Carbon-based catalysts with heteroatom doping and hollow structures are desired for advanced oxidation processes (AOPs). Herein, dual-shelled Co, N, and S codoped hollow carbon nanocages were developed by wrapping zeolitic imidazolate framework-67 (ZIF-67) with trithiocyanuric acid (TCA) and performing subsequent carbonization. The optimal composite catalyst (Co-NC-CoS) exhibited excellent catalytic performance toward different organic pollutants. Almost complete removal of 4-NP (60 mg/L⁻¹) was achieved within 20 min by 10 mg of catalyst and 0.2 g/L⁻¹ peroxymonosulfate (PMS). Moreover, the catalyst showed good stability and reusability. The effects of catalyst and PMS dose, pollutant concentration, pH and common anions were investigated, and reactive oxygen species (ROS) were studied by scavenger experiments and electron paramagnetic resonance (EPR) tests. The results show that multidoped atoms S, Co and N all contributed to the degradation system. Several lines of evidence suggested that S could change the catalytic process from Co³⁺/Co²⁺ to Co³⁺/Co²⁺/Co⁰ reduction due to its low redox potential. Degradation was achieved through both radical and nonradical pathways, where sulfate radicals (SO₄^·̶), hydroxyl radicals (^·OH) and singlet oxygen (¹O₂) were primary reactive species. Overall, this work may suggest that the novel multi heteroatom-doped catalysts with complex structures can be developed for environmental remediation.

高级氧化工艺 (AOP) 需要具有杂原子掺杂和中空结构的碳基催化剂。在此，通过用三硫氰尿酸 (TCA) 包裹沸石咪唑酯骨架-67 (ZIF-67) 并进行后续碳化，开发了双壳 Co、N 和 S 共掺杂中空碳纳米笼。最佳复合催化剂（Co-NC-CoS）对不同有机污染物表现出优异的催化性能。使用 10 mg 催化剂和 0.2 g/L ^-1在 20 分钟内几乎完全去除 4-NP (60 mg/L ^-1 )过硫酸盐 (PMS)。此外，催化剂表现出良好的稳定性和重复使用性。研究了催化剂和 PMS 剂量、污染物浓度、pH 值和常见阴离子的影响，并通过清除剂实验和电子顺磁共振 (EPR) 测试研究了活性氧 (ROS)。结果表明，多掺杂原子 S、Co 和 N 都对降解系统有贡献。一些证据表明，由于其低氧化还原电位，S 可以将催化过程从 Co ³⁺ /Co ²⁺转变为 Co ³⁺ /Co ²⁺ /Co ⁰还原。降解是通过自由基和非自由基途径实现的，其中硫酸根自由基 (SO ₄ ^·̶), 羟基自由基 ( ^· OH) 和单线态氧 ( ¹ O ₂ ) 是主要的反应物种。总体而言，这项工作可能表明可以开发具有复杂结构的新型多杂原子掺杂催化剂用于环境修复。