Surface passivation and an increase in pH may restrain the efficiency and capacity of the zero-valent iron (ZVI) activated persulfate (PS) process. Mechanochemically sulfidated ZVI (S-ZVI^bm) shows an extraordinary increase in the activation of PS. Ball-milling avoids the complex liquid reactions of traditional methods of activation and is easier to upscale. However, the effects of the sulfur dose and milling conditions have not been sufficiently investigated in the application of S-ZVI^bm to the PS activation process. S-ZVI^bm was pH-independent compared with similar catalysts. The best performance was obtained for S-ZVI^bm with 25% sulfur synthesized at 300 rev min⁻¹ for 5 h. Almost complete degradation of 50 μM ATZ was obtained after 40 min reaction with 6 mM PS and 0.3 g L^-1 S-ZVI^bm. Structural and species characterizations revealed the effects of the milling conditions and showed that sulfide (S²⁻) might be the predominant sulfur species. The primary facilitation mechanisms of S-ZVI^bm were the mitigation of passivation, an increase in hydrophobicity, an increase in electron transfer and the accelerated regeneration of Fe²⁺. ⁵⁷Fe Mössbauer spectrum confirmed that the Fe⁰ left in S-ZVI^bm was about two times higher than that in reacted ZVI^bm. Fe⁰ acted as the predominant PS activator, but FeS₂, FeS and SO₃²⁻ also contributed to PS activation. The degradation pathway of atrazine was clarified based on the detection of intermediates and density functional theory calculations. S-ZVI^bm is a promising catalyst for the activation of PS used to remediate refractory contaminants and is amenable to upscaling from the laboratory scale.

表面钝化和pH值升高可能会限制零价铁（ZVI）活化过硫酸盐（PS）工艺的效率和容量。机械化学硫化的ZVI（S-ZVI ^bm）显示PS的活化异常增加。球磨避免了传统活化方法的复杂液体反应，并且更易于规模化。但是，在将S-ZVI ^bm应用于PS活化过程中，尚未充分研究硫剂量和研磨条件的影响。与类似的催化剂相比，S-ZVI ^bm不依赖于pH。对于S-ZVI ^bm而言，以300转/分钟^-1合成的25％硫获得了最佳性能持续5小时。与6 mM PS和0.3 g L ^-1 S-ZVI ^bm反应40分钟后，几乎可以完全降解^50μMATZ。结构和物种特征揭示了研磨条件的影响，并表明硫化物（S ²⁻）可能是主要的硫物种。S-ZVI ^bm的主要促进机制是钝化的减轻，疏水性的增加，电子转移的增加以及Fe ²⁺的加速再生。⁵⁷ FeMössbauer光谱证实，S-ZVI ^bm中剩余的Fe ⁰约为反应ZVI ^bm中的Fe ²。铁⁰充当了主要的PS活化剂，但FeS ₂，FeS和SO ₃ ^2-也是促成PS活化的原因。基于中间体的检测和密度泛函理论的计算，阐明了r去津的降解途径。S-ZVI ^bm是一种用于活化PS的催化剂，可用于修复难处理的污染物，并且可以从实验室规模进行升级。