Intrinsic molecular characteristics of micropollutants-oriented directional modulation and transformation of nonradical pathways in heterogeneous advanced oxidation processes for safe micropollutant removal

Nonradical-mediated heterogeneous advanced oxidation processes (HAOPs) show promise for efficiently eliminating toxic and refractory micropollutants (MPs) in wastewater. However, the modulation of nonradical systems is predominantly catalyst-centered, while the intrinsic molecular characteristics of MPs have been largely overlooked. This review systematically analyzes the structure–reactivity relationships of target MPs, with emphasis on recent breakthroughs in multiscale computational approaches–including density functional theory (DFT) and machine learning (ML)–that enable precise prediction of the electronic structures and preferential attack sites of MPs. On the basis of the matching principle between MPs-specific structures and nonradical reactive oxygen species (ROS) properties, this review elucidates the directional modulation strategy and mechanisms of nonradical ROS and rational catalytic system design via the integration of DFT and ML. Additionally, this work further reveals the safe transformation pathways of MPs and their intrinsic mechanism, and proposes current challenges and future research priorities for nonradical pathways. This review clarifies the guiding role of the molecular characteristics of MPs in the modulation of nonradical pathways, providing key theoretical support for the design of efficient and safe targeted nonradical water treatment technologies.