rate increased by 8.16–19.16 times with Co-xP-C₃N₅ compared to conventional activators under similar reaction conditions (e.g., PMS concentration). The state-of-the-art techniques, including X-ray absorption spectroscopy and electron paramagnetic resonance etc., were applied to explore the mechanism of P doping for enhancing Co-xP-C₃N₅ activation. Results showed that P doping induced the formation of Co-P and Co-N-P species, which increased the contents of coordinated Co and improved Co-xP-C₃N₅ catalytic performance. The Co mainly coordinated with the first shell layer of Co₁-N₄, with successful P doping occurring in the second shell layer of Co₁-N₄. The P doping favored electron transfer from the C to N atom near Co sites and thus strengthened PMS activation owing to its higher electronegativity. These findings provide new strategy for enhancing the performance of single atom-based catalysts for oxidant activation and environmental remediation.

已经进行了越来越多的研究来探索通过杂原子掺杂提高金属掺杂 CN 基材料（例如，钴 (Co) 掺杂的 C ₃ N _{5 ）的催化性能的策略。}然而，此类材料很少掺杂具有更高电负性和配位能力的磷（P）。在当前的研究中，开发了一种新型 P 和 Co 共掺杂 C ₃ N ₅ (Co-xP-C ₃ N _{5 )，用于过氧单硫酸盐 (PMS) 活化和 2,4,4'-三氯联苯 (PCB28) 降解。Co-xP-C 3} N ₅的 PCB28 降解率提高了 8.16–19.16 倍与类似反应条件（例如 PMS 浓度）下的常规活化剂相比。应用X射线吸收光谱、电子顺磁共振等前沿技术探索了P掺杂增强Co-xP-C 3 N 5_活化的_机理。结果表明，P掺杂诱导了Co-P和Co-NP物种的形成，增加了配位Co的含量，提高了Co-xP-C ₃ N ₅的催化性能。_{Co主要与Co 1} -N ₄的第一层壳层配位，成功的P掺杂发生在Co ₁ -N ₄的第二层壳层. P 掺杂有利于电子从 C 原子转移到 Co 位点附近的 N 原子，因此由于其较高的电负性而加强了 PMS 活化。这些发现为提高单原子基催化剂在氧化剂活化和环境修复方面的性能提供了新的策略。