Recently there is vigorous growth of reports on persulfate (PS)-based advanced oxidation processes (AOPs), inclining to development of newfangled catalysts and treatment of a wide range of organic pollutants. PS-related non-radical oxidation pathways are lately proposed, whereas there still exist debatable observations and explanation on these issues. Whilst non-radical reactions in heterogeneous systems have been well commented, this review focuses on the latest discovery of non-radical oxidation in homogeneous persulfate (especially peroxymonosulfate (PMS)) systems. The application of direct oxidation process is firstly summarized and the roles of PMS distal oxygen in attack on organic pollutants like antibiotics are highlighted. Besides, the effects of exogenic and endogenic halogen on the reactivity and mechanisms of HOX in PS activation are discussed. Then the formation and reaction pathways of singlet oxygen (¹O₂) triggered by phenol/carbonyl compounds and nucleophiles are elaborated. Recent discovery on formation of high valent metal species by PS activation and their reactivity is reviewed lastly. By sorting out a large number of cutting-edge research reports, this review conducts a detailed and critical analysis and overview on the homogeneous PS non-radical mechanisms, and points out the controversies and challenges so as to better understand the reaction mechanism and further improve their treatment performance.

最近，关于基于过硫酸盐（PS）的高级氧化工艺（AOP）的报道激增，倾向于开发新型催化剂和处理各种有机污染物。最近提出了与PS有关的非自由基氧化途径，但在这些问题上仍存在有争议的观察和解释。尽管已经对异质系统中的非自由基反应进行了很好的评论，但本综述着重于均相过硫酸盐（尤其是过氧一硫酸盐（PMS））系统中非自由基氧化的最新发现。首先总结了直接氧化工艺的应用，并着重介绍了PMS远端氧在攻击抗生素等有机污染物中的作用。除了，讨论了外源和内源卤素对PS活化中HOX反应性和机理的影响。然后单线态氧的形成和反应途径阐述了由苯酚/羰基化合物和亲核试剂引发的¹ O ₂）。最后综述了通过PS活化形成高价金属物种及其反应性的最新发现。通过对大量前沿研究报告的梳理，对同质PS非自由基机理进行了详细，批判性的分析和概述，指出了争议和挑战，以便更好地理解反应机理并进一步改进。他们的治疗表现。